WO2019172651A1 - Polarizing plate and image display device comprising same - Google Patents

Polarizing plate and image display device comprising same Download PDF

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Publication number
WO2019172651A1
WO2019172651A1 PCT/KR2019/002606 KR2019002606W WO2019172651A1 WO 2019172651 A1 WO2019172651 A1 WO 2019172651A1 KR 2019002606 W KR2019002606 W KR 2019002606W WO 2019172651 A1 WO2019172651 A1 WO 2019172651A1
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WO
WIPO (PCT)
Prior art keywords
polarizing plate
polarizer
layer
hard coat
coat layer
Prior art date
Application number
PCT/KR2019/002606
Other languages
French (fr)
Korean (ko)
Inventor
서정현
홍경기
장영래
박진영
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP19763725.9A priority Critical patent/EP3677935B1/en
Priority to CN201980005100.4A priority patent/CN111213078A/en
Priority to JP2020519739A priority patent/JP7330469B2/en
Priority to US16/760,528 priority patent/US20210223453A1/en
Priority claimed from KR1020190025662A external-priority patent/KR102181559B1/en
Publication of WO2019172651A1 publication Critical patent/WO2019172651A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Definitions

  • the present invention relates to a polarizing plate constituting an image display device and an image display device including the same.
  • the substrate for display As a material for the display window or the front plate of the mobile device, glass or tempered glass having excellent mechanical properties such as strength and tensile strength and excellent shock absorption against external shock is generally used.
  • the glass has a high reflectance and thus lowers the visibility of the display, the weight of the glass itself increases the weight of the mobile device, and there is a problem of breakage due to external impact.
  • plastic resin is being researched as a substitute material for glass.
  • Plastic resin films are lightweight and less prone to break, making them suitable for the trend toward lighter mobile devices.
  • a film coated with a hard coat layer on a supporting substrate has been proposed.
  • a method using a polarizer protective film for protecting the polarizer disposed on the image display surface side of the display is known.
  • the polarizer protective film generally consists of a light transmissive base film, and the light transmissive base film is triacetyl cellulose. Cellulose ester-based film represented by the most widely used.
  • Such a cellulose ester-based film has advantages such as excellent transparency and optical isotropy, little retardation in the plane, no interference fringe, and almost no adverse effect on the display quality of the display device. 2019/172651 1 »(: 1 ⁇ 1 ⁇ 2019/002606
  • the cellulose ester-based film is not only a material having a disadvantage in terms of cost, but also has disadvantages of high moisture permeability and poor water resistance. Due to this high moisture permeability and poor water resistance, a considerable amount of water permeation can occur continuously during use, causing the phenomenon of lifting from the polarizer, which can cause light leakage.
  • polyester-based film such as polyethylene terephthalate seedling film as a base film of the polarizer protective film.
  • Such a polyester-based film is inexpensive, has excellent water resistance, hardly causes light leakage, and has excellent mechanical properties.
  • such a polyester-based film includes an aromatic ring having a high refractive index in the structure, and has a disadvantage of generating a refractive index difference (in-plane birefringence) and an in-plane retardation caused by a difference in elongation in the 3 ⁇ 4 ⁇ / 10 direction during the film forming process. .
  • a refractive index difference in-plane birefringence
  • the present invention effectively suppresses the occurrence of the rainbow phenomenon derived from the polyester-based substrate film, excellent visibility and mechanical properties of the polarizing plate that can be appropriately applied to the window or front plate of the image display device and an image display device comprising the same It is to provide.
  • a polarizer According to an embodiment of the present invention, a polarizer
  • a light-transmitting substrate on the first hard coating layer having a retardation # 3 3 011) of 3000 ⁇ 1 or more, and having a birefringence in plane; And a binder resin positioned on the light transmissive substrate; And a second hard coat layer including; and solid inorganic nanoparticles dispersed in the binder resin.
  • a polarizing plate having an angle between the slow axis of the light transmissive substrate and the absorption axis of the polarizer may be 5 to 85 ° .
  • an image display device including the polarizing plate may be provided.
  • first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from other components.
  • (meth) acryl [(meth) acryl] is meant to include both acryl and methacryl.
  • the inorganic nanoparticles of the hollow structure refers to particles having a form in which an empty space exists on the surface and / or inside of the inorganic nanoparticles.
  • a (co) polymer is meant to include both copolymers and homopolymers.
  • the present inventors use a light-transmissive substrate having a birefringence in-plane as a supporting substrate, and in the light-transmissive substrate having a birefringence in the plane, an acute angle formed between a slow axis having the largest refractive index and an absorption axis of the polarizer is formed.
  • the retardation of the light-transmitting substrate having a birefringence in the plane to at least 3, 000nm, 4,000 to 10,000nm, or 5,000 to 8,000nm, the rainbow phenomenon due to destructive interference is suppressed, It was confirmed that the visibility of the image display device can be improved based on the cellulose ester-based film.
  • any of the angle and the retardation of the light transmissive substrate is not controlled to an appropriate range, the mechanical properties may be deteriorated, the rainbow phenomenon may occur due to the birefringence of the light transmissive substrate, and the visibility of the image display apparatus may be degraded. .
  • the polarizing plate including the polarizer and the laminate formed on the polarizer can be suitably applied to the window or the front plate of the image labeling device because of excellent visibility and mechanical properties.
  • the polarizing plate of the embodiment includes a polarizer.
  • the polarizer may be a film made of polyvinyl alcohol (1/1) including a polarizer well known in the art, for example, iodine or a dichroic dye.
  • the polarizer may be prepared by dyeing and stretching an iodine or a dichroic dye on a polyvinyl alcohol film, but a method of manufacturing the same is not particularly limited.
  • the polyvinyl alcohol film may be used without particular limitation as long as it includes a polyvinyl alcohol resin or a derivative thereof.
  • examples of the derivative of the polyvinyl alcohol resin include, but are not limited to, polyvinyl formal resin, polyvinyl acetal resin, and the like.
  • the polyvinyl alcohol film is a commercially available polyvinyl alcohol film generally used in the manufacture of polarizers in the art, for example,? 30,? £ 30,? £ 60 by Gurere, 3000, 3 ⁇ 46000 etc. can be used. '
  • the polyvinyl alcohol film is not limited thereto, but the polymerization degree may be 1000 to 10000 or 1500 to 5000. When the degree of polymerization satisfies the above range, the molecular motion is free and can be mixed flexibly with iodine or dichroic dye.
  • the polarizer may have a thickness of 30 m 1 or less, 20 m or less, 1 to 20 / mm, or 1 to 10 m. In this case, the polarizer Thin weight reduction of devices, such as a polarizing plate and an image display apparatus, is included.
  • the first hard coating layer on one surface of the polarizer, a light transmissive substrate having a birefringence in the surface, and a laminate in which the second hard coating layer is sequentially laminated may be bonded.
  • the light transmissive substrate there is little possibility of causing light leakage due to excellent water resistance, and a polyethylene terephthalate (PET) film having excellent mechanical properties may be used.
  • PET polyethylene terephthalate
  • the first and second hard coating layers are formed on both sides of the light transmissive substrate, respectively, mechanical properties capable of replacing a glass material are provided. Accordingly, the polarizing plate on which the laminate is formed may be a window or front surface of the image display device. Applicable to the edition as appropriate.
  • a quarter wave plate may be bonded to the other surface of the polarizer facing the first hard coating layer.
  • the quarterwave plate has a wave plate that changes the polarization direction of light by 45 °.
  • the incident polarization which is linearly polarized light
  • the incident polarization may be converted into circularly polarized light.
  • the outgoing polarization may be right circularly polarized light (ri ght handed ci rcu l ar po i ar i za t i on).
  • a method of bonding a laminate including the first hard coating layer to one surface of the polarizer and a quarter wave plate to the other surface may include, for example, a roll coater, a gravure coater, a bar coater, a knife coater, or a capillary.
  • After coating the adhesive on the surface of the polarizer, the first hard coating layer or the quarter wave plate using a coater or the like they may be carried out by heating or laminating them with a lamination roll, or laminating by pressing at room temperature, or laminating or UV irradiation.
  • various polarizing plate adhesives used in the art for example, polyvinyl alcohol-based adhesives, polyurethane-based adhesives, acrylic adhesives, cationic or radical-based adhesives, and the like may be used without limitation.
  • the branch includes a first hard coat layer located between the light transmissive substrates.
  • the first hard coating certificate may include a binder resin including a (meth) acrylate-based (co) polymer.
  • the (meth) acrylate type (co) polymer contained in the said binder resin is a monofunctional or polyfunctional (meth) acrylate type repeating unit, and a urethane.
  • Including a (meth) acrylate type repeating unit, high hardness, flexibility, and impact resistance can be imparted to the first hard coat layer.
  • the monofunctional or polyfunctional (meth) acrylate-based repeating unit is derived from a monofunctional or polyfunctional (meth) acrylate-based compound, and the urethane (meth) acrylate-based repeating unit is a urethane (meth) acrylate-based It is derived from a compound. Therefore, the said (meth) acrylate type (co) polymer is the said monofunctional or polyfunctional (meth) acrylate type compound, and urethane.
  • the (meth) acrylate compound may be formed by crosslinking polymerization.
  • the monofunctional or polyfunctional (meth) acrylate-based compound is a compound containing at least one (meth) acrylate structure in the molecule capable of curing the coating film by the cross-linking reaction proceeds by ultraviolet rays, infrared rays, seedlings and heat.
  • the urethane (meth) acrylate compound is a (meth) acrylate compound is bonded through a urethane bond, may be in the form of a monomer or oligomer.
  • the average molecular weight of the urethane (meth) acrylate monomer or oligomer may be 500 to 200, 000, 700 to 150, 000, 1, 000 to 120, 000, or 2,000 to 100, 000.
  • the polarizing plate according to the embodiment includes a light transmissive substrate having a birefringence in the plane located on the first hard coat layer.
  • the light transmissive substrate is a retardation More than 3, 00011111, from 4, 000 2019/172651 1 »(: 1 ⁇ 1 ⁇ 2019/002606
  • the rainbow by arranging on the first hard coating layer so that the acute angle between the slow axis of the light transmissive substrate and the absorption axis of the polarizer is 5 to 85 ° It is possible to exhibit the effect of excellent visibility and excellent mechanical properties without the phenomenon.
  • the retardation is a refractive index in the slow axis direction (3 ⁇ 4), which is the direction of the largest refractive index in the plane of the light transmissive substrate, a refractive index in the fast axis direction (), which is orthogonal to the slow axis direction, and the thickness of the light transmissive substrate.
  • (1 (unit: 11111) 1- may be calculated by substituting into Equation 1 below).
  • the retardation can also be obtained by the following method.
  • two axial refractive indices (3 ⁇ 4,%) which are provided in the alignment axis direction of the light-transmitting substrate using two polarizing plates and orthogonal to the orientation axis direction are obtained by Shore 6 Refractive Index Function-4.
  • Shore 6 Refractive Index Function-4 the axis showing a larger refractive index is defined as the slow axis.
  • the thickness of the light transmissive substrate is measured using an electric micrometer, for example, and the refractive index using the refractive index obtained above Calculation is referred to as bus 11) and can be determined by the product between the thickness of the retardation (1 (ä) of the refractive index difference between switch 11 and the light-transmitting substrate.
  • the refractive index difference (s11) is less than 0.05, the light transmissive substrate required to obtain the retardation value described above is on the other hand, if the refractive index difference 11 exceeds 0.20, it is necessary to excessively increase the draw ratio, so that the light-transmissive substrate is likely to be torn and broken, which may significantly reduce the practicality as an industrial material. And damp-heat resistance may be lowered.
  • the refractive index (3 ⁇ 4) in the slow axis direction of the light transmissive substrate is 1.60 to 2019/172651 1 »(: 1 ⁇ 1 ⁇ 2019/002606
  • the refractive index (%) in the fast axis direction of the light transmissive substrate having the birefringence in the plane may be 1.50 to 1.70, or 1.55 to 1.65.
  • the thickness of the light transmissive substrate having the birefringence in the plane is not limited thereto, but may be 10 to 500 // III, 30 to 400, or 50 to 350 /.
  • the thickness of the light transmissive substrate is less than 10 / thickness, the thickness of the hard coating layer is too thin, so that warpage may occur, and the flexibility of the light transmissive substrate may be difficult to control the process.
  • the thickness is greater than 500, the transmittance of the light transmissive substrate is reduced. Optical properties may decrease, and it is difficult to thin an image display device including the same.
  • the light-transmitting base material is excellent in water resistance and hardly cause a light leakage phenomenon, it is possible to use a polyethylene terephthalate seed film excellent mechanical properties.
  • the polarizing plate of the embodiment includes a second hard coat layer positioned on the light transmissive substrate having a birefringence in the plane.
  • the second hard coat layer is a binder resin; And solid-type inorganic nanoparticles dispersed in the binder resin, to impart high hardness, flexibility, and impact resistance to the second hard coating layer.
  • the binder resin of the second hard coat layer may include a photocurable resin and a (co) polymer (hereinafter, referred to as a high molecular weight (co) polymer) having a weight average molecular weight of 10, 001 ⁇ 2 /
  • the photocurable resin is a polymer of a photopolymerizable compound which can cause a polymerization reaction when light such as ultraviolet rays is irradiated, such as urethane acrylate oligomer, epoxide acrylate oligomer, polyester acrylate and polyether acrylate.
  • One or more kinds selected from the group consisting of polyfunctional acrylate monomers made may be used.
  • the high molecular weight (co) polymer is, for example, at least one polymer selected from the group consisting of cellulose depolymers, acrylic polymers, styrene polymers, epoxide polymers, nylon polymers, urethane polymers and polyolefin polymers. It may include.
  • Solid-type inorganic nanoparticles dispersed in the binder resin of the second hard coating layer refers to particles having a maximum diameter of less than 100 11111 and no empty space therein.
  • the solid inorganic nanoparticles may have a diameter of 0.5 to 100, or 1 to 30
  • the solid inorganic nanoparticles may have a density of 2.00 yaw / to 5.01 ⁇ 2 / 01 sec.
  • the solid inorganic nanoparticles may contain at least one reactive functional group selected from the group consisting of a (meth) acrylate group, an epoxide group, a vinyl group (1) and a thiol group (3 ⁇ 4 ratio1) on the surface.
  • a reactive functional group selected from the group consisting of a (meth) acrylate group, an epoxide group, a vinyl group (1) and a thiol group (3 ⁇ 4 ratio1) on the surface.
  • the thickness ratio of the first hard coat layer and the second hard coat layer may be 1: 0.5 to 1: 1.5, 1: 0.6 to 1.4, or 1: 0.8 to 1.3.
  • the thickness ratio of the first hard coat layer and the second hard coat layer is less than 1: 0.5 or more than 1: 1.5, the whip of the film is generated and it is difficult to maintain a flat film form and cannot be used as an optical film.
  • the thickness ratio of the light transmissive substrate and the second hard coat layer may be 1: 0.1 to 1: 1, 1: 0.2 to 0.9, or 1: 0.3 to 0.8.
  • the light transmissive substrate and the second hard coating layer have a thickness ratio of less than 1: 0.1, the hardness and scratch resistance of the film may be lowered to protect the polarizing plate from external impact. In the bonding process and the first hard coating layer cotang process, the film may be broken without bending.
  • the composition for forming the first and second hard coating layers on the face of the light transmissive substrate respectively, roll coater, gravure Coater, Bar Coater, 2019/172651 1 »(: 1 ⁇ 1 ⁇ 2019/002606
  • the solvent may be volatilized, and then heat / photocured to prepare a laminate including the first and second hard coat layers.
  • the polarizer or the laminate is coated with an adhesive using a roll coater, a gravure coater, a bar coater, a knife coater or a capillary coater, and then laminating them with a lamination roll, or laminating by pressing at room temperature or laminating. It may be carried out by a method such as irradiation.
  • the adhesive various polarizing plate adhesives used in the art, for example, polyvinyl alcohol-based adhesives, polyurethane-based adhesives, acrylic adhesives, cationic or radical-based adhesives and the like can be used without limitation.
  • the polarizing plate It can manufacture.
  • the polarizing plate of the embodiment may further include a low reflection layer positioned on the second hard coating layer.
  • a low reflection layer is a binder resin; And inorganic nanoparticles dispersed in the binder resin.
  • the inorganic nanoparticles may be hollow inorganic nanoparticles, solid inorganic nanoparticles, or a mixture thereof.
  • the binder resin includes a (co) polymer containing a polyfunctional (meth) acrylate-based repeating unit, and the repeating unit is, for example, trimethylolpropane triacrylamide Trimethylolpropaneethoxy triacrylic
  • It may be derived from a polyfunctional (meth) acrylate-based compound such as glycerin propoxylated triacrylate 1 ⁇ 2 ⁇ / ⁇ ), pentaerythritol tetraacrylate oxy, or dipentaerythritol nuxaacrylate ( ⁇ ). .
  • a polyfunctional (meth) acrylate-based compound such as glycerin propoxylated triacrylate 1 ⁇ 2 ⁇ / ⁇ ), pentaerythritol tetraacrylate oxy, or dipentaerythritol nuxaacrylate ( ⁇ ).
  • the low reflection layer may further include a fluorine-containing compound having a photoreactive functional group and / or a silicon-based compound having a photoreactive functional group.
  • the photoreactive functional group contained in the compound or silicone compound may include one or more functional groups selected from the group consisting of (meth) acrylate groups, epoxide groups, vinyl groups (1 1) and thiol groups (1 ⁇ 01). .
  • the fluorine-containing compound including the photoreactive functional group may include 1) an aliphatic compound or an aliphatic ring compound in which one or more photoreactive functional groups are substituted and at least one fluorine is substituted for at least one carbon; ) A hetero near aliphatic compound substituted with one or more photoreactive functional groups, at least one hydrogen substituted with fluorine, and one or more carbons substituted with silicon; or a hetero (11 li-0) aliphatic ring compound; 1 1 1) polydialkylsiloxane polymers in which at least one photoreactive functional group is substituted and at least one fluorine is substituted in at least one silicon; And a polyether compound substituted with at least one photoreactive functional group and at least one hydrogen is replaced with fluorine.
  • the hollow inorganic nanoparticles refer to particles having a maximum diameter of less than 200 L and have a void space on the surface and / or inside thereof.
  • the hollow inorganic nanoparticles may include one or more selected from the group consisting of solid inorganic fine particles having a number average particle diameter of 1 to 200 11111, or 10 to 100 11111.
  • the hollow inorganic nanoparticles may have a density of 1.5 ⁇ / 011 1 to 3.50 ⁇ / (.
  • the hollow inorganic nanoparticles may contain at least one reactive functional group selected from the group consisting of a (meth) acrylate group, an epoxide group, a vinyl group (1), and a thiol group (3 ⁇ 4 ratio1) on the surface.
  • a reactive functional group selected from the group consisting of a (meth) acrylate group, an epoxide group, a vinyl group (1), and a thiol group (3 ⁇ 4 ratio1) on the surface.
  • the solid inorganic nanoparticles may include at least one member selected from the group consisting of solid inorganic fine particles having a number average particle diameter of 0.5 to 100 ⁇ .
  • the low reflection layer is 10 to 400 parts by weight of the inorganic nanoparticles relative to 100 parts by weight of an additive (co) polymer; And 20 to 300 parts by weight of a fluorine-containing compound and / or a silicon-based compound including the photoreactive functional group.
  • the polarizer includes such a low reflection layer, the first 2019/172651 1 »(: 1 ⁇ 1 ⁇ 2019/002606
  • the reflection itself in the transparent substrate positioned on the hard coating layer can be reduced, and as a result, it is possible to effectively suppress the occurrence of the rainbow phenomenon in the polarizing plate of one embodiment. In addition, it is possible to further improve the resolution and visibility by reducing the diffuse reflection on the display surface of the image display device including the low reflection layer.
  • Such a low reflection layer is, for example, 1.3 to 1.5, 1.35 to 1.45, or 1.38 to 1, in order to effectively suppress reflection on a light transmissive substrate having a birefringence in the surface, or diffuse reflection on a display surface of an image display device. It has a refractive index of 1.43 and may have a thickness of 1 to 300ä, 5 to 200ä, or 50 to 150ä.
  • the polarizing plate of the embodiment may further include a fouling resistant layer positioned on the second hard coating layer.
  • the stain resistant layer is a binder resin; Solid inorganic nanoparticles dispersed in the binder resin; And fluorine-based compounds.
  • the binder resin of the fouling resistant layer may include a copolymer containing a (meth) acrylate-based repeating unit.
  • the (meth) acrylate-based repeating unit is, for example, trimethylolpropane triacrylamide
  • Trimethylolpropaneethoxy triacrylic It may be derived from polyfunctional (meth) acrylate-based compounds such as glycerin propoxylated triacrylate 1 ⁇ 2-70, pentaerythritol triacrylate ⁇ / ⁇ ), or dipentaerythritol nuxaacrylate ().
  • the binder resin of the fouling resistant layer may be used by mixing two or more kinds in order to maintain appropriate dispersibility and crosslinking degree when mixed with solid inorganic nanoparticles.
  • the solid inorganic nanoparticles may have a diameter of 0.5 to 100 11 microns, or 1 to 30 1ä.
  • the solid inorganic nanoparticles may have a density of 2.00 ⁇ / 011 1 to kr /.
  • the solid inorganic nanoparticles may contain at least one reactive functional group selected from the group consisting of (meth) acrylate groups, epoxide groups, vinyl groups (1) and thiol groups (1 ⁇ 01) on the surface. . By including the reactive functional group described above on the surface of the solid inorganic nanoparticles, it may have a higher degree of crosslinking, thereby ensuring more improved antifouling properties.
  • the fluorine-based compound is at least one fluorine element of the compound 2019/172651 1 »(: 1 ⁇ 1 ⁇ 2019/002606
  • the fouling resistant layer may include a fluorine-based compound, or may include a crosslinked (co) polymer between the fluorine-based compounds.
  • the fluorine-based compound has a weight average molecular weight of 2,000, 200, 000, or 5, 000 to 100, 000
  • the weight average molecular weight of polystyrene conversion measured by " can be used.
  • the weight average molecular weight of the fluorine-based compound is less than 2,000, the fluorine-based compounds may not be uniformly and effectively arranged, and the stain resistance of the fouling-resistant layer may be lowered, and when it exceeds 200, 000, compatibility with other components may be lowered.
  • the polarizing plate may further include an adhesive layer formed on the other surface of the quarterwave plate to face the polarizer.
  • the polarizer may be positioned on one surface of the quarterwave plate, and the adhesive layer may be positioned on the opposite surface of the quarter wave plate of the polarizer.
  • the adhesive layer may enable attachment of the polarizing plate of the embodiment and the image panel of the image display device.
  • the adhesive layer may be formed using various adhesives well known in the art, and the kind thereof is not particularly limited.
  • the pressure-sensitive adhesive layer may be a rubber pressure sensitive adhesive, an acrylic pressure sensitive adhesive, a silicone pressure sensitive adhesive, a urethane pressure sensitive adhesive, a polyvinyl alcohol pressure sensitive adhesive, a polyvinylpyrrolidone pressure sensitive adhesive, a polyacrylamide pressure sensitive adhesive, a cellulose pressure sensitive adhesive, a vinyl alkyl ether pressure sensitive adhesive, or the like. It can be formed using.
  • the pressure-sensitive adhesive layer may be formed by applying a pressure-sensitive adhesive on the upper portion of the quarter wave plate, or may be formed by attaching a pressure-sensitive adhesive sheet prepared by applying an adhesive on a release sheet and then drying the pressure-sensitive adhesive sheet on the upper portion of the quarter wave plate. .
  • the laminate including the light-transmitting substrate having a birefringence in the surface and the first and second hard coating layers formed on both sides of the light-transmissive substrate is bonded, hardness, etc. Its mechanical properties are very good.
  • the polarizer may have a pencil hardness greater than or equal to, 9 to 9, or even at 500 ⁇ load.
  • the polarizing plate may include a structure excluding the polarizer, that is, the first hard coating layer, the light transmissive substrate, and the second hard motor layer.
  • the pencil hardness under load may be greater than or equal to, or less than, or less than. Further, it may be a laminate, and the laminate of the low reflection layer formed on (or stain layer) over the anti-reflection film has a pencil hardness ⁇ from lkg load, including, 7H to 9H, or 8H to 9H.
  • the light transmissive substrate having a birefringence in the plane included in the polarizing plate since the acute angle between the slow axis of the light transmissive substrate and the absorption axis of the polarizer is arranged to be 5 to 85 °, the rainbow phenomenon is There is an advantage that is suppressed.
  • the reflectance of the polarizing plate is measured, and the difference between the average reflectance and the maximum reflectance and the minimum reflectance is measured from the measured reflectance data, and then substituted into the following Equation 1
  • the rainbow variable ratio can be checked regularly.
  • the reflectance measurement of the polarizing plate using Shimadzu's UV-VIS spectrometer (UV-VIS spectrometer, model name: UV2550), 5 ° reflection mode, the slit width (siit width) 2imi, and the analysis wavelength range of 380 to 780 nni
  • UV-VIS spectrometer model name: UV2550
  • the slit width (siit width) 2imi
  • the analysis wavelength range 380 to 780 nni
  • the difference between the reflectance average and the maximum reflectance and the minimum reflectance at 450 to 650iim was calculated and substituted into the following Equation 1 for the variation ratio of the rainbow: (A Rb) can be calculated.
  • the rainbow variable ratio may be 10% or less, or 1% to 10%.
  • ARb (maximum reflectance at 450 to 650 nm-minimum reflectance at 450 to 650 nm) ⁇ (reflection average at 450 to 650 nm) x 100
  • an image display device including the polarizing plate.
  • the image display device includes a display panel; And the polarizing plate disposed on at least one surface of the display panel.
  • the display panel may be a liquid crystal panel, a plasma panel, and an organic light emitting panel.
  • the image display device may be a liquid crystal display (LCD), a plasma display device) and an organic light emitting display device (0LED).
  • the image display device may be a liquid crystal display device including a liquid crystal panel and a light laminated body provided on both surfaces of the liquid crystal panel, wherein at least one of the polarizing plates described above It may be a polarizing plate including a polarizer according to the embodiment.
  • the type of liquid crystal panel included in the liquid crystal display device is not particularly limited, but, for example, TN (twi sted nematic) type, STN (super twisted nematic) type, F (ferroelectic) type or PD (polymer dispersed) Passive matrix panels such as type; Active matrix panels such as two terminal or three terminal; All known panels, such as an In Plane Switching (IPS) panel and a Vertical Alignment (VA) panel, can be applied.
  • TN twi sted nematic
  • STN super twisted nematic
  • F ferrroelectic
  • PD polymer dispersed
  • Passive matrix panels such as type
  • Active matrix panels such as two terminal or three terminal
  • All known panels such as an In Plane Switching (IPS) panel and a Vertical Alignment (VA) panel, can be applied.
  • IPS In Plane Switching
  • VA Vertical Alignment
  • the polarizing plate and the image display including the same which can be preferably applied to the window or the front plate of the image display device while including a polyester-based film, but the rainbow phenomenon does not appear, and excellent visibility and mechanical properties
  • An apparatus may be provided.
  • Aekyung Chemical's DN980S which is an HDI-based trimer, is used as a polyethylene glycol-modified (meth) acrylate compound, and includes different repeating numbers of polyethylene glycol repeating units with different number average molecular weights.
  • PMMA Polymethylmethacrylate
  • PBA polybutylacrylate
  • a high molecular weight copolymer (PMMA-PBA block copolymer) was prepared by RAFT polymerization (Reversible addition fragment chain transfer polymerization). At this time, the volume ratio of PMMA and PBA was about 1: 1, and the number average molecular weight was about 30,000 g / mol. In addition, the average particle diameter of the micelle structure formed by self-assembly of PMMA-PBA block copolymer was about 15 nm.
  • TMPTA trimethylpropyl triacrylate
  • MMPTA trimethylpropyl triacrylate
  • MIBK methyl isobutyl ketone
  • Pentaerythritol triacrylate (PETA) 12.48 g, C165 (solid silica nanoparticles with an average diameter of 12 nni and pentaerythritol triacrylate in a 1: 1 weight ratio product) 49.90 g, Synthesis Example 2 4.80 g of high molecular weight copolymer, 2.69 g of TP0 (Ciba photocuring initiator), 0.13 g of T270 (Tego leveling agent), 20 g of ethyl methyl ketone (MEX) as a solvent, and methyl isobutyl ketone (MIBK)
  • Dipentaerythritol nucleoacrylate 4.12 g, C165 (average size) 12 nm hollow nanoparticles and pentaerythritol triacrylate in a 1: 1 weight ratio.
  • NanoResin 51.49 g, 6.18 g of the high molecular weight copolymer prepared in Synthesis Example 2, 3.09 g of TP0 (Initiator for Ciba photocuring), 0.12 g of T270 (Tego leveling agent), ethyl methyl ketone solvent (MEIO 23.33 g and methyl isobutyl ketone (MIBK) are mixed to form a coating solution for forming a second hard coat layer (B-
  • TMPTA trimethylolpropane triacrylate
  • hollow silica nanoparticles hollow silica nanoparticles (diameter range: about 42 nm to 66 nni, manufactured by JSC catalyst and chemicals) 283 g
  • solid silica nanoparticles solid silica nanoparticles (diameter range: about 12 nni) 19 nm) 59 g
  • 1st fluorine-containing compound X-71-1203M, ShinEtsu
  • 2nd fluorine-containing compound RS-537, DIC) 15.5g
  • initiator Irgacure 127, Ciba
  • MIBK A coating solution (C) for forming a low reflection layer was prepared by diluting the solvent to (methyl isobutyl ketone) to a solid content concentration of 3% by weight.
  • PETA pentaerythritol triacrylate
  • reactant of toluene diisocyanate and penta erythritol triacrylate as urethane acrylate U-306T, Kyoeisha
  • Coating solution for forming a first hard coat layer prepared in Preparation Example 1 on a polyethylene terephthalate film having a thickness of 250 II and 3000 ä retardation (coating the city with # 85 and drying at 80 ° (: 2 minutes, It hardened
  • the lamp was used for 0 ⁇ ⁇ , and the curing reaction was carried out under nitrogen atmosphere.
  • the amount of light irradiated during curing is 10001111/0111 2 .
  • the coating thickness was 71.
  • [IV curing of the second hard coating was a zero ratio lamp, which was cured under a nitrogen atmosphere. The amount of light irradiated upon curing is 1801111/011 2 . The thickness of the second hard coat layer was measured with a thickness gauge, and the coating thickness was 45.
  • the coating liquid for forming a low reflection layer prepared in Preparation Example 4 (0 to # 10 It was coated so as to have a thickness of about 100 ⁇ , dried for 1 minute in a 90 oven, and cured to form a low reflection layer. At the time of the curing, the coating dried under nitrogen purge was irradiated with ultraviolet light of 252 /.
  • Quarter wave plates were laminated to one side of the polyvinyl alcohol polarizer using a ⁇ curable adhesive and then bonded. On the other side of the polyvinyl alcohol polarizer to which the quarter wave plate film was not bonded, the surface of the first hard coat layer of the laminate was bonded with a curable adhesive. At this time, polyvinyl alcohol 2019/172651 1 »(: 1 ⁇ 1 ⁇ 2019/002606
  • a laminate was prepared in the same manner as in Example 1, except that the thickness of the first hard coat layer was 75, and the thickness of the second hard coat layer was 42 11.
  • the stain resistant layer prepared in Preparation Example 5 It was coated to a thickness of about 3 ⁇ 17)-, dried for 2 minutes in a 90 oven, and cured to form a fouling resistant layer. At the time of curing, the dried coating was irradiated with ultraviolet rays of 252111 ⁇ 1/01 / under nitrogen purge.
  • a polarizing plate was manufactured in the same manner as in Example 1 except that the angle formed between the absorption axis of the polyvinyl alcohol polarizer and the slow axis of the polyethylene terephthalate film was controlled to 50 ° .
  • Example 3
  • a second hard coat layer is formed by using the second hard coat layer forming coating liquid ⁇ -2) instead of the second hard coating layer forming coating liquid ⁇ -1), the thickness of the first hard coating layer is controlled to 100, and the second hard coating layer is formed.
  • a laminate was produced in the same manner as in Example 1, except that the thickness of was controlled to 70.
  • a fouling resistant layer was formed on the second hard coat layer in the same manner as in the fouling resistant layer forming method of Example 2.
  • a polarizing plate was manufactured in the same manner as in Example 1, except that the angle formed between the absorption axis of the polyvinyl alcohol polarizer and the slow axis of the polyethylene terephthalate film was controlled at 50 ° .
  • Example 4
  • a laminate was manufactured in the same manner as in Example 1, except that the polyethylene terephthalate film had a thickness of 80 ⁇ 1 , the thickness of the first hard coat layer was 22 / thickness, and the thickness of the second hard coat layer was 21. did.
  • the stain resistant layer was formed on the second hard coat layer in the same manner as the stain resistant layer forming method of Example 2, except that the thickness of the stain resistant layer was 2.8 1.
  • Example 2 The same method as in Example 1, except that a triacetyl cellulose film having a thickness of 80 is used instead of the polyethylene terephthalate film, the thickness of the first hard coating layer is 24, and the thickness of the second hard coating layer is 21 /.
  • the laminate was manufactured. 2019/172651 1 »(: 1 ⁇ 1 ⁇ 2019/002606
  • a fouling resistant layer was formed on the second hard coat layer in the same manner as in the fouling resistant layer forming method of Example 2.
  • the polarizing plate was manufactured in the same manner as in Example 1, but the triacetyl cellulose film was a non-stretched film, so the distinction between the slow axis and the fast axis was ambiguous. Comparative Example 2
  • a laminate was manufactured in the same manner as in Example 1, except that the thickness of the first hard coat layer was 73 ⁇ and the thickness of the second hard coat layer was 42.
  • the stain resistant layer was formed on the second hard coat layer in the same manner as the stain resistant layer forming method of Example 2, except that the thickness of the stain resistant layer was 2.7 //.
  • a polarizing plate was manufactured in the same manner as in Example 1 except that the angle formed between the absorption axis of the polyvinyl alcohol polarizer and the slow axis of the polyethylene terephthalate film was controlled to 0 ° . Comparative Example 3
  • a laminate was prepared in the same manner as in Example 1, except that the first hard coat layer was not formed. 2019/172651 1 »(: 1 ⁇ 1 ⁇ 2019/002606
  • the stain resistant layer was formed on the second hard coat layer in the same manner as the stain resistant layer forming method of Example 2, except that the thickness of the stain resistant layer was 2.8 /.
  • a structure in which polarizers are not laminated that is, a laminate including (1) the first hard coat layer, the light-transmissive substrate, and the second hard coat layer, and (2) the stain resistant layer (or with respect to the low-hard coating film comprising a reflective layer), and then it scratched 5 times with a load angle, 45 ° for 1, 4.01, according to the measurement standard 1 (5400 using a pencil hardness tester to visually determine the maximum hardness without flaws It evaluated and the result was shown in following Table 1.
  • the polarizing plate was cut to a size of 4 cm X 4 cm, a black tape (Vinyl tape 472 Bl ack, manufactured by 3M) was attached to the second hard coating layer, and then a Shimadzu UV-VIS spectrometer (UV-VIS spectrometer, Model name: UV2550) was used to measure reflectance at 5 ° reflection mode, slit width 2nm, analysis wavelength range 380-780nm, and reflectance data between 450-650nni was derived.
  • a black tape Vinyl tape 472 Bl ack, manufactured by 3M
  • UV2550 Shimadzu UV-VIS spectrometer
  • ARb (maximum reflectance at 450 to 650 nm-minimum reflectance at 450 to 650 nm) ⁇ (reflection average at 450 to 650 nm) x 100
  • the stain resistant layer or the low reflection layer of the polarizing plates of Examples and Comparative Examples cut to the size of 10cm x 10cm face up, and pressed the middle part of the polarizing plate with a rod having a diameter of lcm or less so that the center part touches the bottom. At this time, the height of the four vertices was measured from the bottom surface, and then the average of the heights was calculated to obtain the warpage value. The warpage values thus obtained were expressed as positive numbers. If the film is bent in the direction of the first hard coating layer, the polarizing plate is inverted to bring the stain resistant layer or the low reflection layer to the bottom, and the warpage value is obtained by the same method, and the warpage value at this time is negatively expressed.
  • Examples 1 to 4 have excellent pencil hardness, no rainbow phenomenon, low rainbow fluctuation ratio and whip value was confirmed that the excellent optical and mechanical properties.
  • Comparative Example without using a light-transmitting substrate having a birefringence in plane
  • Comparative Example 1 shows low mechanical properties due to low pencil hardness
  • Comparative Example 2 having an angle of 0 ° formed by the slow axis of the light transmissive substrate and the absorption axis of the polarizer exhibits a rainbow phenomenon and a high rainbow fluctuation ratio, resulting in low optical characteristics.
  • Comparative Example 3 which does not include a hard coat layer, confirmed that the whip value was very high.

Abstract

The present invention relates to a polarizing plate and a display device, the polarizing plate comprising: a polarizer; a first hard coating layer positioned on the polarizer and containing a binder resin comprising (meth)acrylate-based (co)polymer; a light transmissive base material positioned on the first hard coating layer, having a retardation of 3,000 nm or more and having an in-plane birefringence; and a second hard coating layer positioned on the light transmissive base material and comprising a binder resin and solid inorganic nano particles dispersed in the binder resin, wherein the angle formed by a slow axis of the light transmissive base material and an absorption axis of the polarizer is 5 to 85 degrees.

Description

2019/172651 1»（：1^1{2019/002606  2019/172651 1 »（： 1 ^ 1 {2019/002606
【발명의 명칭】 [Name of invention]
편광판 및 이를 포함하는 화상 표시 장치  Polarizing plate and image display device including the same
【기술분야】  Technical Field
관련 출원（들）과의 상호 인용  Cross Citation with Related Application (s)
본 출원은 2018 년 3 월 6 일자 한국 특허 출원 제 10-2018-0026390 호 및 2019 년 3 월 6 일자 한국 특허 출원 제 10-2019-0025662 호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원들의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.  This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0026390 dated March 6, 2018 and Korean Patent Application No. 10-2019-0025662 dated March 6, 2019. All content disclosed in the literature is included as part of this specification.
본 발명은 화상 표시 장치를 구성하는 편광판 및 이를 포함하는 화상 표시 장치에 관한 것이다.  The present invention relates to a polarizing plate constituting an image display device and an image display device including the same.
【발명의 배경이 되는 기술】  [Technique to become background of invention]
최근 스마트폰, 태블릿 ᄄ 와 같은 모바일 기기의 발전과 함께 디스플레이용 기재의 박막화 및 슬림화가 요구되고 있다. 이러한 모바일 기기의 디스플레이용 원도우 또는 전면판의 소재로는, 강도 및 인장 등의 기계적 특성이 우수해 외부 충격에 대한 충격 흡수가 뛰어난 유리 또는 강화 유리가 일반적으로 사용되고 있다. 그러나, 유리는 반사율이 높아 디스플레이의 시인성이 저하되고, 유리 자체의 무게로 인해 모바일 장치가 고중량화되고, 외부 충격에 의한 파손의 문제가 있다.  Recently, with the development of mobile devices such as smartphones and tablets, there is a demand for thinning and slimming the substrate for display. As a material for the display window or the front plate of the mobile device, glass or tempered glass having excellent mechanical properties such as strength and tensile strength and excellent shock absorption against external shock is generally used. However, the glass has a high reflectance and thus lowers the visibility of the display, the weight of the glass itself increases the weight of the mobile device, and there is a problem of breakage due to external impact.
이에 유리를 대체할 수 있는 소재로 플라스틱 수지가 연구되고 있다. 플라스틱 수지 필름은 경량이면서도 깨질 우려가 적어 보다 가벼운 모바일 기기를 추구하는 추세에 적합하다. 특히, 고경도 및 내마모성의 특성을 갖는 필름을 달성하기 위해 지지 기재에 하드코팅층이 코팅된 필름이 제안되고 있다. 이러한 하드코팅층이 코팅된 지지 기재로는 디스플레이의 화상 표시면 측에 배치된 편광자를 보호하는 편광자 보호 필름을 이용하는 방법이 알려져 있다. 편광자 보호 필름은 일반적으로 광투과성 기재 필름으로 이루어져 있으며, 이러한 광투과성 기재 필름으로서는 트리아세틸 셀룰로오스
Figure imgf000002_0001
로 대표되는 셀룰로오스에스테르계 필름이 가장 널리 사용되고 있다. 이러한 셀룰로오스에스테르계 필름은 투명성 및 광학 등방성이 우수하고, 면 내에 위상차를 거의 나타내지 않아서 간섭 무늬를 발생시키지 않고， 표시 장치의 표시 품질에 악영향을 미치는 점이 거의 없는 등의 장점을 가지고 있다. 2019/172651 1»（：1^1{2019/002606 Therefore, plastic resin is being researched as a substitute material for glass. Plastic resin films are lightweight and less prone to break, making them suitable for the trend toward lighter mobile devices. In particular, in order to achieve a film having characteristics of high hardness and wear resistance, a film coated with a hard coat layer on a supporting substrate has been proposed. As a support base material coated with such a hard coating layer, a method using a polarizer protective film for protecting the polarizer disposed on the image display surface side of the display is known. The polarizer protective film generally consists of a light transmissive base film, and the light transmissive base film is triacetyl cellulose.
Figure imgf000002_0001
Cellulose ester-based film represented by the most widely used. Such a cellulose ester-based film has advantages such as excellent transparency and optical isotropy, little retardation in the plane, no interference fringe, and almost no adverse effect on the display quality of the display device. 2019/172651 1 »（： 1 ^ 1 {2019/002606
그러나, 상기 셀룰로오스에스테르계 필름은 비용적으로 불리한 점이 있는 소재일 뿐 아니라， 투습도가 높고 내수성이 열악한 단점이 있다. 이러한 높은 투습도와 열악한 내수성으로 인해, 사용 중에 계속적으로 상당량의 수분 투과가 발생하여 편광자로부터 들뜸 현상이 발생할 수 있으며， 이 때문에 빛샘 현상을 야기할 수 있다. However, the cellulose ester-based film is not only a material having a disadvantage in terms of cost, but also has disadvantages of high moisture permeability and poor water resistance. Due to this high moisture permeability and poor water resistance, a considerable amount of water permeation can occur continuously during use, causing the phenomenon of lifting from the polarizer, which can cause light leakage.
이러한 셀룰로오스에스테르계 필름의 단점으로 인해, 최근에는 상기 편광자 보호 필름의 기재 필름으로 폴리에틸렌테레프탈레이트계 묘 필름 등 폴리에스테르계 필름을 대체 적용하려는 시도가 이루어지고 있다. 이러한 폴리에스테르계 필름은 저가이며, 내수성이 우수하여 빛샘 현상을 유발할 가능성이 거의 없고, 기계적 물성이 뛰어난 장점이 있다.  Due to the shortcomings of the cellulose ester-based film, an attempt has recently been made to replace a polyester-based film such as polyethylene terephthalate seedling film as a base film of the polarizer protective film. Such a polyester-based film is inexpensive, has excellent water resistance, hardly causes light leakage, and has excellent mechanical properties.
그러나, 이러한 폴리에스테르계 필름은 구조 중에 높은 굴절율을 갖는 방향족 고리를 포함하며， 필름 제막 과정에서 ¾©/10 방향의 연신율 차이 등으로 인한 굴절율 차이（면내 복굴절） 및 면내 위상차를 발생시키는 단점이 있다. 그 결과, 상기 폴리에스테르계 필름을 편광자 보호 필름의 기재 필름으로 적용할 경우, 빛의 투과/반사에 의해 레인보우 현상이 발생하여 화상 표시 장치의 시인성이 저하되는 문제점이 발생하게 된다.  However, such a polyester-based film includes an aromatic ring having a high refractive index in the structure, and has a disadvantage of generating a refractive index difference (in-plane birefringence) and an in-plane retardation caused by a difference in elongation in the ¾ © / 10 direction during the film forming process. . As a result, when the polyester-based film is applied as the base film of the polarizer protective film, a rainbow phenomenon occurs due to the transmission / reflection of light, thereby causing a problem that the visibility of the image display device is lowered.
【발명의 내용】  [Content of invention]
【해결하고자 하는 과제】  Problem to be solved
본 발명은 폴리에스테르계 기재 필름에서 유래하는 레인보우 현상의 발생을 효과적으로 억제하고， 시인성 및 기계적 물성이 우수하여 화상 표시 장치의 윈도우 또는 전면판에 적절하게 적용될 수 있는 편광판 및 이를 포함하는 화상표시 장치를 제공하기 위한 것이다.  The present invention effectively suppresses the occurrence of the rainbow phenomenon derived from the polyester-based substrate film, excellent visibility and mechanical properties of the polarizing plate that can be appropriately applied to the window or front plate of the image display device and an image display device comprising the same It is to provide.
【과제의 해결 수단】  [Measures of problem]
본 발명의 일 구현예에 따르면， 편광자;  According to an embodiment of the present invention, a polarizer;
상기 편광자 상에 위치하고, （메트）아크릴레이트계 （공）중합체를 포함하는 바인더 수지를 함유하는 제 1 하드코팅층 ;  A first hard coat layer on the polarizer and containing a binder resin containing a (meth) acrylate-based (co) polymer;
상기 제 1 하드코팅층 상에 위치하고， 3000^1 이상의 리타데이션犯 3 3 011）을 가지고, 면 내에 복굴절률을 갖는 광투과성 기재; 및 상기 광투과성 기재 상에 위치하고， 바인더 수지; 및 상기 바인더 수지에 분산된 솔리드형 무기 나노 입자;를 포함하는 제 2 하드코팅층을 포함하고, 상기 광투과성 기재의 지상축과, 상기 편광자의 흡수축이 이루는 각도가 5 내지 85° 인, 편광판이 제공될 수 있다. A light-transmitting substrate on the first hard coating layer, having a retardation # 3 3 011) of 3000 ^ 1 or more, and having a birefringence in plane; And a binder resin positioned on the light transmissive substrate; And a second hard coat layer including; and solid inorganic nanoparticles dispersed in the binder resin. A polarizing plate having an angle between the slow axis of the light transmissive substrate and the absorption axis of the polarizer may be 5 to 85 ° .
본 발명의 다른 구현예에 따르면, 상기 편광판을 포함하는 화상 표시 장치가 제공될 수 있다.  According to another embodiment of the present invention, an image display device including the polarizing plate may be provided.
이하, 발명의 구체적인 구현예에 따른 편광판 및 화상 표시 장치에 관하여 보다상세하게 설명하기로 한다.  Hereinafter, a polarizing plate and an image display device according to specific embodiments of the present invention will be described in detail.
본 발명에서， 제 1 , 제 2 등의 용어는 다양한 구성요소들을 설명하는데 사용되며， 상기 용어들은 하나의 구성 요소를 다른 구성 요소로부터 구별하는 목적으로만 사용된다.  In the present invention, terms such as first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from other components.
또한， (메트)아크릴 [ (meth)acryl ]은 아크릴 (acryl ) 및 메타크릴 (methacryl ) 양쪽 모두를 포함하는 의미이다.  In addition, (meth) acryl [(meth) acryl] is meant to include both acryl and methacryl.
또한, 중공 구조의 무기 나노입자라 함은 무기 나노입자의 표면 및/또는 내부에 빈 공간이 존재하는 형태의 입자를 의미한다.  In addition, the inorganic nanoparticles of the hollow structure refers to particles having a form in which an empty space exists on the surface and / or inside of the inorganic nanoparticles.
또한, (공)중합체는 공중합체 (co-polymer ) 및 단독 중합체 (homo- polymer ) 양쪽 모두를 포함하는 의미이다. 본 발명자들은， 지지 기재로 면 내에 복굴절률을 가지는 광투과성 기재를 사용하고, 상기 면 내에 복굴절률을 가지는 광투과성 기재에 있어서 굴절률이 가장 큰 방향인 지상축과, 상기 편광자의 흡수축이 이루는 예각의 각도가 5 내지 85° ， 10 내지 80° , 20 내지 80° , 20 내지 70 , 30 내지 70° , 35 내지 65° 또는 35 내지 50° 가 되도록, 상기 편광자에 대한 상기 광투과성 기재의 배열 방향을 제어함으로써 편광판의 레인보우 현상이 억제되고 휘도가 높아져 시인성이 향상되고, 강도 등의 기계적 특성이 향상된다는 점을 실험을 통해서 확인하고 발명을 완성하였다. In addition, a (co) polymer is meant to include both copolymers and homopolymers. The present inventors use a light-transmissive substrate having a birefringence in-plane as a supporting substrate, and in the light-transmissive substrate having a birefringence in the plane, an acute angle formed between a slow axis having the largest refractive index and an absorption axis of the polarizer is formed. Arrangement direction of the light transmissive substrate with respect to the polarizer such that the angle of 5 to 85 ° , 10 to 80 ° , 20 to 80 ° , 20 to 70, 30 to 70 ° , 35 to 65 ° or 35 to 50 ° The experiment confirmed that the rainbow phenomenon of the polarizing plate is suppressed, the luminance is increased, the visibility is improved, and the mechanical properties such as the strength are improved by controlling through the experiment.
또한, 이와 함께 상기 면 내에 복굴절률을 가지는 광투과성 기재의 리타데이션을 3 , 000nm 이상, 4 ,000 내지 10 ,000nm , 또는 5,000 내지 8 ,000nm 으로 제어함으로서 상쇄 간섭으로 인한 레인보우 현상이 억제되고, 셀룰로오스에스테르계 필름에 준하게 화상 표시 장치의 시인성을 향상시킬 수 있음이 확인되었다.  In addition, by controlling the retardation of the light-transmitting substrate having a birefringence in the plane to at least 3, 000nm, 4,000 to 10,000nm, or 5,000 to 8,000nm, the rainbow phenomenon due to destructive interference is suppressed, It was confirmed that the visibility of the image display device can be improved based on the cellulose ester-based film.
만일， 상기 광투과성 기재의 지상축과 편광자의 흡수축이 이루는 2019/172651 1»（：1^1{2019/002606 If the slow axis of the light transmissive substrate and the absorption axis of the polarizer 2019/172651 1 »（： 1 ^ 1 {2019/002606
각도와, 상기 광투과성 기재의 리타데이션 중 하나라도 적절한 범위로 제어되지 못하는 경우， 기계적 특성이 저하되고, 광투과성 기재의 복굴절성으로 인해 레인보우 현상이 발생하고 화상 표시 장치의 시인성이 저하될 수 있다. If any of the angle and the retardation of the light transmissive substrate is not controlled to an appropriate range, the mechanical properties may be deteriorated, the rainbow phenomenon may occur due to the birefringence of the light transmissive substrate, and the visibility of the image display apparatus may be degraded. .
또한, 상기 광투과성 기재의 양면에 각각 제 1 및 제 2 하드코팅층을 형성한 적층체를 편광자의 일면에 접합함에 따라, 외부 환경에 취약한 편광자를 보호할 수 있는 동시에, 편광판 전체의 기계적 물성을 향상시킬 수 있음이 확인되었다. 따라서, 편광자와 상기 편광자 상에 형성된 적층체를 포함하는 편광판은， 시인성 및 기계적 물성이 모두 우수함으로 인해 화상 표지 장치의 윈도우 또는 전면판에 적절하게 적용될 수 있다. 이하, 일 구현예의 편광판을 각 요소별로 구체적으로 설명하기로 한다. 상기 일 구현예의 편광판은 편광자를 포함한다. 상기 편광자는 당해 기술분야에 잘 알려진 편광자， 예를 들면 요오드 또는 이색성 염료를 포함하는 폴리비닐알콜（1 /0로 이루어진 필름을 사용할 수 있다. 이때, 상기 편광자는 폴리비닐알코올 필름에 요오드 또는 이색성 염료를 염착시키고 연신하여 제조될 수 있으나, 이의 제조방법은 특별히 한정되지 않는다.  In addition, by bonding the laminates having the first and second hard coating layers respectively formed on both surfaces of the light transmissive substrate to one surface of the polarizer, polarizers that are vulnerable to the external environment can be protected and mechanical properties of the entire polarizing plate are improved. It was confirmed that it can be made. Therefore, the polarizing plate including the polarizer and the laminate formed on the polarizer can be suitably applied to the window or the front plate of the image labeling device because of excellent visibility and mechanical properties. Hereinafter, the polarizing plate of one embodiment will be described in detail for each element. The polarizing plate of the embodiment includes a polarizer. The polarizer may be a film made of polyvinyl alcohol (1/1) including a polarizer well known in the art, for example, iodine or a dichroic dye. In this case, the polarizer may be prepared by dyeing and stretching an iodine or a dichroic dye on a polyvinyl alcohol film, but a method of manufacturing the same is not particularly limited.
한편 , 상기 편광자가 폴리비닐알코올 필름인 경우, 폴리비닐알코올 필름은 폴리비닐알코올 수지 또는 그 유도체를 포함하는 것이면 특별한 제한 없이 사용이 가능하다. 이때 , 상기 폴리비닐알코올 수지의 유도체로는， 이에 한정되는 것은 아니나, 폴리비닐포르말 수지, 폴리비닐아세탈 수지 등을 들 수 있다. 또는, 상기 폴리비닐알코올 필름은 당해 기술분야에 있어서 편광자 제조에 일반적으로 사용되는 시판되는 폴리비닐알코올 필름, 예를 들어, 구라레 사의 ?30 , ?£30, ?£60 , 일본합성사의 3000 , ¾6000 등을 사용할 수 있다. ' Meanwhile, when the polarizer is a polyvinyl alcohol film, the polyvinyl alcohol film may be used without particular limitation as long as it includes a polyvinyl alcohol resin or a derivative thereof. In this case, examples of the derivative of the polyvinyl alcohol resin include, but are not limited to, polyvinyl formal resin, polyvinyl acetal resin, and the like. Alternatively, the polyvinyl alcohol film is a commercially available polyvinyl alcohol film generally used in the manufacture of polarizers in the art, for example,? 30,? £ 30,? £ 60 by Gurere, 3000, ¾6000 etc. can be used. '
한편， 상기 폴리비닐알코올 필름은, 이로써 한정되는 것은 아니나, 중합도가 1000 내지 10000 또는 1500 내지 5000 일 수 있다. 중합도가 상기 범위를 만족할 때， 분자 움직임이 자유롭고, 요오드 또는 이색성 염료 등과 유연하게 혼합될 수 있다. 또한, 상기 편광자가두께는 30쎈 1 이하, 20 이하， 1 내지 20 /께， 또는 1 내지 10 ，일 수 있다. 이 경우, 상기 편광자를 포함하는 편광판이나 화상 표시 장치 등의 디바이스의 박형 경량화가 가능하다. 상기 일 구현예에 따른 편광판은， 상기 편광자의 일면에 제 1 하드코팅층， 면 내에 복굴절률을 가지는 광투과성 기재， 및 제 2 하드코팅층이 순차적으로 적층된 적층체가 접합될 수 있다. 이때， 상기 광투과성 기재로는 내수성이 우수하여 빛샘 현상을 유발할 가능성이 거의 없고， 기계적 물성이 우수한 폴리에틸렌 테레프탈레이트 (PET) 필름을 사용할 수 있다. 또한, 상기 광투과성 기재의 양면에 제 1 및 제 2 하드코팅층이 각각 형성됨으로 인해 유리 소재를 대체할 수 있는 기계적 물성을 갖게 되고, 이로 인해, 상기 적층체가 형성된 편광판은 화상 표시 장치의 윈도우 또는 전면판에 적절하게 적용될 수 있다. On the other hand, the polyvinyl alcohol film is not limited thereto, but the polymerization degree may be 1000 to 10000 or 1500 to 5000. When the degree of polymerization satisfies the above range, the molecular motion is free and can be mixed flexibly with iodine or dichroic dye. In addition, the polarizer may have a thickness of 30 m 1 or less, 20 m or less, 1 to 20 / mm, or 1 to 10 m. In this case, the polarizer Thin weight reduction of devices, such as a polarizing plate and an image display apparatus, is included. In the polarizing plate according to the embodiment, the first hard coating layer on one surface of the polarizer, a light transmissive substrate having a birefringence in the surface, and a laminate in which the second hard coating layer is sequentially laminated may be bonded. In this case, as the light transmissive substrate, there is little possibility of causing light leakage due to excellent water resistance, and a polyethylene terephthalate (PET) film having excellent mechanical properties may be used. In addition, since the first and second hard coating layers are formed on both sides of the light transmissive substrate, respectively, mechanical properties capable of replacing a glass material are provided. Accordingly, the polarizing plate on which the laminate is formed may be a window or front surface of the image display device. Applicable to the edition as appropriate.
한편, 상기 제 1 하드코팅층과 대향하는 편광자의 다른 일면에 쿼터웨이브 플레이트 (Quar t er Wave P l at e )가 접합될 수 있다. 상기 쿼터웨이브 플레이트는 빛의 편광방향을 45° 변화시키는 파장판 (WaveA quarter wave plate may be bonded to the other surface of the polarizer facing the first hard coating layer. The quarterwave plate has a wave plate that changes the polarization direction of light by 45 °.
P l at e)으로, 선편광인 입사편광을 원편광으로 바꾸는 역할을 할 수 있다. 예를 들어， 선편광과 광축과의 각도가 45° 인 경우 출사편광은 우원편광 ( r i ght handed c i rcu l ar po l ar i zat i on)이 될 수 있다. P l at e), the incident polarization, which is linearly polarized light, may be converted into circularly polarized light. For example, when the angle between the linearly polarized light and the optical axis is 45 ° , the outgoing polarization may be right circularly polarized light (ri ght handed ci rcu l ar po i ar i za t i on).
상기 편광자의 양면에 각각 상기 쿼터웨이브 플레이트 및 적층체를 위치시키고, 상기 편광자의 흡수축과 상기 광투성 기재의 지상축이 이루는 각도가 5 내지 85° 로 제어함으로 인해 , 본 발명의 일 실시예에 따른 편광판의 레인보우 현상이 억제되고 휘도가 높아져 시인성이 향상될 수 있다. Positioning the quarter wave plate and the laminate on each side of the polarizer, and the angle between the absorption axis of the polarizer and the slow axis of the light transmissive substrate is controlled to 5 to 85 ° , in an embodiment of the present invention The rainbow phenomenon of the polarizing plate is suppressed and the luminance is increased, so that visibility can be improved.
상기 편광자의 일면에 상기 제 1 하드코팅층을 포함하는 적층체를 접합하고, 다른 일면에 쿼터웨이브 플레이트를 접합하는 방법은， 예를 들어, 롤 코터, 그라비어 코터， 바 코터, 나이프 코터 또는 캐필러리 코터 등을 사용하여 편광자, 제 1 하드코팅층 또는 쿼터웨이브 플레이트 표면에 접착제를 코팅한 후 , 이들을 합지 롤로 가열 합지하거나， 상온 압착하여 합지하는 방법 또는 합지 후 UV 조사하는 방법 등에 의해 수행될 수 있다. 한편, 상기 접착제로는 당해 기술 분야에서 사용되는 다양한 편광판용 접착제들, 예를 들면, 폴리비닐알코올계 접착제， 폴리우레탄계 접착제, 아크릴계 접착제， 양이온계 또는 라디칼계 접착제 등이 제한 없이 사용될 수 있다.  A method of bonding a laminate including the first hard coating layer to one surface of the polarizer and a quarter wave plate to the other surface may include, for example, a roll coater, a gravure coater, a bar coater, a knife coater, or a capillary. After coating the adhesive on the surface of the polarizer, the first hard coating layer or the quarter wave plate using a coater or the like, they may be carried out by heating or laminating them with a lamination roll, or laminating by pressing at room temperature, or laminating or UV irradiation. Meanwhile, as the adhesive, various polarizing plate adhesives used in the art, for example, polyvinyl alcohol-based adhesives, polyurethane-based adhesives, acrylic adhesives, cationic or radical-based adhesives, and the like may be used without limitation.
상기 일 구현예의 편광판은, 상기 편광자 및 면 내에 복굴절률을 2019/172651 1»（：1^1{2019/002606 The polarizing plate of the embodiment, the birefringence in the plane and the polarizer 2019/172651 1 »（： 1 ^ 1 {2019/002606
가지는 광투과성 기재 사이에 위치하는 제 1 하드코팅층을 포함한다. The branch includes a first hard coat layer located between the light transmissive substrates.
상기 제 1 하드코팅증은 （메트）아크릴레이트계 （공）중합체를 포함하는 바인더 수지를 포함할 수 있다.  The first hard coating certificate may include a binder resin including a (meth) acrylate-based (co) polymer.
또한, 상기 바인더 수지에 함유된 （메트）아크릴레이트계 （공）중합체는, 단관능 혹은 다관능 （메트）아크릴레이트계 반복단위 및 우레탄 Moreover, the (meth) acrylate type (co) polymer contained in the said binder resin is a monofunctional or polyfunctional (meth) acrylate type repeating unit, and a urethane.
（메트）아크릴레이트계 반복단위를 포함하여, 제 1 하드코팅층에 고경도, 유연성 및 내충격성을 부여할 수 있다. Including a (meth) acrylate type repeating unit, high hardness, flexibility, and impact resistance can be imparted to the first hard coat layer.
상기 단관능 혹은 다관능 （메트）아크릴레이트계 반복단위는 단관능 혹은 다관능 （메트）아크릴레이트계 화합물로부터 유래한 것이고, 상기 우레탄 （메트）아크릴레이트계 반복단위는 우레탄 （메트）아크릴레이트계 화합물로부터 유래한 것이다. 따라서， 상기 （메트）아크릴레이트계 （공）중합체는, 상기 단관능 혹은 다관능 （메트）아크릴레이트계 화합물 및 우레탄 The monofunctional or polyfunctional (meth) acrylate-based repeating unit is derived from a monofunctional or polyfunctional (meth) acrylate-based compound, and the urethane (meth) acrylate-based repeating unit is a urethane (meth) acrylate-based It is derived from a compound. Therefore, the said (meth) acrylate type (co) polymer is the said monofunctional or polyfunctional (meth) acrylate type compound, and urethane.
（메트）아크릴레이트계 화합물이 가교 중합되어 형성될 수 있다. The (meth) acrylate compound may be formed by crosslinking polymerization.
상기 단관능 혹은 다관능 （메트）아크릴레이트계 화합물은 자외선, 적외선, 묘 근 , 열에 의해 가교반응이 진행되어 도막을 경화시킬 수 있는 （메타）아크릴레이트 구조가 분자 내에 1 개 이상 포함한 화합물인 것으로, 예를 들어, 테트라하이드로퍼퓨릴 아크릴레이트, 하이드록시 에틸 아크릴레이트, 하이드록시 프로필 아크릴레이투, 하이드록시 부틸 아크릴레이트， 트리메틸올프로판 트리아크릴레이트 1미70 , 트리메틸올프로판에톡시 트리아크릴레이트（1 ¾끄70 , 글리세린 프로폭실화 트리아크릴레이트 ½ /0 , 펜타에리트리톨
Figure imgf000007_0001
또는 디펜타에리트리톨 핵사아크릴레이트（ ） 등 일 수 있다. The monofunctional or polyfunctional (meth) acrylate-based compound is a compound containing at least one (meth) acrylate structure in the molecule capable of curing the coating film by the cross-linking reaction proceeds by ultraviolet rays, infrared rays, seedlings and heat. For example, tetrahydrofurfuryl acrylate, hydroxy ethyl acrylate, hydroxy propyl acrylate, hydroxy butyl acrylate, trimethylolpropane triacrylate 1mi70, trimethylolpropaneethoxy triacrylate ( 1 ¾ off 70, glycerin propoxylated triacrylate ½ / 0, pentaerythritol
Figure imgf000007_0001
Or dipentaerythritol nucliacrylate () or the like.
한편, 상기 우레탄 （메트）아크릴레이트계 화합물은 우레탄 결합을 매개로 （메트）아크릴레이트계 화합물이 결합된 것으로， 모노머 형태 혹은 올리고머 형태일 수 있다. 상기 우레탄 （메타）아크릴레이트계 모노머 혹은 올리고머의 평균 분자량은 500 내지 200 , 000， 700 내지 150 , 000 , 1 , 000 내지 120 , 000 , 또는 2 , 000 내지 100 , 000일 수 있다.  On the other hand, the urethane (meth) acrylate compound is a (meth) acrylate compound is bonded through a urethane bond, may be in the form of a monomer or oligomer. The average molecular weight of the urethane (meth) acrylate monomer or oligomer may be 500 to 200, 000, 700 to 150, 000, 1, 000 to 120, 000, or 2,000 to 100, 000.
상기 일 구현예에 따른 편광판은, 상기 제 1 하드코팅층 상에 위치하는 면 내에 복굴절률을 가지는 광투과성 기재를 포함한다. 앞서 언급한 바와 같이, 상기 광투과성 기재는， 리타데이션
Figure imgf000007_0002
이 3 , 00011111 이상, 4 , 000 내지 2019/172651 1»（：1^1{2019/002606 The polarizing plate according to the embodiment includes a light transmissive substrate having a birefringence in the plane located on the first hard coat layer. As mentioned above, the light transmissive substrate is a retardation
Figure imgf000007_0002
More than 3, 00011111, from 4, 000 2019/172651 1 »（： 1 ^ 1 {2019/002606
10 , 00011111 , 또는 5 , 000 내지 8 , 000· 이고， 광투과성 기재의 지상축과 편광자의 흡수축이 이루는 예각의 각도가 5 내지 85° 가 되도록, 상기 제 1 하드코팅층 상에 배열함으로 인해 레인보우 현상이 나타나지 않으면서 시인성이 우수한 효과 및 기계적 물성이 우수한 효과를 나타낼 수 있다. 10, 00011111, or 5, 000 to 8, 000 ·, the rainbow by arranging on the first hard coating layer so that the acute angle between the slow axis of the light transmissive substrate and the absorption axis of the polarizer is 5 to 85 ° It is possible to exhibit the effect of excellent visibility and excellent mechanical properties without the phenomenon.
상기 리타데이션은 광투과성 기재의 면 내에서 가장 굴절률이 큰 방향인 지상축 방향의 굴절률 (¾) , 상기 지상축 방향과 직교하는 방향인 진상축 방향의 굴절률 ( )， 및 상기 광투과성 기재의 두께 (1 (단위: 11111)1- , 하기 수학식 1에 대입하여 계산한 것일 수 있다.  The retardation is a refractive index in the slow axis direction (¾), which is the direction of the largest refractive index in the plane of the light transmissive substrate, a refractive index in the fast axis direction (), which is orthogonal to the slow axis direction, and the thickness of the light transmissive substrate. (1 (unit: 11111) 1-may be calculated by substituting into Equation 1 below).
[수학식 1]
Figure imgf000008_0001
[Equation 1]
Figure imgf000008_0001
측정각: 0° , 측정파장: 548.21페)를 이용하여 측정된 값일 수 있다. 또는, 상기 리타데이션은 다음 방법에서도 구할 수 있다. 우선 2 매의 편광판을 이용하여 상기 광투과성 기재의 배향축 방향으로 구비하고, 배향축 방향에 대해서 직교하는 두 개의 축 굴절률 (¾， %)을 쇼애6 식 굴절률계어能-4 에 의해 구한다. 이때， 보다 큰 굴절률을 나타내는 축을 지상축으로 정의한다. 또한， 상기 광투과성 기재의 두께를 예를 들어 전기 마이크로 미터를 이용하여 측정하고, 앞서 얻은 굴절률을 이용해 굴절률
Figure imgf000008_0002
스11 라 한다)를 산출하고， 이 굴절률 차이 스11 와 광투과상 기재의 두께 (1(ä)와의 곱에 의해 리타데이션을 구할 수 있다. Measurement angle: 0 ° , measurement wavelength: 548.21). Alternatively, the retardation can also be obtained by the following method. First, two axial refractive indices (¾,%) which are provided in the alignment axis direction of the light-transmitting substrate using two polarizing plates and orthogonal to the orientation axis direction are obtained by Shore 6 Refractive Index Function-4. At this time, the axis showing a larger refractive index is defined as the slow axis. In addition, the thickness of the light transmissive substrate is measured using an electric micrometer, for example, and the refractive index using the refractive index obtained above
Figure imgf000008_0002
Calculation is referred to as bus 11) and can be determined by the product between the thickness of the retardation (1 (ä) of the refractive index difference between switch 11 and the light-transmitting substrate.
상기 광투과성 가재의 리타데이션이 3000 11111 이상이므로， 굴절률 차이 (스 , 즉， 지상축 방향의 굴절률 (¾)과, 상기 지상축 방향과 직교하는 방향인 진상축 방향의 굴절률 (%)의 차 (ᅀ 11 = ¾-%)는 0.05 이상, 0.05 내지 0.20， 또는 0.08 내지 0. 13 일 수 있다. 상기 굴절률 차이 (스11)가 0.05 미만이면 상술한 리타데이션 값을 얻기 위해 필요한 상기 광투과성 기재의 두께가 두꺼워질 수 있다. 한편, 굴절률 차이스11 가 0.20 을 초과하면， 연신 배율을 과도하게 높일 필요가 발생하므로, 상기 광투과성 기재가 찢어지고 파괴되기 쉬어 공업 재료로서의 실용성이 현저하게 저하될 수 있고， 내습열성이 저하될 수 있다.  Since the retardation of the light-transmitting crawfish is 3000 11111 or more, the difference between the refractive index difference (s, i.e., the refractive index (¾) in the slow axis direction and the refractive index (%) in the fast axis direction which is a direction orthogonal to the slow axis direction) ᅀ 11 = ¾-%) may be 0.05 or more, 0.05 to 0.20, or 0.08 to 0.3. When the refractive index difference (s11) is less than 0.05, the light transmissive substrate required to obtain the retardation value described above is On the other hand, if the refractive index difference 11 exceeds 0.20, it is necessary to excessively increase the draw ratio, so that the light-transmissive substrate is likely to be torn and broken, which may significantly reduce the practicality as an industrial material. And damp-heat resistance may be lowered.
상기 광투과성 기재의 지상축 방향에서의 굴절률 (¾)은 1.60 내지 2019/172651 1»（：1^1{2019/002606 The refractive index (¾) in the slow axis direction of the light transmissive substrate is 1.60 to 2019/172651 1 »（： 1 ^ 1 {2019/002606
1 .80 또는 1 .65 내지 1 .75 일 수 있다. 한편, 상기 면 내에 복굴절률을 가지는 광투과성 기재의 진상축 방향에서의 굴절률（%）은 1.50 내지 1 .70 , 또는 1 .55 내지 1 .65일 수 있다. 1.80 or 1.65 to 1.75. Meanwhile, the refractive index (%) in the fast axis direction of the light transmissive substrate having the birefringence in the plane may be 1.50 to 1.70, or 1.55 to 1.65.
상기 면 내에 복굴절률을 가지는 광투과성 기재의 두께는 이로써 제한되는 것은 아니지만, 10 내지 500 / /III , 30 내지 400 ，， 또는 50 내지 350 / 일 수 있다. 상기 광투과성 기재의 두께가 10 /께 미만이면 하드코팅층의 두께보다 지나치게 얇아 휨이 발생하고， 광투과성 기재의 유연성이 떨어져 공정을 제어하기 어려울 수 있으며， 500 초과하면 광투과성 기재의 투과율이 감소하여 광학 물성이 하락할 수 있으며, 이를 포함하는 화상 표시 장치를 박막화하기 어렵다는 문제점이 있다.  The thickness of the light transmissive substrate having the birefringence in the plane is not limited thereto, but may be 10 to 500 // III, 30 to 400, or 50 to 350 /. When the thickness of the light transmissive substrate is less than 10 / thickness, the thickness of the hard coating layer is too thin, so that warpage may occur, and the flexibility of the light transmissive substrate may be difficult to control the process. When the thickness is greater than 500, the transmittance of the light transmissive substrate is reduced. Optical properties may decrease, and it is difficult to thin an image display device including the same.
한편， 상기 광투과성 기재로는 내수성이 우수하여 빛샘 현상을 유발할 가능성이 거의 없고， 기계적 물성이 뛰어난 폴리에틸렌 테레프탈레이트 묘 필름을 사용할 수 있다.  On the other hand, the light-transmitting base material is excellent in water resistance and hardly cause a light leakage phenomenon, it is possible to use a polyethylene terephthalate seed film excellent mechanical properties.
상기 일 구현예의 편광판은 상기 면 내에 복굴절률을 가지는 광투과성 기재 상에 위치하는 제 2 하드코팅층을 포함한다. 상기 제 2 하드코팅층은 바인더 수지; 및 상기 바인더 수지에 분산된 솔리드형 무기 나노 입자를 포함하여 , 제 2 하드코팅층에 고경도, 유연성 및 내충격성을 부여할 수 있다. 상기 제 2 하드코팅층의 바인더 수지는, 광경화성 수지 및 중량평균분자량이 10 , 00½/|1101 이상인 （공）중합체（이하， 고분자량 （공）중합체라 함）를 포함할 수 있다.  The polarizing plate of the embodiment includes a second hard coat layer positioned on the light transmissive substrate having a birefringence in the plane. The second hard coat layer is a binder resin; And solid-type inorganic nanoparticles dispersed in the binder resin, to impart high hardness, flexibility, and impact resistance to the second hard coating layer. The binder resin of the second hard coat layer may include a photocurable resin and a (co) polymer (hereinafter, referred to as a high molecular weight (co) polymer) having a weight average molecular weight of 10, 00½ / | 1101 or more.
상기 광경화성 수지는 자외선 등의 광이 조사되면 중합 반응을 일으킬 수 있는 광중합성 화합물의 중합체로서, 예를 들어， 우레탄 아크릴레이트 올리고머, 에폭사이드 아크릴레이트 올리고머, 폴리에스테르 아크릴레이트 및 폴리에테르 아크릴레이트로 이루어진 반응성 아크릴레이트 올리고머 군; 및 디펜타에리스리톨 핵사아크릴레이트, 디펜타에리스리톨 펜타아크릴레이트， 펜타에리스리톨 테트라아크릴레이트， 펜타에리스리톨 트리아크릴레이트， 트리메틸올프로판 트리아크릴레이트， 글리세린 프로폭시레이트 트리아크릴레이트， 트리메틸프로판 에톡시레이트 트리아크릴레이트 , 트리메틸프로필 트리아키를레이트 , 1 , 6 -핵산디올 디아크릴레이트, 트리프로필렌글리콜 디아크릴레이트 및 에틸렌글리콜 디아크릴레이트로 2019/172651 1»（：1^1{2019/002606 The photocurable resin is a polymer of a photopolymerizable compound which can cause a polymerization reaction when light such as ultraviolet rays is irradiated, such as urethane acrylate oligomer, epoxide acrylate oligomer, polyester acrylate and polyether acrylate. Reactive acrylate oligomer group; And dipentaerythritol nuxaacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, glycerin propoxylate triacrylate, trimethylpropane ethoxylate triacrylate With trimethylpropyl triarylate, 1,6-nucleic acid diol diacrylate, tripropylene glycol diacrylate and ethylene glycol diacrylate 2019/172651 1 »（： 1 ^ 1 {2019/002606
이루어진 다관능성 아크릴레이트 단량체로 이루어진 군에서 선택되는 1 종 이상이 사용될 수 있다. One or more kinds selected from the group consisting of polyfunctional acrylate monomers made may be used.
상기 고분자량 （공）중합체는 , 예를 들어 , 셀룰로오스계 들리머， 아크릴계 폴리머, 스티렌계 폴리머， 에폭사이드계 폴리머, 나일론계 폴리머, 우레탄계 폴리머 및 폴리올레핀계 폴리머로 이루어진 군에서 선택되는 1 종 이상의 폴리머를 포함할 수 있다 .  The high molecular weight (co) polymer is, for example, at least one polymer selected from the group consisting of cellulose depolymers, acrylic polymers, styrene polymers, epoxide polymers, nylon polymers, urethane polymers and polyolefin polymers. It may include.
상기 제 2 하드코팅층의 바인더 수지에 분산된 솔리드형 무기 나노 입자는 100 11111미만의 최대 직경을 가지며 그 내부에 빈 공간이 존재하지 않는 형태의 입자를 의미한다. 상기 솔리드형 무기 나노 입자는 0.5 내지 100 , 또는 1 내지 30 |ᅵ미 의 직경을 가질 수 있다. 또한， 상기 솔리드형 무기 나노 입자는 2.00요/ 내지 5.0½/01섹 밀도를 가질 수 있다.  Solid-type inorganic nanoparticles dispersed in the binder resin of the second hard coating layer refers to particles having a maximum diameter of less than 100 11111 and no empty space therein. The solid inorganic nanoparticles may have a diameter of 0.5 to 100, or 1 to 30 | | US. In addition, the solid inorganic nanoparticles may have a density of 2.00 yaw / to 5.0½ / 01 sec.
상기 솔리드형 무기 나노 입자는 표면에 （메트）아크릴레이트기， 에폭사이드기, 비닐기（ 1） 및 싸이올기（¾比1）로 이루어진 군에서 선택된 1 종 이상의 반응성 작용기를 함유할 수 있다. 상기 솔리드형 무기 나노 입자 표면에 상술한 반응성 작용기를 함유함에 따라서， 보다높은 가교도를 가질 수 있어 제 2하드코팅층에 고경도， 유연성 및 내충격성을 부여할수 있다.  The solid inorganic nanoparticles may contain at least one reactive functional group selected from the group consisting of a (meth) acrylate group, an epoxide group, a vinyl group (1) and a thiol group (¾ ratio1) on the surface. By containing the reactive functional group on the surface of the solid inorganic nanoparticles, it can have a higher degree of crosslinking can impart high hardness, flexibility and impact resistance to the second hard coating layer.
상기 제 1하드코팅층 및 제 2 하드코팅층의 두께비는 1:0.5 내지 1:1.5, 1:0.6 내지 1.4, 또는 1:0.8 내지 1.3 일 수 있다. 상기 제 1 하드코팅층과 제 2 하드코팅층의 두께비가 1:0.5 미만이거나 1:1.5 초과하면, 필름의 휩이 발생하여 편평한 필름 형태를 유지하기 어렵고 광학필름으로 활용할 수 없게 된다.  The thickness ratio of the first hard coat layer and the second hard coat layer may be 1: 0.5 to 1: 1.5, 1: 0.6 to 1.4, or 1: 0.8 to 1.3. When the thickness ratio of the first hard coat layer and the second hard coat layer is less than 1: 0.5 or more than 1: 1.5, the whip of the film is generated and it is difficult to maintain a flat film form and cannot be used as an optical film.
상기 광투과성 기재 및 제 2 하드코팅층의 두께비는 1:0.1 내지 1:1, 1:0.2 내지 0.9, 또는 1:0.3 내지 0.8 일 수 있다. 상기 광투과성 기재 및 제 2 하드코팅층은 두께비가 1:0.1 미만이면 필름의 경도와 내스크래치성이 낮아져 외부 충격으로부터 편광판을 보호할 수 없으며 , 1:1 초과하면 필름의 경도가 지나치게 높아져 편광자와의 접합공정과 제 1 하드코팅층 코탕 공정 시 필름이 휘어지지 않고 부러질 수 있다.  The thickness ratio of the light transmissive substrate and the second hard coat layer may be 1: 0.1 to 1: 1, 1: 0.2 to 0.9, or 1: 0.3 to 0.8. When the light transmissive substrate and the second hard coating layer have a thickness ratio of less than 1: 0.1, the hardness and scratch resistance of the film may be lowered to protect the polarizing plate from external impact. In the bonding process and the first hard coating layer cotang process, the film may be broken without bending.
상기 광투과성 기재의 양면에 각각 제 1 하드코팅층 및 제 2 하드코팅층을 형성하는 방법은, 예를 들어， 상기 광투과성 기재의 앙면에 각각 제 1 및 제 2 하드코팅층 형성용 조성물을 롤 코터, 그라비어 코터, 바 코터, 2019/172651 1»（：1^1{2019/002606 In the method for forming the first hard coating layer and the second hard coating layer on both surfaces of the light transmissive substrate, for example, the composition for forming the first and second hard coating layers on the face of the light transmissive substrate, respectively, roll coater, gravure Coater, Bar Coater, 2019/172651 1 »（： 1 ^ 1 {2019/002606
나이프 코터 또는 캐필러리 코터 등의 방법으로 코팅하고, 용매를 휘발시킨 후 열/광경화하여 상기 제 1 및 제 2 하드코팅층을 포함하는 적층체를 제조할 수 있다. Coating by a method such as a knife coater or capillary coater, the solvent may be volatilized, and then heat / photocured to prepare a laminate including the first and second hard coat layers.
이후， 상기 편광자 또는 적층체에 롤 코터, 그라비어 코터, 바 코터, 나이프 코터 또는 캐필러리 코터 등을 사용하여 접착제를 코팅한 후 , 이들을 합지 롤로 가열 합지하거나 , 상온 압착하여 합지하는 방법 또는 합지 후 조사하는 방법 등에 의해 수행될 수 있다. 한편， 상기 접착제로는 당해 기술 분야에서 사용되는 다양한 편광판용 접착제들， 예를 들면 , 폴리비닐알코올계 접착제, 폴리우레탄계 접착제， 아크릴계 접착제， 양이온계 또는 라디칼계 접착제 등이 제한 없이 사용될 수 있다.  Thereafter, the polarizer or the laminate is coated with an adhesive using a roll coater, a gravure coater, a bar coater, a knife coater or a capillary coater, and then laminating them with a lamination roll, or laminating by pressing at room temperature or laminating. It may be carried out by a method such as irradiation. On the other hand, as the adhesive, various polarizing plate adhesives used in the art, for example, polyvinyl alcohol-based adhesives, polyurethane-based adhesives, acrylic adhesives, cationic or radical-based adhesives and the like can be used without limitation.
또는， 편광자에 제 1 하드코팅층 형성용 조성물을 코팅 및 열/광경화하여 제 1 하드코팅층을 형성하고, 상기 제 1 하드코팅층에 대향하도록 상기 편광자의 다른 일면에 위치하는 쿼터웨이브 플레이트를 접합하고， 상기 제 1 하드코팅층 상에 상기 광투과성 기재를 접합한 이후, 상기 광투과성 기재 상에 제 2 하드코팅층 형성용 조성물을 코팅 및 열/광경화하여 제 2 하드코팅층을 형성하는 방법으로, 상기 편광판을 제조할 수 있다.  Or coating and heat / photocuring a composition for forming a first hard coat layer on the polarizer to form a first hard coat layer, and bonding a quarterwave plate positioned on the other side of the polarizer so as to face the first hard coat layer, After bonding the light transmissive substrate on the first hard coat layer, by coating and heat / photocuring the composition for forming a second hard coat layer on the light transmissive substrate to form a second hard coat layer, the polarizing plate It can manufacture.
상기 일 구현예의 편광판은, 상기 제 2 하드코팅층 상에 위치하는 저반사층을 더 포함할 수 있다. 이러한 저반사층은 바인더 수지; 및 상기 바인더 수지에 분산된 무기 나노 입자를 포함할 수 있다. 이때, 상기 무기 나노 입자는 중공형 무기 나노 입자， 솔리드형 무기 나노 입자, 또는 이들의 혼합물일 수 있다.  The polarizing plate of the embodiment may further include a low reflection layer positioned on the second hard coating layer. Such a low reflection layer is a binder resin; And inorganic nanoparticles dispersed in the binder resin. In this case, the inorganic nanoparticles may be hollow inorganic nanoparticles, solid inorganic nanoparticles, or a mixture thereof.
상기 바인더 수지는 다관능 （메트）아크릴레이트계 반복단위를 포함하는 （공）중합체를 포함하고, 이러한 반복단위는 예를 들어, 트리메틸올프로페인 트리아크릴레이
Figure imgf000011_0002
트리메틸올프로판에톡시 트리아크릴레이
Figure imgf000011_0001
The binder resin includes a (co) polymer containing a polyfunctional (meth) acrylate-based repeating unit, and the repeating unit is, for example, trimethylolpropane triacrylamide
Figure imgf000011_0002
Trimethylolpropaneethoxy triacrylic
Figure imgf000011_0001
글리세린 프로폭실화 트리아크릴레이트 ½肝/\）， 펜타에리트리톨 테트라아크릴레이트 肝시 , 또는 디펜타에리트리톨 핵사아크릴레이트（卵 ） 등의 다관능 （메트）아크릴레이트계 화합물로부터 유래한 것일 수 있다. It may be derived from a polyfunctional (meth) acrylate-based compound such as glycerin propoxylated triacrylate ½ 肝 / \), pentaerythritol tetraacrylate oxy, or dipentaerythritol nuxaacrylate (卵). .
상기 저반사층은 광반응성 작용기를 갖는 함불소 화합물 및/또는 광반응성 작용기를 갖는 실리콘계 화합물을 더 포함할 수 있다. 상기 함불소 2019/172651 1»（：1^1{2019/002606 The low reflection layer may further include a fluorine-containing compound having a photoreactive functional group and / or a silicon-based compound having a photoreactive functional group. Fluorine-containing 2019/172651 1 »（： 1 ^ 1 {2019/002606
화합물 또는 실리콘계 화합물에 포함되는 광반응성 작용기는 （메트）아크릴레이트기， 에폭사이드기, 비닐기（ 1 1） 및 싸이올기（1^ 01）로 이루어진 군에서 선택된 1종 이상의 작용기를 포함할 수 있다. The photoreactive functional group contained in the compound or silicone compound may include one or more functional groups selected from the group consisting of (meth) acrylate groups, epoxide groups, vinyl groups (1 1) and thiol groups (1 ^ 01). .
상기 광반응성 작용기를 포함한 함불소 화합물은 1） 하나 이상의 광반응성 작용기가 치환되고, 적어도 하나의 탄소에 1 이상의 불소가 치환된 지방족 화합물 또는 지방족 고리 화합물; ） 1 이상의 광반응성 작용기로 치환되고， 적어도 하나의 수소가 불소로 치환되고, 하나 이상의 탄소가 규소로 치환된 헤테로 근 ） 지방족 화합물 또는 헤테로（11 리-0）지방족 고리 화합물; 1 1 1） 하나 이상의 광반응성 작용기가 치환되고, 적어도 하나의 실리콘에 1 이상의 불소가 치환된 폴리디알킬실록산계 고분자; 및 ᅵ\0 1 이상의 광반응성 작용기로 치환되고 적어도 하나의 수소가 불소로 치환된 폴리에테르 화합물;로 이루어진 군에서 선택된 1종 이상의 화합물일 수 있다. 상기 중공형 무기 나노 입자는 200 ᅵä 미만의 최대 직경을 가지며 그 표면 및/또는 내부에 빈 공간이 존재하는 형태의 입자를 의미한다. 상기 중공형 무기 나노 입자는 1 내지 200 11111 , 또는 10 내지 100 11111 의 수평균 입경을 갖는 솔리드형 무기 미세 입자로 이루어진 군에서 선택된 1 종 이상을 포함할 수 있다. 또한， 상기 중공형 무기 나노 입자는 1 .5始/0111 내지 3.50§/（ 의 밀도를 가질 수 있다. The fluorine-containing compound including the photoreactive functional group may include 1) an aliphatic compound or an aliphatic ring compound in which one or more photoreactive functional groups are substituted and at least one fluorine is substituted for at least one carbon; ) A hetero near aliphatic compound substituted with one or more photoreactive functional groups, at least one hydrogen substituted with fluorine, and one or more carbons substituted with silicon; or a hetero (11 li-0) aliphatic ring compound; 1 1 1) polydialkylsiloxane polymers in which at least one photoreactive functional group is substituted and at least one fluorine is substituted in at least one silicon; And a polyether compound substituted with at least one photoreactive functional group and at least one hydrogen is replaced with fluorine. The hollow inorganic nanoparticles refer to particles having a maximum diameter of less than 200 L and have a void space on the surface and / or inside thereof. The hollow inorganic nanoparticles may include one or more selected from the group consisting of solid inorganic fine particles having a number average particle diameter of 1 to 200 11111, or 10 to 100 11111. In addition, the hollow inorganic nanoparticles may have a density of 1.5 始 / 011 1 to 3.50 § / （.
상기 중공형 무기 나노 입자는 표면에 （메트）아크릴레이트기, 에폭사이드기， 비닐기（ 1） 및 싸이올기（¾比1）로 이루어진 군에서 선택된 1 종 이상의 반응성 작용기를 함유할 수 있다. 상기 중공형 무기 나노 입자 표면에 상술한 반응성 작용기를 함유함에 따라서, 보다 높은 가교도를 가질 수 있다、  The hollow inorganic nanoparticles may contain at least one reactive functional group selected from the group consisting of a (meth) acrylate group, an epoxide group, a vinyl group (1), and a thiol group (¾ ratio1) on the surface. By containing the reactive functional group described above on the surface of the hollow inorganic nanoparticles, it may have a higher degree of crosslinking,
상기 솔리드형 무기 나노입자는 0.5 내지 100· 의 수평균 입경을 갖는 솔리드형 무기 미세 입자로 이루어진 군에서 선택된 1 종 이상을 포함할 수 있다.  The solid inorganic nanoparticles may include at least one member selected from the group consisting of solid inorganic fine particles having a number average particle diameter of 0.5 to 100 ·.
상기 저반사층은 상가 （공）중합체 100 중량부 대비 상기 무기 나노 입자 10 내지 400 중량부; 및 상기 광반응성 작용기를 포함한 함불소 화합물 및/또는 실리콘계 화합물 20 내지 300중량부를 포함할 수 있다.  The low reflection layer is 10 to 400 parts by weight of the inorganic nanoparticles relative to 100 parts by weight of an additive (co) polymer; And 20 to 300 parts by weight of a fluorine-containing compound and / or a silicon-based compound including the photoreactive functional group.
상기 편광판은 이러한 저반사층을 포함함에 따라， 상기 제 1 2019/172651 1»（：1^1{2019/002606 As the polarizer includes such a low reflection layer, the first 2019/172651 1 »（： 1 ^ 1 {2019/002606
하드코팅층 상에 위치하는 광투과성 기재에서의 반사자체가줄어들 수 있으며, 그 결과 일 구현예의 편광판에서 레인보우 현상의 발생을 효과적으로 억제할 수 있다. 또한， 상기 저반사층을 포함한 화상 표시 장치의 표시면에서의 난반사를 줄여 해상도 및 시인성을 보다 향상시킬 수 있다. The reflection itself in the transparent substrate positioned on the hard coating layer can be reduced, and as a result, it is possible to effectively suppress the occurrence of the rainbow phenomenon in the polarizing plate of one embodiment. In addition, it is possible to further improve the resolution and visibility by reducing the diffuse reflection on the display surface of the image display device including the low reflection layer.
이러한 저반사층은 상기 면 내에 복굴절률을 가지는 광투과성 기재에서의 반사나, 화상 표시 장치의 표시면에서의 난반사 등을 효과적으로 억제하기 위해, 예를 들어, 1.3 내지 1.5， 1.35 내지 1.45 , 혹은 1.38 내지 1.43의 굴절율을 가지며 , 1 내지 300ä , 5 내지 200ä , 혹은 50 내지 150ä의 두께를 가질 수 있다.  Such a low reflection layer is, for example, 1.3 to 1.5, 1.35 to 1.45, or 1.38 to 1, in order to effectively suppress reflection on a light transmissive substrate having a birefringence in the surface, or diffuse reflection on a display surface of an image display device. It has a refractive index of 1.43 and may have a thickness of 1 to 300ä, 5 to 200ä, or 50 to 150ä.
상기 일 구현예의 편광판은 상기 제 2 하드코팅층 상에 위치하는 내오염층을 더 포함할 수 있다. 상기 내오염층은 바인더 수지; 상기 바인더 수지에 분산된 솔리드형 무기 나노 입자; 및 불소계 화합물을포함할 수 있다. 상기 내오염층의 바인더 수지는 （메트）아크릴레이트계 반복단위를 함유한 공중합체를 포함할 수 있다. 상기 （메트）아크릴레이트계 반복단위는 예를 들어, 트리메틸올프로판 트리아크릴레이
Figure imgf000013_0001
The polarizing plate of the embodiment may further include a fouling resistant layer positioned on the second hard coating layer. The stain resistant layer is a binder resin; Solid inorganic nanoparticles dispersed in the binder resin; And fluorine-based compounds. The binder resin of the fouling resistant layer may include a copolymer containing a (meth) acrylate-based repeating unit. The (meth) acrylate-based repeating unit is, for example, trimethylolpropane triacrylamide
Figure imgf000013_0001
트리메틸올프로판에톡시 트리아크릴레이
Figure imgf000013_0002
글리세린 프로폭실화 트리아크릴레이트 ½的70 , 펜타에리트리톨 트리아크릴레이트 附/\） , 또는 디펜타에리트리톨 핵사아크릴레이트（ ） 등의 다관능 （메트）아크릴레이트계 화합물로부터 유래한 것일 수 있다. 상기 내오염층의 바인더 수지는 솔리드형 무기 나노 입자와 혼합해서 사용시 적절한 분산성과 가교도를 유지하기 위해 2종 이상혼합하여 사용할 수 있다. Trimethylolpropaneethoxy triacrylic
Figure imgf000013_0002
It may be derived from polyfunctional (meth) acrylate-based compounds such as glycerin propoxylated triacrylate ½-70, pentaerythritol triacrylate 附 / \), or dipentaerythritol nuxaacrylate (). The binder resin of the fouling resistant layer may be used by mixing two or more kinds in order to maintain appropriate dispersibility and crosslinking degree when mixed with solid inorganic nanoparticles.
상기 솔리드형 무기 나노 입자는 0.5 내지 100 11미 , 또는 1 내지 30 1ä 의 직경을 가질 수 있다. 또한, 상기 솔리드형 무기 나노 입자는 2.00§/0111 내지 크 / 의 밀도를 가질 수 있다. 또한， 상기 솔리드형 무기 나노 입자는 표면에 （메트）아크릴레이트기, 에폭사이드기, 비닐기（ 1） 및 싸이올기（1^01）로 이루어진 군에서 선택된 1 종 이상의 반응성 작용기를 함유할 수 있다. 상기 솔리드형 무기 나노 입자 표면에 상술한 반응성 작용기를 함유함에 따라서， 보다 높은 가교도를 가질 수 있으며, 이에 따라 보다 향상된 방오성을 확보할 수 있다. The solid inorganic nanoparticles may have a diameter of 0.5 to 100 11 microns, or 1 to 30 1ä. In addition, the solid inorganic nanoparticles may have a density of 2.00 § / 011 1 to kr /. In addition, the solid inorganic nanoparticles may contain at least one reactive functional group selected from the group consisting of (meth) acrylate groups, epoxide groups, vinyl groups (1) and thiol groups (1 ^ 01) on the surface. . By including the reactive functional group described above on the surface of the solid inorganic nanoparticles, it may have a higher degree of crosslinking, thereby ensuring more improved antifouling properties.
상기 불소계 화합물은 화합물 중 적어도 1 개 이상의 불소 원소가 2019/172651 1»（：1^1{2019/002606 The fluorine-based compound is at least one fluorine element of the compound 2019/172651 1 »（： 1 ^ 1 {2019/002606
포함된 화합물을 의미하는 것으로, 상기 내오염층에는 불소계 화합물이 포함되거나， 상기 불소계 화합물 간의 가교 （공）중합체를 포함할 수 있다. Meaning the included compound, the fouling resistant layer may include a fluorine-based compound, or may include a crosslinked (co) polymer between the fluorine-based compounds.
상기 불소계 화합물은 2 , 000 내지 200 , 000 , 또는 5 , 000 내지 100 , 000의 중량평균분자량
Figure imgf000014_0001
의해 측정한 폴리스티렌 환산의 중량 평균 분자량）을 가질 수 있다. 상기 불소계 화합물의 중량평균분자량이 2 , 000 미만이면 불소계 화합물들이 균일하고 효과적으로 배열하지 못하여 내오염층의 방오성이 저하될 수 있고, 200 , 000초과하면 다른 성분들과의 상용성이 낮아질 수 있다. The fluorine-based compound has a weight average molecular weight of 2,000, 200, 000, or 5, 000 to 100, 000
Figure imgf000014_0001
The weight average molecular weight of polystyrene conversion measured by ") can be used. When the weight average molecular weight of the fluorine-based compound is less than 2,000, the fluorine-based compounds may not be uniformly and effectively arranged, and the stain resistance of the fouling-resistant layer may be lowered, and when it exceeds 200, 000, compatibility with other components may be lowered.
상기 편광판은， 상기 편광자에 대향하도록 상기 쿼터웨이브 플레이트의 다른 일면에 형성된 점착층을 더 포함할 수 있다. 상기 쿼터웨이브 플레이트의 일면에는 편광자가 위치하며, 상기 편광자가 쿼터웨이브 플레이트의 일면의 반대면에는 상기 점착층이 위치할 수 있다.  The polarizing plate may further include an adhesive layer formed on the other surface of the quarterwave plate to face the polarizer. The polarizer may be positioned on one surface of the quarterwave plate, and the adhesive layer may be positioned on the opposite surface of the quarter wave plate of the polarizer.
상기 점착층은 상기 일 구현예의 편광판과 화상 표시 장치의 화상 패널의 부착이 가능하게 할 수 있다. 상기 점착층은 당해 기술 분야에 잘 알려져 있는 다양한 점착제들을 사용하여 형성될 수 있으며, 그 종류가 특별히 제한되는 것은 아니다. 예를 들면, 상기 점착층은 고무계 점착제, 아크릴계 점착제, 실리콘계 점착제, 우레탄계 점착제, 폴리비닐알코올계 점착제, 폴리비닐피롤리돈계 점착제 , 폴리아크릴아미드계 점착제， 셀룰로오스계 점착제， 비닐알킬에테르계 점착제 등을 이용하여 형성될 수 있다.  The adhesive layer may enable attachment of the polarizing plate of the embodiment and the image panel of the image display device. The adhesive layer may be formed using various adhesives well known in the art, and the kind thereof is not particularly limited. For example, the pressure-sensitive adhesive layer may be a rubber pressure sensitive adhesive, an acrylic pressure sensitive adhesive, a silicone pressure sensitive adhesive, a urethane pressure sensitive adhesive, a polyvinyl alcohol pressure sensitive adhesive, a polyvinylpyrrolidone pressure sensitive adhesive, a polyacrylamide pressure sensitive adhesive, a cellulose pressure sensitive adhesive, a vinyl alkyl ether pressure sensitive adhesive, or the like. It can be formed using.
상기 점착층은 쿼터웨이브 플레이트의 상부에 점착제를 도포하는 방법으로 형성될 수도 있고, 이형 시트 상에 점착제를 도포한 후 건조시켜 제조되는 점착 시트를 쿼터웨이브 플레이트 상부에 부착하는 방법으로 형성될 수도 있다.  The pressure-sensitive adhesive layer may be formed by applying a pressure-sensitive adhesive on the upper portion of the quarter wave plate, or may be formed by attaching a pressure-sensitive adhesive sheet prepared by applying an adhesive on a release sheet and then drying the pressure-sensitive adhesive sheet on the upper portion of the quarter wave plate. .
상기 일 구현예에 따른 편광판의 편광자의 일면에는, 면 내에 복굴절률을 가지는 광투과성 기재와 상기 광투과성 기재의 양면에 형성된 제 1 및 제 2 하드코팅층을 포함하는 적층체가 접합되어 있음으로써, 경도 등의 기계적 물성이 매우 우수한 장점이 있다. 구체적으로, 상기 편광판은 500§ 하중에서 연필 경도가抑 이상, 개 내지 9 또는에 내지 애일 수 있습니다. 또한， 상기 편광판에서 편광자를 제외한 구조， 즉， 상기 제 1 하드코팅층, 광투과성 기재 및 제 2 하드모팅층을 포함하는
Figure imgf000014_0002
On one surface of the polarizer of the polarizing plate according to the embodiment, the laminate including the light-transmitting substrate having a birefringence in the surface and the first and second hard coating layers formed on both sides of the light-transmissive substrate is bonded, hardness, etc. Its mechanical properties are very good. Specifically, the polarizer may have a pencil hardness greater than or equal to, 9 to 9, or even at 500 § load. The polarizing plate may include a structure excluding the polarizer, that is, the first hard coating layer, the light transmissive substrate, and the second hard motor layer.
Figure imgf000014_0002
하중에서 연필 경도가抑 이상， 개 내지 애, 또는예 내지 애일 수 있습니다. 나아가, 상기 적층체 , 및 상기 적층체 상에 형성된 저반사층 (또는 내오염층)을 포함하는 반사 방지 필름은， lkg 하중에서 연필 경도가 抑 이상, 7H 내지 9H， 또는 8H 내지 9H일 수 있습니다. The pencil hardness under load may be greater than or equal to, or less than, or less than. Further, it may be a laminate, and the laminate of the low reflection layer formed on (or stain layer) over the anti-reflection film has a pencil hardness抑from lkg load, including, 7H to 9H, or 8H to 9H.
한편, 상기 편광판에 포함된 면 내에 복굴절률을 가지는 광투과성 기재는, 상기 광투과성 기재의 지상축과 상기 편광자의 흡수축이 이루는 예각의 각도가 5 내지 85° 가 되도록 배열됨으로 인해， 레인보우 현상이 억제되는 장점이 있다.  On the other hand, the light transmissive substrate having a birefringence in the plane included in the polarizing plate, since the acute angle between the slow axis of the light transmissive substrate and the absorption axis of the polarizer is arranged to be 5 to 85 °, the rainbow phenomenon is There is an advantage that is suppressed.
상기 편광판의 레인보우 현상을 정량적으로 측정하기 위해， 먼저， 편광판의 반사율을 측정하고， 측정된 반사율 데이터로부터 반사율의 평균 및 최대반사율과 최소반사율의 차이를 계산한 후, 이를 하기 수학식 1 에 대입하여 레인보우의 변동비를 정략적으로 확인할 수 있다.  In order to quantitatively measure the rainbow phenomenon of the polarizing plate, first, the reflectance of the polarizing plate is measured, and the difference between the average reflectance and the maximum reflectance and the minimum reflectance is measured from the measured reflectance data, and then substituted into the following Equation 1 The rainbow variable ratio can be checked regularly.
구체적으로, 편광판의 반사율 측정은 Shimadzu 사의 UV-VIS 분광기 (UV- VIS spect rometer , 모델명: UV2550)를 사용하고, 5° 반사 모드, 슬릿 폭 (s i i t width) 2imi, 및 분석 파장 범위 380 내지 780nni 의 조건에서 반사율을 측정하고, 450 내지 650nm 사이에서의 반사율 데이터를 도출한 후, 450 내지 650iim 에서의 반사율 평균 및 최대반사율과 최소반사율의 차이를 계산하고, 이를 하기 수학식 1 에 대입하여 레인보우의 변동비 ( A Rb)를 계산할 수 있다 . 이때, 상기 레인보우 변동비는 10% 이하, 또는 1%내지 10%일 수 있다. Specifically, the reflectance measurement of the polarizing plate using Shimadzu's UV-VIS spectrometer (UV-VIS spectrometer, model name: UV2550), 5 ° reflection mode, the slit width (siit width) 2imi, and the analysis wavelength range of 380 to 780 nni After measuring the reflectance under the conditions, and extracting the reflectance data between 450 and 650 nm, the difference between the reflectance average and the maximum reflectance and the minimum reflectance at 450 to 650iim was calculated and substituted into the following Equation 1 for the variation ratio of the rainbow: (A Rb) can be calculated. In this case, the rainbow variable ratio may be 10% or less, or 1% to 10%.
[수학식 1]  [Equation 1]
ARb= (450 내지 650nm 에서의 최대반사율 - 450 내지 650nm 에서의 최소 반사율) ÷ (450내지 650nm에서의 반사율 평균) x 100  ARb = (maximum reflectance at 450 to 650 nm-minimum reflectance at 450 to 650 nm) ÷ (reflection average at 450 to 650 nm) x 100
본 발명의 다른 구현예에 따르면, 상기 편광판을 포함하는 화상 표시 장치를 제공한다. 구체적으로， 상기 화상 표시 장치는 표시 패널; 및 상기 표시 패널의 적어도 일면에 위치하는 상기 편광판을 포함할 수 있다.  According to another embodiment of the present invention, an image display device including the polarizing plate is provided. Specifically, the image display device includes a display panel; And the polarizing plate disposed on at least one surface of the display panel.
상기 표시 패널은 액정 패널, 플라즈마 패널 및 유기발광 패널일 수 있으며, 이에 따라, 상기 화상 표시 장치는 액정 표시 장치 (LCD) , 플라즈마 표시 장치 ) 및 유기전계발광 표시 장치 (0LED)일 수 있다.  The display panel may be a liquid crystal panel, a plasma panel, and an organic light emitting panel. Accordingly, the image display device may be a liquid crystal display (LCD), a plasma display device) and an organic light emitting display device (0LED).
보다 구체적으로， 상기 화상 표시 장치는 액정 패널 및 상기 액정 패널의 양면에 각각 구비된 광한 적층체를 포함하는 액정 표시 장치일 수 있으며, 이때, 상기 편광판 중 적어도 하나가 전술한 본 명세서의 일 실시상태에 따른 편광자를 포함하는 편광판일 수 있다. 이때, 상기 액정 표시 장치에 포함되는 액정 패널의 종류는 특별히 한정되지 않으나， 예를 들면, TN(twi sted nematic)형， STN( super twisted nematic)형， F(ferroelectic)형 또는 PD( polymer dispersed)형과 같은 수동 행렬 방식의 패널; 2 단자형 (two terminal ) 또는 3 단자형 (three terminal)과 같은 능동행렬 방식의 패널 ; 횡전계형 (IPS; In Plane Switching) 패널 및 수직배향형 (VA; Vertical Alignment) 패널 등의 공지의 패널이 모두 적용될 수 있다. More specifically, the image display device may be a liquid crystal display device including a liquid crystal panel and a light laminated body provided on both surfaces of the liquid crystal panel, wherein at least one of the polarizing plates described above It may be a polarizing plate including a polarizer according to the embodiment. At this time, the type of liquid crystal panel included in the liquid crystal display device is not particularly limited, but, for example, TN (twi sted nematic) type, STN (super twisted nematic) type, F (ferroelectic) type or PD (polymer dispersed) Passive matrix panels such as type; Active matrix panels such as two terminal or three terminal; All known panels, such as an In Plane Switching (IPS) panel and a Vertical Alignment (VA) panel, can be applied.
【발명의 효과】  【Effects of the Invention】
본 발명에 따르면, 폴리에스테르계 기재 필름을 포함하면서도, 레인보우 현상이 나타나지 않고, 시인성 및 기계적 물성이 우수함에 따라, 화상 표시 장치의 윈도우 또는 전면판에 바람직하게 적용될 수 있는 편광판 및 이를 포함하는 화상 표시 장치가 제공될 수 있다.  According to the present invention, the polarizing plate and the image display including the same, which can be preferably applied to the window or the front plate of the image display device while including a polyester-based film, but the rainbow phenomenon does not appear, and excellent visibility and mechanical properties An apparatus may be provided.
【발명을 실시하기 위한 구체적인 내용】  [Specific contents to carry out invention]
발명을 하기의 실시예에서 보다 상세하게 설명한다. 단, 하기의 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기의 실시예에 의하여 한정되는 것은 아니다. 합성예 1: 폴리변성 우레탄아크릴레이트합성  The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples. Synthesis Example 1 Polymodified Urethane Acrylate Synthesis
3관능 이상의 다가 이소시아네이트계 화합물로서 HDI계 트라이머인 애경화학의 DN980S를 사용하고, 폴리에틸렌글리콜 변성 (메트)아크릴레이트계 화합물로서， 서로 다른 반복수의 폴리에틸렌글리콜 반복 단위를 포함하여 서로 다른 수 평균 분자량을 갖는 폴리에틸렌글리콜 모노 아크릴레이트 (Mn=300)와， 폴리에틸렌글리콜 모노 아크릴레이트 (Mn=500)를 각각 사용하였다.  As the trifunctional or higher polyhydric isocyanate compound, Aekyung Chemical's DN980S, which is an HDI-based trimer, is used as a polyethylene glycol-modified (meth) acrylate compound, and includes different repeating numbers of polyethylene glycol repeating units with different number average molecular weights. Polyethylene glycol mono acrylate (Mn = 300) and polyethylene glycol mono acrylate (Mn = 500) were used, respectively.
상기 다가 이소시아네이트계 화합물 40g, 폴리에틸렌글리콜 모노 아크릴레이트 (Mn=300) 30g, 폴리에틸렌글리콜 모노 아크릴레이트 (Mn=500) The polyhydric isocyanate compound 40g, polyethylene glycol mono acrylate (Mn = 300) 30g, polyethylene glycol mono acrylate (Mn = 500)
30g을 DBTDL(Di butyl tin di laurate) 0. lg 및 메틸 에틸 케톤 (methyl ethyl ketone) 200g과 함께 혼합하고, 60°C에서 약 5 시간 동안 교반하여 우레탄 반응을 진행하였다. 이러한 우레탄 반응의 종료에 의해, 폴리에틸렌글리콜 변성 다관능 우레탄 (메트)아크릴레이트계 바인더를 제조하였다. 30 g of DBTDL (Di butyl tin dilaurate) 0. lg and methyl ethyl ketone (200 mg) were mixed with 200 g, and stirred at 60 ° C. for about 5 hours to proceed the urethane reaction. By the end of this urethane reaction, the polyethyleneglycol modified polyfunctional urethane (meth) acrylate type binder was manufactured.
상기 우레탄 반응의 진행 여부 및 바인더의 생성은 FT-IR을 통하여 확인하였다. FT-IR 분석 시 약 2268.5cm_1의 위치에서 나타나는 이소시아네이트기 (-NCO) 유래 피크가 우레탄 반응 전후 사라지는 것을 통해 상기 우레탄 반응의 진행 여부 및 바인더의 생성을 확인했다. 합성예 2： 고분자량공중합체 합성 The progress of the urethane reaction and the production of the binder through the FT-IR Confirmed. The peak of the isocyanate group (-NCO) appearing at the position of about 2268.5 cm _1 in the FT-IR analysis disappeared before and after the urethane reaction, and it was confirmed whether the urethane reaction proceeded and the formation of the binder. Synthesis Example 2 Synthesis of High Molecular Weight Copolymer
폴리메틸메타크릴레이트 (PMMA) 및 폴리부틸아크릴레이트 (PBA)를 Polymethylmethacrylate (PMMA) and polybutylacrylate (PBA)
RAFT 중합 (Reversible addition fragment chain transfer polymerization) 반응하여 고분자량 공중합체 (PMMA-PBA 블록 공중합체)를 제조하였다. 이때， PMMA와 PBA의 부피비는 약 1:1이고, 수평균 분자량은 약 30,000g/mol이었다. 또한, PMMA-PBA 블록 공중합체의 자기 조립에 의해 형성된 마이쉘 구조의 평균입경은 약 15nm이었다. 제조예 1： 제 1하드코팅층 형성용 코팅액 (A) 제조 A high molecular weight copolymer (PMMA-PBA block copolymer) was prepared by RAFT polymerization (Reversible addition fragment chain transfer polymerization). At this time, the volume ratio of PMMA and PBA was about 1: 1, and the number average molecular weight was about 30,000 g / mol. In addition, the average particle diameter of the micelle structure formed by self-assembly of PMMA-PBA block copolymer was about 15 nm. Preparation Example 1 Preparation of Coating Liquid (A) for Forming First Hard Coating Layer
트리메틸프로필 트리아크릴레이트 (TMPTA) 38.74g, 상기 합성예 1 에서 제조한 폴리변성 우레탄 아크릴레이트 30.99g, 상기 합성예 2 에서 제조한 고분자량 공중합체 7.75g, TPCKCiba사 광경화용 개시제) 2.31g, T270(Tego 사 레벨링제 ) 0.21g, 용매인 에틸메틸케톤 (MEK) 13.33g 및 메틸이소부틸케톤 (MIBK) 6.67g 을 혼합하여 제 2 하드코팅층 형성용 코팅액 (시을 제조하였다. 제조예 2: 제 2 하드코팅층 형성용 코팅액 (B-1) 제조  38.74 g of trimethylpropyl triacrylate (TMPTA), 30.99 g of polymodified urethane acrylate prepared in Synthesis Example 1, 7.75 g of high molecular weight copolymer prepared in Synthesis Example 2, initiator for photocuring TPCKCiba company) 2.31 g, T270 (Tego Leveling Agent) 0.21 g of a solvent, 13.33 g of ethyl methyl ketone (MEK) and 6.67 g of methyl isobutyl ketone (MIBK) were mixed to prepare a coating liquid for forming a second hard coat layer (see FIG. 2). Manufacture coating liquid for hard coat layer formation (B-1)
펜타에리트리톨 트리아크릴레이트 (PETA) 12.48g, C165(평균직경 12nni인 솔리드형 실리카 나노입자와 펜타에리스리톨 트리아크릴레이트가 1:1 중량비로 혼합된 제품. NanoResin사 제품) 49.90g, 상기 합성예 2 에서 제조한 고분자량 공중합체 4.80g, TP0(Ciba 사 광경화용 개시제) 2.69g, T270(Tego 사 레벨링제) 0.13g, 용매인 에틸메틸케톤 (MEX) 20g 및 메틸이소부틸케톤 (MIBK) Pentaerythritol triacrylate (PETA) 12.48 g, C165 (solid silica nanoparticles with an average diameter of 12 nni and pentaerythritol triacrylate in a 1: 1 weight ratio product) 49.90 g, Synthesis Example 2 4.80 g of high molecular weight copolymer, 2.69 g of TP0 (Ciba photocuring initiator), 0.13 g of T270 (Tego leveling agent), 20 g of ethyl methyl ketone (MEX) as a solvent, and methyl isobutyl ketone (MIBK)
10g을 혼합하여 제 2 하드코팅층 형성용 코팅액 (B-1)을 제조하였다. 제조예 3: 제 2하드코팅층 형성용 코팅액 (B-2) 제조 10 g was mixed to prepare a coating solution (B-1) for forming a second hard coat layer. Preparation Example 3 Preparation of Coating Solution for Forming Second Hard Coating Layer (B-2)
다이펜타에리트리톨 핵사아크릴레이트 (DPHA) 4.12g, C165(평균크기 12nm 인 중공형 나노입자와 펜타에리스리톨 트리아크릴레이트가 1:1 중량비로 혼합된 제품. NanoResin사 제품) 51.49g, 상기 합성예 2에서 제조한 고분자량 공중합체 6.18g, TP0(Ciba 사 광경화용 개시제 ) 3.09g, T270(Tego 사 레벨링제) 0.12g, 용매인 에틸메틸케톤 (MEIO 23.33g 및 메틸이소부틸케톤 (MIBK) 11.67g을 혼합하여 제 2 하드코팅층 형성용 코팅액 (B-Dipentaerythritol nucleoacrylate (DPHA) 4.12 g, C165 (average size) 12 nm hollow nanoparticles and pentaerythritol triacrylate in a 1: 1 weight ratio. NanoResin) 51.49 g, 6.18 g of the high molecular weight copolymer prepared in Synthesis Example 2, 3.09 g of TP0 (Initiator for Ciba photocuring), 0.12 g of T270 (Tego leveling agent), ethyl methyl ketone solvent (MEIO 23.33 g and methyl isobutyl ketone (MIBK) are mixed to form a coating solution for forming a second hard coat layer (B-
2)을 제조하였다. 제조예 4： 저반사층 형성용 코팅액 (C)의 제조 2) was prepared. Production Example 4 Preparation of Coating Liquid (C) for Forming Low Reflective Layer
트리메틸올프로페인 트리아크릴레이트 (TMPTA) 100g, 중공형 실리카 나노 입자 (직경범위: 약 42 nm 내지 66 nni , JSC catalyst and chemicals사 제품) 283g, 솔리드형 실리카 나노 입자 (직경범위: 약 12 nni 내지 19 nm) 59g, 제 1 함불소 화합물 (X-71-1203M, ShinEtsu사) 115g, 제 2 함불소 화합물 (RS-537, DIC사) 15.5g 및 개시제 ( Irgacure 127, Ciba사) 10g를， MIBK(methyl isobutyl ketone)용매에 고형분 농도 3 중량%가 되도록 희석하여 저반사층 형성용 코팅액 (C)을 제조하였다. 제조예 5： 내오염층 형성용 코팅액 (D) 제조  100 g of trimethylolpropane triacrylate (TMPTA), hollow silica nanoparticles (diameter range: about 42 nm to 66 nni, manufactured by JSC catalyst and chemicals) 283 g, solid silica nanoparticles (diameter range: about 12 nni) 19 nm) 59 g, 1st fluorine-containing compound (X-71-1203M, ShinEtsu) 115g, 2nd fluorine-containing compound (RS-537, DIC) 15.5g and initiator (Irgacure 127, Ciba) 10g, MIBK A coating solution (C) for forming a low reflection layer was prepared by diluting the solvent to (methyl isobutyl ketone) to a solid content concentration of 3% by weight. Preparation Example 5 Preparation of Coating Liquid (D)
다관능 아크릴레이트로 펜타에리트리톨 트리아크릴레이트 (PETA) 28g, 우레탄 아크릴레이트로 톨루엔 디이소시아네이트와 펜타 에리스리톨트리아크릴레이트의 반응물 (UA-306T, Kyoeisha 제품) 4.5g, 평균입경이 12nm 인 솔리드형 실리카 나노 입자가 메틸이소부틸케톤에 분산된 분산액 (MEK-AC-2202, 고형분 40%, 용매: 메틸에틸케톤 (MEK), Nissan Chemical 제품) lQg, 개시제로 이가큐어 184 및 이가큐어 127 각 1.6g 를 용매인 메틸에틸케톤 35.2g 및 이소프로필알코올 17.6g 과 혼합하였다. 이후, 불소계 화합물인 Opt 001 DAC (고형분 20%, 용매 : 메틸에틸케톤:메틸이소부틸케톤 =3:1, Shinetsu 제품) 1.5g를 첨가하여 내오염층 형성용 코팅액 (D)을 제조하였다. 실시예 1  28 g of pentaerythritol triacrylate (PETA) as polyfunctional acrylate, 4.5 g of reactant of toluene diisocyanate and penta erythritol triacrylate as urethane acrylate (UA-306T, Kyoeisha), solid silica with an average particle diameter of 12 nm Dispersion of the nanoparticles dispersed in methyl isobutyl ketone (MEK-AC-2202, 40% solids, solvent: methyl ethyl ketone (MEK), manufactured by Nissan Chemical) lQg, 1.6 g each of Igacure 184 and Igacure 127 as an initiator It was mixed with 35.2 g of methyl ethyl ketone as a solvent and 17.6 g of isopropyl alcohol. Thereafter, 1.5 g of Opt 001 DAC (solid content 20%, solvent: methyl ethyl ketone: methyl isobutyl ketone = 3: 1, manufactured by Shinetsu), which is a fluorine compound, was added to prepare a coating solution (D) for forming a fouling layer. Example 1
(1) 제 1 하드코팅층, 기재, 및 제 2 하드코팅층을 포함하는 적충체 제조 2019/172651 1»（：1^1{2019/002606 (1) Preparation of a red worm body comprising a first hard coat layer, a base material, and a second hard coat layer 2019/172651 1 »（： 1 ^ 1 {2019/002606
250 II의 두께와 3000ä 리타데이션을 갖는 폴리에틸렌테레프탈레이트 필름 상에 상기 제조예 1 에서 제조된 제 1 하드코팅층 형성용 코팅액 (시을 #85 로 코팅한 후 80°(：에서 2 분 건조하고,
Figure imgf000019_0001
경화하여 제 1 하드코팅층을 형성했다.
Figure imgf000019_0002
램프는 0加比를 이용하였으며 , 질소분위기 하에서 경화반응을 진행하였다. 경화 시 조사된 광량은 10001111/01112 이다. 두께 측정기로 제 1 하드코팅층의 두께를 측정한 결과， 코팅두께는 71，이다. Coating solution for forming a first hard coat layer prepared in Preparation Example 1 on a polyethylene terephthalate film having a thickness of 250 II and 3000 ä retardation (coating the city with # 85 and drying at 80 ° (: 2 minutes,
Figure imgf000019_0001
It hardened | cured and the 1st hard coat layer was formed.
Figure imgf000019_0002
The lamp was used for 0 加 比, and the curing reaction was carried out under nitrogen atmosphere. The amount of light irradiated during curing is 10001111/0111 2 . As a result of measuring the thickness of the first hard coat layer with a thickness meter, the coating thickness was 71.
상기 폴리에틸렌테레프탈레이트 필름의 상기 제 1 하드코팅층과 반대면 측에 상기 제조예 2 에서 제조된 제 2 하드코팅층 형성용 코팅액犯-1 )을 #60
Figure imgf000019_0003
801：에서 2분 건조하고 경화하여 제 2하드코팅층을 형성하였다. 제 2 하드코팅의 [IV 경화는 0 加比 램프로, 질소분위기 하에서 경화하였다. 경화 시 조사된 광량은 1801111/0112 이다. 두께 측정기로 제 2 하드코팅층의 두께를 측정한 결과， 코팅두께는 45 ,이다. Coating liquid 犯 -1) for forming a second hard coat layer prepared in Preparation Example 2 on the side opposite to the first hard coat layer of the polyethylene terephthalate film # 60
Figure imgf000019_0003
801: dried for 2 minutes and cured to form a second hard coat layer. [IV curing of the second hard coating was a zero ratio lamp, which was cured under a nitrogen atmosphere. The amount of light irradiated upon curing is 1801111/011 2 . The thickness of the second hard coat layer was measured with a thickness gauge, and the coating thickness was 45.
(2) 저반사층 형성 (2) forming a low reflection layer
상기 제 2 하드코팅층 상에， 상기 제조예 4에서 제조한 저반사층 형성용 코팅액 (0을 #10
Figure imgf000019_0004
뱌로 두께가 약 100·가 되도록 코팅하고， 90 오븐에서 1분간 건조 후 경화하여 저반사층을 형성하였다. 상기 경화시에는 질소 퍼징하에서 건조된 코팅물에 252 / 의 자외선을 조사하였다. On the second hard coat layer, the coating liquid for forming a low reflection layer prepared in Preparation Example 4 (0 to # 10
Figure imgf000019_0004
It was coated so as to have a thickness of about 100 ·, dried for 1 minute in a 90 oven, and cured to form a low reflection layer. At the time of the curing, the coating dried under nitrogen purge was irradiated with ultraviolet light of 252 /.
이후, 투과전자현미경 묘則을 이용하여 상기 저굴절층에 함유된 중공형 실리카 나노 입자 및 솔리드형 실리카 나노 입자 각각 100 내지 170 개의 최장 직경을 측정하고, 이를 10 회 반복하여 상기 중공형 실리카 나노 입자 및 솔리드형 실리카 나노 입자의 평균 입경을 구하였다. 그 결과, 중공형 실리카 나노 입자의 평균직경은 54.9 11이이고, 솔리드형 실리카 나노 입자의 평균직경은 14.5 1ä임을 확인하였다.  Thereafter, 100 to 170 longest diameters of each of the hollow silica nanoparticles and the solid silica nanoparticles contained in the low refractive index layer were measured using a transmission electron microscope image, and the results were repeated 10 times to repeat the hollow silica nanoparticles. And average particle diameters of the solid silica nanoparticles. As a result, the average diameter of the hollow silica nanoparticles was 54.9 11, it was confirmed that the average diameter of the solid silica nanoparticles is 14.5 1ä.
(3) 편광판제조 (3) Polarizing plate manufacturing
폴리비닐알콜 편광자의 일측면에 ^ 경화형 접착제를 이용하여 쿼터웨이브 플레이트를 라미네이션하여 접착하였다. 쿼터웨이브 플레이트 필름이 접착되지 않은 폴리비닐알콜 편광자의 다른 측면에 상기 적층체의 제 1 하드코팅층의 면을 경화형 접착제로 접착했다. 이때, 폴리비닐알콜 2019/172651 1»（：1^1{2019/002606 Quarter wave plates were laminated to one side of the polyvinyl alcohol polarizer using a ^ curable adhesive and then bonded. On the other side of the polyvinyl alcohol polarizer to which the quarter wave plate film was not bonded, the surface of the first hard coat layer of the laminate was bonded with a curable adhesive. At this time, polyvinyl alcohol 2019/172651 1 »（： 1 ^ 1 {2019/002606
편광자의 흡수축과 상기 폴리에틸렌테레프탈레이트 필름의 지상축이 이루는 각도를 45° 로 제어했다. 이후 점착제 필름을 상기 쿼타웨이브 플레이트 면에 접착하여 점착층을 형성하였다. 실시예 2 The angle which the absorption axis of a polarizer and the slow axis of the said polyethylene terephthalate film make was controlled at 45 degrees . Thereafter, the pressure-sensitive adhesive film was bonded to the quarterwave plate to form an adhesive layer. Example 2
(1) 제 1 하드코팅층, 기재, 및 제 2 하드코팅층을 포함하는 적층체 제조  (1) Manufacture of laminate comprising a first hard coat layer, a substrate, and a second hard coat layer
제 1 하드코팅층의 두께가 75 ，이고, 제 2 하드코팅층의 두께가 42 11라는 점을 제외하고, 실시예 1과 동일한 방법으로 적층체를 제조했다.  A laminate was prepared in the same manner as in Example 1, except that the thickness of the first hard coat layer was 75, and the thickness of the second hard coat layer was 42 11.
(2) 내오염층 형성 (2) forming a fouling resistant layer
상기 제 2 하드코팅층 상에, 상기 제조예 5 에서 제조된 내오염층
Figure imgf000020_0001
두께가 약 3 ^17)- 되도록 코팅하고， 90 오븐에서 2 분간 건조 후 경화하여 내오염층을 형성하였다. 상기 경화시에는 질소 퍼징하에서 상기 건조된 코팅물에 252111^1/01/의 자외선을 조사하였다. On the second hard coat layer, the stain resistant layer prepared in Preparation Example 5
Figure imgf000020_0001
It was coated to a thickness of about 3 ^ 17)-, dried for 2 minutes in a 90 oven, and cured to form a fouling resistant layer. At the time of curing, the dried coating was irradiated with ultraviolet rays of 252111 ^ 1/01 / under nitrogen purge.
(3) 편광판 제조 (3) polarizing plate manufacturing
폴리비닐알콜 편광자의 흡수축과 상기 폴리에틸렌테레프탈레이트 필름의 지상축이 이루는 각도를 50° 로 제어했다는 점을 제외하고， 실시예 1과 동일한 방법으로 편광판을 제조했다. 실시예 3 A polarizing plate was manufactured in the same manner as in Example 1 except that the angle formed between the absorption axis of the polyvinyl alcohol polarizer and the slow axis of the polyethylene terephthalate film was controlled to 50 ° . Example 3
(1) 제 1 하드코팅층, 기재, 및 제 2 하드코팅층을 포함하는 적층체 제조  (1) Manufacture of laminate comprising a first hard coat layer, a substrate, and a second hard coat layer
제 2 하드코팅층 형성용 코팅액犯-1) 대신 제 2 하드코팅층 형성용 코팅액犯-2)을 사용하여 제 2 하드코팅층을 형성하고 , 제 1 하드코팅층의 두께를 100 로 제어하고, 제 2 하드코팅층의 두께를 70 로 제어했다는 점을 제외하고, 실시예 1과 동일한 방법으로 적층체를 제조했다.  A second hard coat layer is formed by using the second hard coat layer forming coating liquid 犯 -2) instead of the second hard coating layer forming coating liquid 犯 -1), the thickness of the first hard coating layer is controlled to 100, and the second hard coating layer is formed. A laminate was produced in the same manner as in Example 1, except that the thickness of was controlled to 70.
(2) 내오염층 형성 2019/172651 1»（：1^1{2019/002606 (2) forming a fouling resistant layer 2019/172651 1 »（： 1 ^ 1 {2019/002606
실시예 2 의 내오염층 형성 방법과 동일한 방법으로 상기 제 2 하드코팅층 상에 내오염층을 형성하였다. A fouling resistant layer was formed on the second hard coat layer in the same manner as in the fouling resistant layer forming method of Example 2.
(3) 편광판제조 (3) Polarizing plate manufacturing
폴리비닐알콜 편광자의 흡수축과 상기 폴리에틸렌테레프탈레이트 필름의 지상축이 이루는 각도를 50° 로 제어했다는 점을 제외하고, 실시예 1과 동일한 방법으로 편광판을 제조했다. 실시예 4 A polarizing plate was manufactured in the same manner as in Example 1, except that the angle formed between the absorption axis of the polyvinyl alcohol polarizer and the slow axis of the polyethylene terephthalate film was controlled at 50 ° . Example 4
(1) 제 1 하드코팅층， 기재, 및 제 2 하드코팅층을 포함하는 적층체 제조  (1) Manufacture of a laminate comprising a first hard coat layer, a base material, and a second hard coat layer
폴리에틸렌테레프탈레이트 필름의 두께가 80쎈 1이고, 제 1 하드코팅층의 두께가 22 /께이고, 제 2 하드코팅층의 두께가 21，라는 점을 제외하고， 실시예 1과 동일한 방법으로 적층체를 제조했다. A laminate was manufactured in the same manner as in Example 1, except that the polyethylene terephthalate film had a thickness of 80 쎈 1 , the thickness of the first hard coat layer was 22 / thickness, and the thickness of the second hard coat layer was 21. did.
(2) 내오염층 형성 (2) forming a fouling resistant layer
내오염층의 두께가 2.8 1이라는 점을 제외하고， 실시예 2 의 내오염층 형성 방법과 동일한 방법으로 제 2 하드코팅층 상에 내오염층을 형성하였다. (3) 편광판제조  The stain resistant layer was formed on the second hard coat layer in the same manner as the stain resistant layer forming method of Example 2, except that the thickness of the stain resistant layer was 2.8 1. (3) Polarizing plate manufacturing
실시예 1과 동일한 방법으로 편광판을 제조했다. 비교예 1  A polarizing plate was manufactured in the same manner as in Example 1. Comparative Example 1
(1) 제 1 하드코팅충, 기재, 및 제 2 하드코팅층을 포함하는 적층체 제조  (1) Manufacture of a laminate comprising a first hard coat worm, a base material, and a second hard coat layer
폴리에틸렌테레프탈레이트 필름 대신 두께가 80 ，인 트리아세틸셀룰로오스 필름을 사용하고, 제 1 하드코팅층의 두께가 24，이고， 제 2 하드코팅층의 두께가 21 / 라는 점을 제외하고， 실시예 1 과 동일한 방법으로 적층체를 제조했다. 2019/172651 1»（：1^1{2019/002606 The same method as in Example 1, except that a triacetyl cellulose film having a thickness of 80 is used instead of the polyethylene terephthalate film, the thickness of the first hard coating layer is 24, and the thickness of the second hard coating layer is 21 /. The laminate was manufactured. 2019/172651 1 »（： 1 ^ 1 {2019/002606
(2) 내오염층 형성 (2) forming a fouling resistant layer
실시예 2 의 내오염층 형성 방법과 동일한 방법으로 제 2 하드코팅층 상에 내오염층을 형성하였다. (3) 편광판제조  A fouling resistant layer was formed on the second hard coat layer in the same manner as in the fouling resistant layer forming method of Example 2. (3) Polarizing plate manufacturing
실시예 1 과 동일한 방법으로 편광판을 제조하였으나, 트리아세틸셀룰로오스 필름은 무연신 필름이어서 지상축과 진상축의 구별이 모호하기 때문에， 방향에 관계없이 접착하였다. 비교예 2  The polarizing plate was manufactured in the same manner as in Example 1, but the triacetyl cellulose film was a non-stretched film, so the distinction between the slow axis and the fast axis was ambiguous. Comparative Example 2
(1) 제 1 하드코팅층, 기재, 및 제 2 하드코팅층을 포함하는 적층체 제조  (1) Manufacture of laminate comprising a first hard coat layer, a substrate, and a second hard coat layer
제 1 하드코팅층의 두께가 73 ᅵ이고, 제 2 하드코팅층의 두께가 42 라는 점을 제외하고， 실시예 1과 동일한 방법으로 적층체를 제조했다.  A laminate was manufactured in the same manner as in Example 1, except that the thickness of the first hard coat layer was 73 ᅵ and the thickness of the second hard coat layer was 42.
(2) 내오염층 형성 (2) forming a fouling resistant layer
내오염층의 두께가 2.7 //이이라는 점을 제외하고, 실시예 2 의 내오염층 형성 방법과 동일한 방법으로 제 2 하드코팅층 상에 내오염층을 형성하였다. (3) 편광판제조  The stain resistant layer was formed on the second hard coat layer in the same manner as the stain resistant layer forming method of Example 2, except that the thickness of the stain resistant layer was 2.7 //. (3) Polarizing plate manufacturing
폴리비닐알콜 편광자의 흡수축과 상기 폴리에틸렌테레프탈레이트 필름의 지상축이 이루는 각도를 0° 로 제어했다는 점을 제외하고， 실시예 1 과 동일한 방법으로 편광판을 제조했다. 비교예 3 A polarizing plate was manufactured in the same manner as in Example 1 except that the angle formed between the absorption axis of the polyvinyl alcohol polarizer and the slow axis of the polyethylene terephthalate film was controlled to 0 ° . Comparative Example 3
(1) 제 1 하드코팅층, 기재, 및 제 2 하드코팅층을 포함하는 적층체 제조  (1) Manufacture of laminate comprising a first hard coat layer, a substrate, and a second hard coat layer
제 1 하드코팅층을 형성하지 않았다는 점을 제외하고, 실시예 1 과 동일한 방법으로 적층체를 제조했다. 2019/172651 1»（：1^1{2019/002606 A laminate was prepared in the same manner as in Example 1, except that the first hard coat layer was not formed. 2019/172651 1 »（： 1 ^ 1 {2019/002606
(2) 내오염층 형성 (2) forming a fouling resistant layer
내오염층의 두께가 2.8 / 이라는 점을 제외하고, 실시예 2 의 내오염층 형성 방법과 동일한 방법으로 제 2 하드코팅층 상에 내오염층을 형성하였다. (3) 편광판제조  The stain resistant layer was formed on the second hard coat layer in the same manner as the stain resistant layer forming method of Example 2, except that the thickness of the stain resistant layer was 2.8 /. (3) Polarizing plate manufacturing
쿼터웨이브 플레이트가 접착되지 않은 폴리비닐알콜 편광자의 다른 측면에 상기 적층체의 폴리에틸렌테레프탈레이트 필름을
Figure imgf000023_0001
경화형 접착제로 접착했다는 점을 제외하고, 실시예 1 과 동일한 방법으로 편광판을 제조하였다. ［평가］ On the other side of the polyvinyl alcohol polarizer to which the quarter wave plate is not bonded, a polyethylene terephthalate film of the laminate
Figure imgf000023_0001
A polarizing plate was produced in the same manner as in Example 1, except that the adhesive was cured with a curable adhesive. [evaluation]
1. 연필 경도측정  1. Pencil hardness measurement
실시예 및 비교예에서 제조된 편광판에 대하여， 연필경도 측정기를 이용하여 측정 표준그 1(5400에 따라 500용의 하중， 45° 의 각도로 5회 긁은 후 육안으로 판별하여 흠집이 없는 최대 경도를 평가하고, 그 결과를 하기 표 1에 나타냈다. For the polarizing plates manufactured in Examples and Comparative Examples, using a pencil hardness tester, the measurement standard 1 (for 500 according to 5400, scraping five times at an angle of 45 ° , and then visually determined to determine the maximum hardness without scratches It evaluated and the result was shown in following Table 1.
또한, 실시예 및 비교예의 편광판에서 편광자가 합지되지 않는 구조， 즉, 상기 ( 1 )제 1 하드코팅층, 광투과성 기재 및 제 2 하드코팅층을 포함하는 적층체, 및 (2)내오염층 (또는 저반사층)을 포함하는 하드 코팅 필름에 대하여， 연필경도 측정기를 이용하여 측정 표준 1(5400 에 따라 1 .01 의 하중, 45° 의 각도로 5 회 긁은 후 육안으로 판별하여 흠집이 없는 최대 경도를 평가하고, 그 결과를 하기 표 1에 나타냈다. In addition, in the polarizing plates of Examples and Comparative Examples, a structure in which polarizers are not laminated, that is, a laminate including (1) the first hard coat layer, the light-transmissive substrate, and the second hard coat layer, and (2) the stain resistant layer (or with respect to the low-hard coating film comprising a reflective layer), and then it scratched 5 times with a load angle, 45 ° for 1, 4.01, according to the measurement standard 1 (5400 using a pencil hardness tester to visually determine the maximum hardness without flaws It evaluated and the result was shown in following Table 1.
2. 선글라스 레인보우현상유무 2. Sunglasses rainbow phenomenon
실시예 및 비교예에서 제조된 필름의 점착층면에 블랙 테이프 ( 1 472미 31\1 사 제조)를 붙인 후 내오염층 혹은 저반사층이 있는 면을 삼파장 램프에 비추어 육안으로 레인보우가 발생하는지 여부를 확인하고 그 결과를 하기 표 1 에 나타냈다. 육안평가 시 암실에서 삼파장 램프 아래에서 평가를 하였다.  After attaching a black tape (manufactured by US 1 472 US 31 \ 1) to the adhesive layer surface of the films prepared in Examples and Comparative Examples, whether the rainbow is generated by visually reflecting the surface having a pollution-resistant layer or a low reflection layer on a three-wavelength lamp. It confirmed and the result was shown in following Table 1. Visual evaluation was performed under a three-wavelength lamp in the dark room.
＜측정 기준 ñ  <Measurement standard ñ
X： 레인보우 얼룩이 존재하지 않음. ◦ : 레인보우 얼룩 존재. X: Rainbow stain does not exist. ◦: Rainbow stains present.
3. 레인보우 변동비 측정 3. Rainbow Variable Ratio Measurement
상기 레인보우의 정도를 정량적으로 비교하기 위해, 실시예 및 비교예의 편광판의 반사율을 다음의 방법으로 측정하고 레인보우 변동비를 계산하였다.  In order to quantitatively compare the degree of the rainbow, the reflectances of the polarizing plates of Examples and Comparative Examples were measured by the following method and the rainbow variation ratio was calculated.
실시예 및 비교예에서 편광판을 4cm X 4cm 크기로 자르고, 제 2 하드코팅층에 블랙 테이프 (Vinyl tape 472 Bl ack， 3M 사 제조)를 붙인 후, Shimadzu 사의 UV-VIS 분광기 (UV-VIS spect rometer , 모델명: UV2550)를 사용하여 5° 반사 모드, 슬릿 폭 (s l i t wi dth) 2nm , 분석 파장 범위 380 내지 780nm 에서 반사율을 측정하고, 450 내지 650nni 사이에서의 반사율을 데이터를 도출했다. 도출된 450 내지 650nm 사이에서의 반사율을 데이터로부터 반사율 평균 및 최대반사율과 최소반사율의 차이를 계산하고, 이를 하기 식에 대입하여 레인보우의 변동비 ( A Rb)를 계산하고, 그 결과를 하기 표 1 에 나타냈다. In Examples and Comparative Examples, the polarizing plate was cut to a size of 4 cm X 4 cm, a black tape (Vinyl tape 472 Bl ack, manufactured by 3M) was attached to the second hard coating layer, and then a Shimadzu UV-VIS spectrometer (UV-VIS spectrometer, Model name: UV2550) was used to measure reflectance at 5 ° reflection mode, slit width 2nm, analysis wavelength range 380-780nm, and reflectance data between 450-650nni was derived. Calculate the difference between the reflectance average and the maximum reflectance and the minimum reflectance from the derived reflectance between 450 and 650 nm, and substitute the result in the following formula to calculate the variation ratio of the rainbow (A Rb), and the results are shown in Table 1 below. Indicated.
ARb= (450 내지 650nm에서의 최대반사율 - 450내지 650nm에서의 최소 반사율) ÷ (450 내지 650nm에서의 반사율 평균) x 100  ARb = (maximum reflectance at 450 to 650 nm-minimum reflectance at 450 to 650 nm) ÷ (reflection average at 450 to 650 nm) x 100
4. 휨 (Curl) 측정 4. Curling Measurement
10cm x 10cm 크기로 재단된 실시예 및 비교예의 편광판의 내오염층 또는 저반사층이 위로 오도록 하고, 정가운데 부분이 바닥에 닿도록 직경 lcm 이하의 막대로 편광판의 정가운데 부분을 눌러줬다. 이때， 네 꼭지점이 바닥면으로부터 뜨는 높이를 측정한 후 높이의 평균을 계산하여 휨 값을 구했다. 이렇게 구해진 휨 값은 양수로 표현했다. 만약 필름이 제 1하드코팅층 방향으로 휘어져 있다면, 편광판을 뒤집어 내오염층 또는 저반사층이 바닥으로 오도록 하고 동일한 방법으로 휨 값을 구하고, 이때의 휨의 값을 음수로 표현했다.  The stain resistant layer or the low reflection layer of the polarizing plates of Examples and Comparative Examples cut to the size of 10cm x 10cm face up, and pressed the middle part of the polarizing plate with a rod having a diameter of lcm or less so that the center part touches the bottom. At this time, the height of the four vertices was measured from the bottom surface, and then the average of the heights was calculated to obtain the warpage value. The warpage values thus obtained were expressed as positive numbers. If the film is bent in the direction of the first hard coating layer, the polarizing plate is inverted to bring the stain resistant layer or the low reflection layer to the bottom, and the warpage value is obtained by the same method, and the warpage value at this time is negatively expressed.
【표 1] 2019/172651 1»(：1^1{2019/002606 [Table 1] 2019/172651 1 »(： 1 ^ 1 {2019/002606
Figure imgf000025_0001
상기 표 1에 따르면, 실시예 1 내지 4는 연필경도가 우수하고, 레인보우 현상이 나타나지 않으며， 레인보우 변동비 및 휩 값이 낮아 광학특성 및 기계적 물성이 우수하다는 점을 확인했다.
Figure imgf000025_0001
According to Table 1, Examples 1 to 4 have excellent pencil hardness, no rainbow phenomenon, low rainbow fluctuation ratio and whip value was confirmed that the excellent optical and mechanical properties.
반면, 면 내에 복굴절률을 갖는 광투과성 기재를 사용하지 않은 비교예 On the other hand, Comparative Example without using a light-transmitting substrate having a birefringence in plane
1은 연필경도가 낮아 기계적 물성이 낮으며, 광투과성 기재의 지상축과 편광자의 흡수축이 이루는 각도가 0° 인 비교예 2는 레인보우 현상이 나타나고 레인보우 변동비가 높아 광학특성이 낮으며, 제 1 하드코팅층을 포함하지 않는 비교예 3은 휩 값이 매우 높음을 확인했다. 1 shows low mechanical properties due to low pencil hardness, and Comparative Example 2 having an angle of 0 ° formed by the slow axis of the light transmissive substrate and the absorption axis of the polarizer exhibits a rainbow phenomenon and a high rainbow fluctuation ratio, resulting in low optical characteristics. Comparative Example 3, which does not include a hard coat layer, confirmed that the whip value was very high.

Claims

【특허청구범위】 [Patent Claims]
【청구항 1 ]  [Claim 1]
편광자;  Polarizer;
상기 편광자 상에 위치하고, (메트)아크릴레이트계 (공)중합체를 포함하는 바인더 수지를 함유하는 제 1 하드코팅층 ;  A first hard coat layer disposed on the polarizer and containing a binder resin containing a (meth) acrylate-based (co) polymer;
상기 제 1 하드코팅층 상에 위치하고， 3000nm 이상의 리타데이션 (Retardat i on)을 가지고, 면 내에 복굴절률을 갖는 광투과성 기재; 상기 광투과성 기재 상에 위치하고， 바인더 수지; 및 상기 바인더 수지에 분산된 솔리드형 무기 나노 입자;를 포함하는 제 2 하드코팅층를 포함하고, 상기 광투과성 기재의 지상축과, 상기 편광자의 흡수축이 이루는 예각의 각도가 5 내지 85° 인， 편광판. A light-transmitting substrate on the first hard coating layer, having a retardation of 3000 nm or more, and having a birefringence in plane; Located on the light transmissive substrate, binder resin; And a second hard coat layer including solid inorganic nanoparticles dispersed in the binder resin, wherein an acute angle between the slow axis of the light transmissive substrate and the absorption axis of the polarizer is 5 to 85 ° . .
【청구항 2] [Claim 2]
제 1항에 있어서，  The method of claim 1,
상기 제 1 하드코팅층에 대향하도록 상기 편광자의 다른 일면에 위치하는 쿼터웨이브 플레이트 (Quarter Wave Pl ate)를 더 포함하는, 편광판.  And a quarter wave plate positioned on the other surface of the polarizer so as to face the first hard coating layer.
【청구항 3] [Claim 3]
제 1항에 있어서，  The method of claim 1,
상기 광투과성 기재는 폴리에틸렌 테레프탈레이트 (PET) 필름인， 편광판.  The light transmissive substrate is a polyethylene terephthalate (PET) film, polarizing plate.
【청구항 4] [Claim 4]
제 1항에 있어서,  The method of claim 1,
상기 광투과성 기재는, 지상축 방향의 굴절률 (nx)과， 상기 지상축 방향과 직교하는 방향인 진상축 방향의 굴절률 (ny)의 차 (nx-ny)가 0.05 이상인, 편광판. The said light-transmitting base material is a polarizing plate whose difference (n x -n y ) of the refractive index (n x ) of a slow axis direction, and the refractive index (n y ) of a fast axis direction which is a direction orthogonal to the said slow axis direction is 0.05 or more.
【청구항 5] [Claim 5]
제 1항에 있어서, 2019/172651 1»（：1^1{2019/002606 The method of claim 1, 2019/172651 1 »（： 1 ^ 1 {2019/002606
상기 광투과성 기재는 두께가 10 내지 500 인, 편광판. The light transmissive substrate has a thickness of 10 to 500, the polarizing plate.
【청구항 6】 [Claim 6]
제 1항에 있어서，  The method of claim 1,
상기 제 1 하드코팅층 및 제 2 하드코팅층은 두께비가 1:0.5 내지 The first hard coat layer and the second hard coat layer have a thickness ratio of 1: 0.5 to
1:1.5인， 편광판. Polarizer plate which is 1: 1.5.
【청구항 71 [Claim 71
제 1항에 있어서，  The method of claim 1,
상기 광투과성 기재 및 제 2 하드코팅층은 두께비가 1:0.1 내지 1:1인, 편광판.  The light transmissive substrate and the second hard coat layer is a polarizer of the thickness ratio 1: 0.1 to 1: 1.
【청구항 8] [Claim 8]
제 1항에 있어서,  The method of claim 1,
상기 제 1 하드코팅증의 （메트）아크릴레이트계 （공）중합체는 단관능 혹은 다관능 （메트）아크릴레이트계 단복단위 및 우레탄 （메트）아크릴레이트계 반복단위를 포함하는， 편광판.  The (meth) acrylate type (co) polymer of the said 1st hard-coating mark contains a monofunctional or polyfunctional (meth) acrylate type | mold unit, and a urethane (meth) acrylate type repeating unit, The polarizing plate.
【청구항 9] [Claim 9]
제 1항에 있어서,  The method of claim 1,
상기 제 2 하드코팅층의 바인더 수지는 광경화성 수지 및 중량평균분자량이 10,00 /!1101 이상인 （공）중합체를 포함하는， 편광판.  The binder resin of the second hard coat layer comprises a photocurable resin and a (co) polymer having a weight average molecular weight of 10,00 /! 1101 or more.
【청구항 10】 [Claim 10]
제 2항에 있어서 ,  The method of claim 2,
상기 편광자에 대향하도록 상기 쿼터웨이브 플레이트의 다른 일면에 위치하는 점착층을 더 포함하는， 편광판.  The polarizing plate further comprises an adhesive layer located on the other side of the quarter wave plate to face the polarizer.
【청구항 11】 [Claim 11]
제 1항에 있어서, 2019/172651 1»（：1^1{2019/002606 The method of claim 1, 2019/172651 1 »（： 1 ^ 1 {2019/002606
상기 제 2 하드코팅층 상에 위치하고, 바인더 수지; 및 상기 바인더 수지에 분산된 무기 나노 입자;를 포함하는 저반사층; 또는 Located on the second hard coating layer, a binder resin; A low reflection layer comprising; and inorganic nanoparticles dispersed in the binder resin; or
상기 제 2 하드코팅층 상에 위치하고， 바인더 수지; 상기 바인더 수지에 분산된 솔리드형 무기 나노 입자; 및 불소계 화합물;을 포함하는 내오염층을 더 포함하는, 편광판.  Located on the second hard coating layer, a binder resin; Solid inorganic nanoparticles dispersed in the binder resin; And a fouling resistant layer comprising a fluorine-based compound.
【청구항 12】 [Claim 12]
제 1항에 있어서,  The method of claim 1,
상기 편광판은 500§하중에서 연필 경도가해 이상인, 편광판. Wherein said polarizing plate is at least a pencil hardness understanding at 500 § load.
【청구항 13】 [Claim 13]
제 1항에 있어서,  The method of claim 1,
상기 제 1 하드코팅층, 광투과성 기재 및 제 2 하드코팅층을 포함하는
Figure imgf000028_0001
중에서 연필 경도가則 이상인 , 편광판. The first hard coating layer, comprising a transparent substrate and a second hard coating layer
Figure imgf000028_0001
The polarizing plate whose pencil hardness is more than in.
【청구항 14】 [Claim 14]
제 1항에 있어서,  The method of claim 1,
상기 편광판에 대한 하기 수학식 1 의 레인보우 변동비（스1¾）가 10% 이하인, 편광판:  The polarizing plate of the rainbow fluctuation ratio (s 1¾) of the following formula 1 with respect to the polarizing plate is 10% or less:
[수학식 1]  [Equation 1]
스1¾= （450 내지 650ä 에서의 최대반사율 - 450 내지 650ä 에서의 최소 반사율） ÷ （450 내지 6501페에서의 반사율 평균） X 100  S1¾ = (maximum reflectance at 450 to 650ä-minimum reflectance at 450 to 650ä) ÷ (reflectance average at 450 to 6501 p) X 100
【청구항 15】 [Claim 15]
제 1항의 편광판을 포함하는 화상 표시 장치 .  An image display device comprising the polarizing plate of claim 1.
PCT/KR2019/002606 2018-03-06 2019-03-06 Polarizing plate and image display device comprising same WO2019172651A1 (en)

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JP2020519739A JP7330469B2 (en) 2018-03-06 2019-03-06 Polarizing plate and image display device containing the same
US16/760,528 US20210223453A1 (en) 2018-03-06 2019-03-06 Polarizing plate and image display device comprising the same

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100956534B1 (en) * 2001-12-25 2010-05-07 후지필름 가부시키가이샤 Circularly polarizing plate and liquid crystal display device
KR20150003709A (en) * 2012-05-31 2015-01-09 다이니폰 인사츠 가부시키가이샤 Optical layered body, polarizing plate, polarizing plate fabrication method, image display device, image display device manufacturing method, and image display device visual recognizability improvement method
KR101661049B1 (en) * 2012-04-13 2016-09-28 후지필름 가부시키가이샤 Phase-difference film, polarizing plate, liquid-crystal display, and method for manufacturing phase-difference film
KR20170086477A (en) * 2014-11-25 2017-07-26 도요보 가부시키가이샤 Liquid crystal display device and polarizing plate
KR101822701B1 (en) * 2014-12-31 2018-01-30 삼성에스디아이 주식회사 Polarizing plate and liquid crystal display comprising the same
KR20180026390A (en) 2015-05-27 2018-03-12 파마케아, 인크. Autotaxin inhibitors and uses thereof
KR20190025662A (en) 2017-07-06 2019-03-11 프라마톰 게엠베하 How to Decontaminate the Metal Surface of a Nuclear Power Plant

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100956534B1 (en) * 2001-12-25 2010-05-07 후지필름 가부시키가이샤 Circularly polarizing plate and liquid crystal display device
KR101661049B1 (en) * 2012-04-13 2016-09-28 후지필름 가부시키가이샤 Phase-difference film, polarizing plate, liquid-crystal display, and method for manufacturing phase-difference film
KR20150003709A (en) * 2012-05-31 2015-01-09 다이니폰 인사츠 가부시키가이샤 Optical layered body, polarizing plate, polarizing plate fabrication method, image display device, image display device manufacturing method, and image display device visual recognizability improvement method
KR20170086477A (en) * 2014-11-25 2017-07-26 도요보 가부시키가이샤 Liquid crystal display device and polarizing plate
KR101822701B1 (en) * 2014-12-31 2018-01-30 삼성에스디아이 주식회사 Polarizing plate and liquid crystal display comprising the same
KR20180026390A (en) 2015-05-27 2018-03-12 파마케아, 인크. Autotaxin inhibitors and uses thereof
KR20190025662A (en) 2017-07-06 2019-03-11 프라마톰 게엠베하 How to Decontaminate the Metal Surface of a Nuclear Power Plant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3677935A4 *

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