JP2003139904A - Antireflection film, and low reflective polarizing plate and display device using the film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antireflection film having favorable display quality and excellent wiping property for dust on the display face and to provide a low reflective polarizing plate using the film and a display device using them. SOLUTION: The antireflection film is obtained by forming a hard coat layer directly or through another layer on one surface of a light transmitting film and further forming a low refractive index layer by coating on the surface of the hard coat layer. The initial electrification voltage of the film measured by using a wool friction cloth described in JIS L 0803 and according to the triboelectric attenuation measurement method described in JIS L 1094 is specified to >=-5 kV and <=+20 kV.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antireflection film suitable for liquid crystal display devices and the like, which is excellent in practicability, in particular dust wiping property, a low reflection polarizing plate using the same, and a display device in which the antireflection film is arranged. .

[0002]

2. Description of the Related Art Liquid crystal panels have been researched and developed in recent years.
It is securing a solid position as a display.
However, in car navigation monitors and video camera monitors that are frequently used under bright lighting, the visibility is significantly reduced due to surface reflection. Therefore, it is becoming indispensable to apply antireflection treatment to the polarizing plate.
Most LCDs that are frequently used outdoors use anti-reflection polarizing plates. Antireflection treatment is generally performed by vacuum deposition method, sputtering method, C
A VD method or the like is used to produce a multilayer stack of a plurality of thin films made of materials having different refractive indices, and a design is performed to reduce reflection in the visible light region as much as possible. However, vacuum equipment is required to form a thin film by the above-mentioned dry processing, and the processing cost becomes very expensive. Therefore, recently, an antireflection film is formed by wet coating.

By the way, the structure of the antireflection film is as follows: transparent film as a base material / resin layer for imparting hard coat property /
It is made of a low refractive index material. From the viewpoint of reflectance, the hard coat resin layer is required to have a high refractive index, and the low refractive index layer is required to have a lower refractive index. For the low refractive index layer, a fluorine compound has been preferably used from the viewpoint of lowering the refractive index and from the viewpoint of antifouling property, but dust adhered to the surface by a normal material such as tissue paper (pulp) or rag (cotton). When the surface of the low refraction material and the fluorine-based material on the surface of the low-refraction material are significantly different from each other, the surface of the low-refraction material is greatly negatively charged, which makes it more difficult to remove dust. Further, the above-mentioned electrification train is a theory that has been treated semi-empirically in the field of static electricity, and it is known that it cannot be generally discussed only by the difference in materials.

[0004]

DISCLOSURE OF THE INVENTION The present invention is an antireflection film having a low refractive index layer formed on a transparent film having a resin hard coat, and measured by a charging property test method used in the textile industry. An object of the present invention is to provide an antireflection film having good dust wiping property, a low reflection polarizing plate using the same, and a display device using the same by controlling the triboelectric charge amount on the surface within a predetermined range.

[0005]

In order to solve the above-mentioned problems, the present invention provides a hard coat layer on one surface of a translucent film directly or through another layer, and further coats the surface of this hard coat layer. In the antireflection film in which the low refractive index layer is laminated by
Using the bristling cloth of hair described in L 0803, JIS L
The present invention provides an antireflection film having an initial charged voltage value measured according to the triboelectrification attenuation measurement method described in 1094 of -5 kV or more and +20 kV or less.

[0006] In the antireflection film, it is preferable that the hard coat layer has an uneven surface shape and has an antiglare property.

In the antireflection film,
It is preferable to contain an inorganic or resin spherical or amorphous filler in the hard coat layer.

Next, the present invention is a polarizing plate having protective layers on both sides of an absorbing dichroic polarizer, wherein at least one of the protective layers is the antireflection film. The present invention provides a polarizing plate.

Further, the present invention provides a display device characterized in that the antireflection film is arranged.

Further, the present invention provides a liquid crystal display device or an organic EL display device, characterized in that the polarizing plate is arranged.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the antireflection film of the present invention, a hard coat layer is provided on one surface of a light-transmitting film directly or through another layer, and the surface of this hard coat layer is coated to have a low refractive index. It is a stack of layers. The surface of the coated low refractive index layer is JIS
Using the bristling cloth of hair described in L 0803, JIS L
The value of the initial charged voltage measured according to the triboelectric charge decay measurement method described in 1094 is in the range of -5 kV to +20 kV.

The triboelectric charge amount in the present invention is measured by "J
IS L 1094 (1997): Method for testing triboelectrification of woven and knitted fabrics ”, the test piece is an antireflection film or a low reflection polarizing plate using the antireflection film. As a measurement. First, the measurement was performed on the friction element 1 as shown in FIG.
A friction cloth (white cloth attached to wool) 2 specified in L 0803 is folded in two in the lateral direction (along the weft thread), and is covered with the friction surface of the friction element 1 and fixed with a rubber band. Next, the test piece 3 is shown in FIG.
Test piece holder 5 provided on the test piece table 4 shown in FIG.
The test piece 3 and the friction cloth 2 are initially charged by a static eliminator. The test piece
1 at a rate of twice per second so that the friction direction is unidirectional
At the same time as rubbing 0 times and rubbing 10 times, the test piece is quickly moved to the lower part of the power receiving section, the charged voltage and its decay curve are recorded, and the initial charged voltage is measured from the curve. By the way,
The power receiving unit is set such that the distance between the power receiving unit and the test piece is 50 mm when the test piece is moved. Further, the test is carried out in an environment of 20 ° C. and 60% RH.

A comparison between the friction electrification voltage measured by the above method and the actual dust wiping property shows that when the initial electrification voltage of the antireflection film is -5 kV or less or +20 kV or more, it adheres to the antireflection film. Dust is hard to wipe off.
Therefore, the value of the initial charging voltage needs to be in the range of -5 kV or more and +20 kV or less, and -3 kV or more 20
It is preferably in the range of kV or less.

Next, the structure of the antireflection film of the present invention will be described.

The light-transmitting film used in the antireflection film of the present invention should be one having excellent visible light transmittance (light transmittance of greater than 90%) and excellent transparency (haze of less than 1%). Therefore, there is no particular limitation. Usually, since the antireflection film of the present invention is often used by being provided on the surface of a polarizing plate, the translucent film can also serve as the transparent protective layer of the polarizing plate. In fact, when the antireflection film is provided on the surface of the polarizing plate, the transparent protective layer of the polarizing plate can also be used as the translucent film of the antireflection film of the present invention, and the thickness of the display does not become thick, It is preferable because there are few causes of deterioration of optical characteristics such as surface reflection loss due to generation of interfaces having different refractive indexes due to the increase in the number of layers. Therefore, as the translucent film, a film made of the same polymer as the transparent protective layer of the polarizing plate described later can be used.

From the viewpoint of use as a protective layer of a polarizing plate,
Cellulose type polymers such as cellulose diacetate and cellulose triacetate, acrylic type polymers such as polymethylmethacrylate (PMMA), polycarbonate type polymers, polyolefin type polymers having a cyclo ring or norbornene structure are preferable.

The hard coat layer forming the antireflection film of the present invention is not particularly limited as long as it has excellent hard coat properties and light transmittance. The hard coat layer may be provided directly on one surface of the translucent film, or may be provided via another layer. The hard coat layer may have an uneven structure (preferably a fine uneven structure) formed on the surface for the purpose of imparting antiglare properties.

The fine concavo-convex structure provided on the surface of the hard coat layer may be formed by an appropriate method. For example, sandblasting, embossing rolls, chemical etching or other suitable methods for roughening the surface to give a fine uneven structure to the surface, a transfer method using a mold to give a fine uneven structure to the surface, and fine particles. And a resin layer containing dispersed therein. The fine concavo-convex structure is an additional layer consisting of a hard coat coating layer having fine concavities and convexities on the translucent film, or a surface of the hard coat layer applied on the translucent film is roughened to be fine A processed layer provided with an uneven structure, or a hard coat layer provided on a light-transmitting film having a fine uneven structure formed on the surface by roughening treatment, to the extent that the fine uneven structure does not disappear It can also be formed as.

Further, the fine uneven structure has a structure in which the surface of the hard coat layer itself is roughened as described above to form a fine uneven structure, and a resin layer is further buried in the fine uneven structure to be flat. It is a combination of two or more of the above-mentioned states, such as coating with a thickness of about 100 μm and roughening the surface of the coating layer to give a fine concavo-convex structure. It may be formed as a composite layer.

From the viewpoint of the formation of unevenness characteristics, the fine unevenness structure of the antiglare layer is preferably made of a resin layer containing solid fine particles. Such a resin layer can be formed, for example, by dispersing and containing solid fine particles (hereinafter, simply referred to as fine particles) in a resin solution and coating the solid fine particles on a translucent film. The coating method is not particularly limited,
For example, a method of forming a coating film by coating on a translucent film by an appropriate method such as a doctor blade method or a gravure roll coater method, or a resin film containing fine particles is separately preliminarily formed and It can be formed by an appropriate method such as a method of adhering on the transparent film.

As the resin for forming the hard coat layer, the polymers and the like exemplified in the transparent protective layer of the polarizing plate described later can be appropriately selected and used in consideration of the hardness and the like. A resin that can be particularly preferably used is an ultraviolet curable resin. If you use a UV curable resin, in the curing treatment of the coating layer by UV irradiation, a layer made of UV curable resin containing fine particles if necessary, with a simple processing operation such as embossing with a stamper, It can be formed efficiently. Further, by forming the ultraviolet curable resin layer on the surface of the roughened translucent film, it is possible to easily reflect the surface unevenness of the translucent film on the outermost surface.

Examples of the ultraviolet curable resin include polyester, acrylic, urethane, amide,
Use an appropriate one such as a monomer or oligomer or polymer capable of forming a resin such as a silicone type or an epoxy type, which is mixed with an ultraviolet polymerization initiator so that a resin layer can be formed by curing treatment by ultraviolet irradiation. You can

As the fine particles, spherical or amorphous filler made of inorganic or resin can be used. For example, polymethylmethacrylate (PMMA),
Polyurethane, polystyrene, crosslinked or uncrosslinked organic polymer particles made of various polymers such as melamine resin,
Silica, alumina, calcium oxide, and titania,
Appropriate ones such as zirconia and conductive inorganic particles such as tin oxide, indium oxide, cadmium oxide, antimony oxide and the like can be used. In particular, for the purpose of controlling the refractive index and imparting conductivity, it is preferable to use conductive inorganic particles based on the metal oxide.

The material for forming the antireflection layer is a resin system such as an ultraviolet curable acrylic resin, a hybrid system in which inorganic fine particles such as colloidal silica are dispersed in the resin, RS
i (OR) ₃ , Si (OR) ₄ , RTi (OR) ₃ , Ti
Sol-gel using alkyltrialkoxysilane or tetraalkoxysilane such as (OR) ₄ (wherein R represents a lower alkyl group having 10 or less carbon atoms) or metal alkoxide such as alkyltitanium tetraalkoxide or titanium tetraalkoxide. A system etc. are mentioned. However, the refractive index of the material forming the antireflection layer is smaller than that of the hard coat layer.

The material for forming the antireflection layer as described above can be selected from those containing a fluorine group-containing component for imparting antifouling property to the surface. From the viewpoint of scratch resistance, those having a high content of inorganic components tend to be superior, and among these, sol-gel materials are preferable. The sol-gel system using a metal alkoxide means hydrolysis using a metal alkoxide such as the above-mentioned silicon lower alkoxides and titanium lower alkoxides (all preferably fluorine group-containing alkoxides) as described above. , A gel is formed by heat treatment to form a transparent glass layer, and water and / or lower alcohols such as methanol and ethanol are used as a dispersion medium of such alkoxide, and are required. As the hydrolysis catalyst used according to the above, an acid or alkali such as hydrochloric acid or ammonia is used. When gelling a metal alkoxide sol, it is common to add a hydrolysis catalyst, hydrolyze and heat-treat.

However, in general, the lower the refractive index of the antireflection layer is, the more preferable it is, and the larger the difference in the refractive index with the layer below the antireflection layer is, the greater the antireflection effect is. In order to obtain a preferable antireflection effect in the present invention, a material in which the refractive index of the antireflection layer is the square root of the refractive index of the hard coat layer is preferable. However, in reality, it is generally difficult to find a material having such a refractive index, as already known, and it is necessary to select a material that is as close as possible. On the other hand, the thickness of the antireflection layer is determined by the refractive index of the material used and the design wavelength of the incident light. For example, the refractive index n ₁ of the hard coat layer is 1.51 and the refractive index n _{2 of the} antireflection layer is 1 .3
8. If the design wavelength of the incident light on the antireflection layer is 550 nm, the target thickness of the antireflection layer is calculated to be about 0.1 μm.

That is, specifically, the target thickness of the antireflection layer can be calculated by the following equation. [Equation 1] d = (1 / n ₂ ) × (λ / 4) where d is the target thickness (μm) of the antireflection layer, λ is the design wavelength (μm) of the incident light, and n ₂ is the antireflection layer. The refractive index is shown and the refractive index of the hard coat layer is n ₁ > n ₂ .

The antireflection layer can be formed by coating the hard coat layer by an appropriate method. For example, a method of applying an antireflection layer-forming coating liquid on the hard coat layer to form a coating film, or forming an antireflection film separately in advance and adhering it to the translucent film. It can be formed by an appropriate method such as a method. When the hard coat layer has an antiglare property, it is preferably formed by a method of applying a coating solution for forming an antireflection layer. For example, it can be formed by an appropriate method such as a doctor blade method, a gravure roll coater method, or a dipping method.

Means for forming an antireflection film satisfying the above-mentioned range of frictional electrification voltage is not particularly limited, and for example, the hard coat resin layer may be made conductive to quickly generate static electricity generated by friction. Examples thereof include a method of forming a structure that can be neutralized and a structure of using a conductivity of adsorbed water on the surface by adding a surfactant to the low refractive index layer.

The thus obtained antireflection film of the present invention can be usually laminated or combined with a polarizing plate to form a polarizing plate having an antireflection film. A suitable polarizing plate can be used, but the type thereof is not particularly limited. As the polarizer constituting the polarizing plate, for example, a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, an ethylene / vinyl acetate copolymer partially saponified film, iodine or dichroic Examples thereof include absorption dichroic polarizers obtained by adsorbing and stretching dichroic substances such as dyes, and polarizers such as polyene oriented films such as dehydration products of polyvinyl alcohol and dehydrochlorination products of polyvinyl chloride. Above all, an absorbing dichroic polarizer is preferably used because of its excellent polarization characteristics. The thickness of the polarizer is 5 to 80 μm.
m is common, but not limited to this.

The polarizing plate may be a polarizing plate consisting of a polarizer alone, but the polarizing plate is usually used for the purpose of protecting one side or both sides of the above-mentioned polarizer (polarizing film) such as water resistance. Those provided with a transparent protective layer composed of a polymer coating layer, a film laminate layer, and the like are preferably used. Although an appropriate material such as a transparent polymer can be used for forming the transparent protective layer, an excellent material such as transparency, mechanical strength, thermal stability and moisture barrier property is preferably used. Further, it is often preferable that the transparent protective layer has less optical anisotropy such as retardation. The thickness of the transparent protective layer is generally 10 to 300 μm, but is not limited thereto. As described above, the transparent protective layer of the polarizing plate can also serve as the translucent film of the antireflection film of the present invention.

Incidentally, as the polymer for forming the transparent protective layer, for example, polyester type polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose type polymers such as cellulose diacetate and cellulose triacetate, polymethylmethacrylate (PMM).
Examples thereof include acrylic polymers such as A), styrene polymers such as polystyrene and acrylonitrile / styrene copolymer (AS resin), and polycarbonate polymers.

Further, polyethylene, polypropylene, polyolefin having a cyclo ring or norbornene structure, polyolefin polymer such as ethylene / propylene copolymer, vinyl chloride polymer, amide polymer such as nylon or aromatic polyamide, imide such as polyimide. -Based polymers, sulfone-based polymers such as polysulfone, other, polyether sulfone-based polymers, polyether ether ketone-based polymers, polyphenylene sulfide-based polymers, vinyl alcohol-based polymers,
Vinylidene chloride-based polymers, vinyl butyral-based polymers, arylate-based polymers, polyoxymethylene-based polymers, epoxy-based polymers, and blends of the aforementioned polymers are also examples of polymers forming the transparent protective layer.

The antireflection film of the present invention may be laminated on a polarizing plate. When the polarizing plate has a transparent protective layer as described above, the transparent protective layer may be used as a light transmitting material for the antireflection film of the present invention. It may also be used as a low-reflecting polarizing plate by also being used as a film. The stacking method is not particularly limited, but may be stacked via an adhesive or the like. Further, it may be provided on one side or both sides of the polarizing plate.

An adhesive layer may be provided on the polarizing plate if necessary. Such an adhesive layer is intended to adhere the polarizing plate to another member such as a liquid crystal cell. The adhesive layer can be formed with an appropriate adhesive such as an acrylic-based, rubber-based or silicone-based pressure-sensitive adhesive or a hot-melt adhesive, and is preferably one having excellent transparency and weather resistance.

In the polarizing plate according to the present invention, an optical functional layer selected from a reflective layer, a semi-transmissive reflective layer, and a retardation plate is further provided on the interlayer and / or surface of the polarizing plate having a multi-layer structure, if necessary. At least one layer may be interposed and / or provided and laminated to be used for various applications such as a display device. Further, if necessary, various properties such as scratch resistance, durability, weather resistance, moist heat resistance, heat resistance, moisture resistance, moisture permeability, antistatic property, conductivity, improved adhesion between layers, and improved mechanical strength, It is also possible to perform a process for imparting a function or the like, or to insert or laminate a functional layer. Between the layers of the polarizing plate having a multilayer structure, for example, a hard coat layer, a primer layer, an adhesive layer, a pressure-sensitive adhesive layer, an antistatic layer, a conductive layer, a gas barrier layer,
A water vapor barrier layer, a moisture barrier layer or the like may be inserted or these layers may be laminated on the surface of the polarizing plate. Also. At the stage of forming each layer of the polarizing plate, for example, conductive particles, antistatic agents, various fine particles, a plasticizer, etc. may be added to each layer, and mixing and the like may be improved as necessary.

FIG. 3 shows a schematic sectional view of an example of the antireflection film of the present invention in which a hard coat layer and an antireflection layer are provided on a translucent film. In FIG. 3, 13
Is a translucent film, 14 is fine particles, 12 is a hard coat layer containing the fine particles, that is, an antiglare layer, and 11 is an antireflection layer having an initial charged voltage value of -5 kV or more and +20 kV or less. 4 is a schematic cross-sectional view of an example of a low reflection polarizing plate having an antireflection film in which the antireflection film of the present invention is laminated on a polarizing plate.
Reference numeral 6 denotes a polarizer, and the transparent protective layer 15 is provided on the upper and lower surfaces of the polarizer 16. In this embodiment, the polarizer 1
The transparent protective layer 15 provided on the upper surface side of 6 also serves as the transparent film 13 of the antireflection film shown in FIG. Reference numeral 14 is fine particles, 12 is a hard coat layer containing the fine particles, that is, an antiglare layer, and 11 is an antireflection layer having an initial charged voltage value of -5 kV or more and +20 kV or less.

The antireflection film and polarizing plate of the present invention can be preferably used for forming various display devices such as liquid crystal display devices and organic EL display devices. For example, it can be used for a liquid crystal display device such as a reflective type or a semi-transmissive type, or a transmissive / reflective type in which a polarizing plate is arranged on one side or both sides of a liquid crystal cell. The liquid crystal cell forming the liquid crystal display device is arbitrary, and an appropriate type such as an active matrix drive type represented by a thin film transistor type, a simple matrix drive type represented by a twist nematic type or a super twist nematic type, etc. The liquid crystal cell may be used.

When polarizing plates and optical members are provided on both sides of the liquid crystal cell, they may be the same or different. Further, when forming the liquid crystal display device, one or two or more layers can be arranged at appropriate positions with appropriate components such as a prism array sheet, a lens array sheet, a light diffusion plate, and a backlight.

[0040]

The present invention will be described in more detail with reference to the following examples.

Example 1 An average particle size of 60 nm was formed on a TAC (triacetyl cellulose) film having a thickness of 60 μm.
Of ATO (antimony-doped tin oxide) ultrafine particles dispersed with a methyl ethyl ketone solution of a UV-curable acrylic hard coat resin is applied using a wire bar, and after solvent drying, UV irradiation is performed with a low-pressure UV lamp to obtain a hard coating of 5 μm thickness. A coat layer was formed. Subsequently, a low refractive index layer made of a fluorine compound polymer produced by a sol-gel reaction of a mixture of polysiloxane and fluoroalkylsilane is applied so that the thickness after curing becomes about 100 nm,
An antireflection film was obtained.

(Example 2) When forming a hard coat layer, an antiglare function was obtained by using a coating liquid in which 5 parts by mass of silica beads having a particle diameter of 2 μm were added to 100 parts by mass of the solid content of the resin. An antireflection film was obtained in the same manner as in Example 1 except that the attached hard coat layer was used.

(Example 3) The dispersion concentration of ATO in Example 1
An antireflection film was obtained in the same manner as in Example 1 except that the thickness was changed to 2/3.

Example 4 An antireflection film was obtained in the same manner as in Example 1 except that a commercially available epoxy-containing acrylic resin was used as the resin.

Comparative Example 1 Example 1 was repeated except that a commercially available UV-curable acrylic hard coat resin was used as the resin.
An antireflection film was obtained according to the above.

Comparative Example 2 An antireflection film was obtained in the same manner as in Example 1 except that a commercially available silicon hard coat resin was used as the resin.

(Evaluation) The triboelectric charge amount was measured according to the method described above. By the way, as a measuring device, a friction electrification voltage measuring device E.K. manufactured by Kanebo Engineering Co., Ltd. was used. S. T-7 was used. To remove dust, commercially available tissue paper (pulp 100%) is disentangled even on the antireflection film, the generated lint is adhered, and the easiness of wiping with a cotton rag is visually observed according to the following criteria. evaluated. ○: Lint adheres to the waste side and can be removed. ×: Lint does not separate from the antireflection film even if it is wiped with static electricity.

Table 1 shows the above evaluation results.

A polarizing plate was produced by using the antireflection film produced in Examples 1 to 4 as a protective layer on the upper surface side (viewing side) of the polarizer. As a result, a highly practical polarizing plate with an antireflection function, which maintains the characteristics shown in Table 1, was obtained.

[0050]

According to the present invention, it is possible to obtain an antireflection film having good display quality and excellent in wiping off dust on the surface, and a polarizing plate provided with the antireflection film. in addition,
The antireflection layer can be formed by a wet coating method, which is a very simple method as compared with a forming method such as a vacuum deposition method.

[Brief description of drawings]

FIG. 1 is an external view of a friction element used for measuring a charged voltage according to the present invention.

FIG. 2 is a schematic view of an apparatus of a method for testing a charged voltage according to the present invention.

FIG. 3 is a schematic sectional view of an example of the antireflection film of the present invention.

FIG. 4 is a schematic sectional view of an example of a polarizing plate on which the antireflection film of the present invention is formed.

[Explanation of symbols]

1: Friction element 2: Friction cloth 3: Test piece (antireflection film or low reflection polarizing plate) 4: Test piece table 5: Test piece holder 6: Friction table 11: Antireflection layer 12: Hard coat layer (anti-glare layer) 13: Translucent film 14: Fine particles 15: Transparent protective layer 16: Polarizer

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Claims (7)

[Claims] 1. An antireflection film in which a hard coat layer is provided on one surface of a translucent film directly or via another layer, and a low refractive index layer is laminated on the surface of the hard coat layer by coating. The value of the initial charged voltage measured on the surface according to the frictional charge attenuation measurement method described in JIS L 1094 using a friction cloth of hair described in JIS L 0803 is -5 kV or more +
An antireflection film having a voltage of 20 kV or less. 2. The antireflection film according to claim 1, wherein the hard coat layer has an uneven surface shape and has an antiglare property. 3. The antireflection film according to claim 1, wherein the hard coat layer contains an inorganic or resin spherical or amorphous filler. 4. A polarizing plate having protective layers on both sides of an absorptive dichroic polarizer, wherein at least one of the protective layers is the antireflection film according to claim 1. A polarizing plate characterized by that. 5. A display device comprising the antireflection film according to claim 1. 6. A liquid crystal display device comprising the polarizing plate according to claim 4. 7. An organic EL display device, comprising the polarizing plate according to claim 4.