KR20090110661A - Anti-static polarizing plate and liquid crystal display device using the same - Google Patents

Abstract

PURPOSE: An anti-static polarizing plate and a liquid crystal display device using the same are provided to prevent a scratch or a scrape generated from a contact due to an external impact by using a polarizing plate. CONSTITUTION: In an anti-static polarizing plate and a liquid crystal display device using the same, a polarizing plate is composed of a polarizer(114), a first polarizer protection film(113), and a second polarizer protection film(115). The first polarizer protection films protect the polarizer, and the second polarizer protection films include a decompression adhesive layer attached to the liquid crystal cell. An antistatic property hard-coating layer(112) and a surface protection film(111) are laminated on the first polarizer protection films. The antistatic property decompression adhesive layer(116) and a separator film(117) are laminated on the second polarizer protection films.

Description

Antistatic polarizing plate and liquid crystal display device having the same {ANTI-STATIC POLARIZING PLATE AND LIQUID CRYSTAL DISPLAY DEVICE USING THE SAME}

The present invention is excellent in antistatic properties and polarizing plate that can simultaneously solve the static electricity generated during the peeling removal of the separator film of the pressure-sensitive adhesive layer as well as the static electricity generated during the peeling removal of the surface protective film in the manufacturing process of the liquid crystal display device and It relates to a liquid crystal display device.

Recently, liquid crystal display devices (LCDs), which are used for various purposes such as notebooks, mobile phones, and liquid crystal TVs, are generally liquid crystal cells and liquid crystal cells including liquid crystals, adhesive layers or adhesive layers for bonding them. It is composed. In addition, the polarizing plate includes a polarizer (or 'polarizing film') in which an iodine-based compound or a dichroic polarizing material is adsorbed on a polyvinyl alcohol (PVA) resin film arranged in a predetermined direction, The first polarizer protective film for protecting the polarizer on one side, and the anti-reflective, anti-glare, high hardness, antistatic coating layer is further included on the first polarizer protective film, the polyester base film on the functional coating layer And a surface protective film having a pressure-sensitive adhesive layer laminated thereon. And on the other side of the polarizer is a multilayer structure provided with a second polarizer protective film, a pressure-sensitive adhesive layer and a separator film to be affixed with the liquid crystal cell on the second polarizer protective film.

Various optical films and functional coating layers of the polarizing plate having such a structure have high surface resistance, and thus, static electricity is easily generated, and static electricity is generated during peeling and removal of unnecessary surface protection film and separator film in the assembly process of the external charge and the LCD substrate. The static electricity generated in this way causes surface contamination problems such as foreign material adsorption to the optical member, staining due to unnecessary liquid crystal alignment, and the like, and may cause damage to the integrated circuit chip of the liquid crystal display device. In particular, as the size and thickness of liquid crystal display devices have increased in recent years, the size of the polarizing plate used in the manufacture of liquid crystal display devices has also increased, and the amount of static electricity has increased as the process speeds up.

In order to solve the electrostatic problem that occurs when peeling and removing the separator film as described above, a method using an antistatic pressure-sensitive adhesive layer added with a conductive material on the polarizer protective film has been proposed. Specifically, a method of adding a substance having a conductive component such as a conductive polymer, metal oxide particles, and carbon particles to an adhesive, a method of adding an ionic substance such as a metal salt, an organic salt, or a surfactant has been performed. Patent No. 1998-0081608, Korean Patent Publication No. 1989-0013673, Korean Patent Publication No. 2001-0111715, Korean Patent Publication No. 2004-0032058, Korean Patent Publication No. 2006-0018495, Korean Patent Publication No. 2004-0030919 Korean Patent Laid-Open No. 2001-0010433, Korean Patent Laid-Open No. 2005-0072567, Japanese Patent Laid-Open No. 2006-111856, Japanese Patent Laid-Open No. 2006-111846, Japanese Patent Laid-Open No. 2006-104434). However, this method has a disadvantage in that it is difficult to solve the electrostatic problem generated when the surface protection film is peeled off.

On the other hand, in order to solve the electrostatic problem in the peeling removal of the surface protection film, a method of applying an antistatic layer containing ITO (indiumtinoxide), ATO (antimontinoxide) on the first polarizer protective film of the polarizing plate has been proposed (Japanese Patent Publication No. 1994-051121). However, in the case of this method, the problem of static electricity generated when the surface protection film is peeled off can be solved to some extent, but the problem of static electricity generated when peeling off the separator film laminated on the pressure-sensitive adhesive layer on the other side of the polarizing plate can be completely solved. none. In addition, coating liquids containing ITO and ATO are not very economical because they are very expensive and increase the cost of the final product, and are not suitable for commercial applications.

Therefore, while maintaining the existing physical properties of the pressure-sensitive adhesive or hard coating agent, there is a need for a study on a more economic method that can simultaneously solve the electrostatic problem that occurs during the peeling removal of the surface protective film and the separator film of the polarizing plate.

The present invention is to provide a polarizing plate which is excellent in antistatic properties and at the same time can solve the static electricity generated during the peeling removal of the separator film of the pressure-sensitive adhesive layer as well as the static electricity generated during the peeling removal of the surface protection film in the manufacturing process of the liquid crystal display device. For the purpose.

Another object of the present invention is to provide a liquid crystal display device having the polarizing plate.

In order to achieve the above object, the inventors of the present invention use a low-cost ionic solid as an antistatic agent instead of expensive metal oxides such as ITO and ATO, which have been pointed out as disadvantages in the prior art. The antistatic hard coating layer was laminated on the first polarizer protective film, and the antistatic pressure-sensitive adhesive layer was laminated on the second polarizer protective film on the opposite side. As a result, through the interaction between the antistatic hard coating layer and the pressure-sensitive adhesive layer, not only the electrostatic problem caused by the peeling removal of the surface protection film but also the electrostatic problem occurring during the peeling removal of the separator film that is difficult to solve by the conventional antistatic hard coating layer at the same time It was confirmed that the invention, based on this it was completed the present invention.

The present invention is a polarizing plate comprising an antistatic hard coating layer and an antistatic pressure-sensitive adhesive layer, the surface resistivity of the antistatic hard coating layer is 1 x 10 ¹¹ to 1 x 10 ¹³ Ω / □, the antistatic pressure The polarizing plate whose surface specific resistance of an adhesive layer is 1 x 10 ^11-1 x 10 ¹² ohms / square.

In another aspect, the present invention provides a liquid crystal display device having the polarizing plate on at least one side of the liquid crystal cell.

The polarizing plate according to the present invention is excellent in mechanical properties such as high hardness and abrasion resistance to prevent scratches or scrapes generated by contact due to external impact, and excellent adhesion durability, and at the same time Since the antistatic property is excellent, in addition to the static electricity generated during the peeling removal of the surface protection film in the manufacturing process of the liquid crystal display device, the static electricity problem generated during the peeling removal of the separator film of the pressure-sensitive adhesive layer can be simultaneously solved. In addition, by using inexpensive ionic solids instead of expensive metal oxides such as ITO or ATO in the hard coating layer and providing antistatic properties to the pressure-sensitive adhesive layer, these interactions can solve the static problem in a more economical way. have.

The present invention is excellent in antistatic properties and polarizing plate that can simultaneously solve the static electricity generated during the peeling removal of the separator film of the pressure-sensitive adhesive layer as well as the static electricity generated during the peeling removal of the surface protective film in the manufacturing process of the liquid crystal display device and It relates to a liquid crystal display device.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Polarizing plate of the present invention is a polarizing plate comprising an antistatic hard coating layer and an antistatic pressure-sensitive adhesive layer, the surface resistivity of the antistatic hard coating layer is 1 x 10 ¹¹ to 1 x 10 ¹³ Ω / □, the antistatic The surface specific resistance of the pressure-sensitive adhesive layer is 1 x 10 ¹¹ to 1 x 10 ¹² Ω / □.

The polarizer may be one in which the dichroic dye is adsorbed and oriented on a film made of polyvinyl alcohol-based resin as an optical film for converting incident natural light into a desired single polarization state (linear polarization state).

Polyvinyl alcohol-type resin which comprises the said polarizer can be manufactured by saponifying polyvinyl acetate type resin. Examples of the polyvinyl acetate-based resin include copolymers of vinyl acetate and other monomers copolymerizable therewith, in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate. Specific examples of the other monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, unsaturated sulfonic acids, olefins, vinyl ethers, acrylamides having an ammonium group, and the like. The degree of saponification of the polyvinyl alcohol-based resin is usually about 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used. Moreover, the polymerization degree of polyvinyl alcohol-type resin is about 1,000 to 10,000 normally, Preferably it is about 1,500 to 5,000.

The polarizer is usually a step of uniaxially stretching the polyvinyl alcohol-based resin film as described above, a step of dyeing the polyvinyl alcohol-based resin film with a dichroic dye to adsorb the dichroic dye, and a polyvinyl alcohol adsorbed with the dichroic dye. It can manufacture through the process of processing a system resin film with the boric acid aqueous solution, and the process of washing with water after the process by this boric acid aqueous solution. At this time, an iodine or a dichroic organic dye can be used as a dichroic dye.

The first polarizer protective film is a film disposed on the viewing side, and the second polarizer protective film is a film on which a pressure-sensitive adhesive layer for bonding to a liquid crystal cell is laminated.

The first and second polarizer protective films are preferably excellent in transparency, mechanical strength, thermal stability, moisture shielding, isotropy, etc., for example, polyester-based such as polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate film; Cellulose films such as diacetyl cellulose and triacetyl cellulose; Polycarbonate film; Acrylic films such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Styrene films such as polystyrene and acrylonitrile-styrene copolymers; Polyolefin-based films such as polyethylene, polypropylene, cyclo-based or norbornene-structured polyolefin and ethylene propylene copolymer; Polyimide film; Polyether sulfone-based film; Conventional films, such as a sulfone type film, can be used.

On the first polarizer protective film, a surface treatment layer such as an antireflection layer and an antiglare layer may be further included as necessary. For example, the anti-reflection layer is for preventing reflection of external light on the surface of the polarizing plate, and may be formed by a known method. It may be formed by a roughening method by a sandblasting method, an embossing method, or the like, or a method of applying and curing a composition in which transparent fine particles are mixed with an ultraviolet curable resin.

An antistatic hard coating layer is a layer for solving the electrostatic problem generated when the surface protective film and the separator film is peeled off by being laminated on the first polarizer protective film, an antistatic hard coating agent containing an ionic solid as an antistatic agent Consists of a composition.

The antistatic hard coating agent composition includes an ionic solid as an antistatic agent in a hard coating agent composition including an ultraviolet curable acrylic monomer, a reactive silica particle, an organic solvent, and a photopolymerization initiator.

The ultraviolet curable acrylic monomer is not particularly limited as long as it is a known acrylic monomer having one or more functional groups. Specific examples include allyl methacrylate, 2-ethoxyethyl (meth) acrylate, isodecyl (meth) acrylate, 2-dodecylthioethyl methacrylate, octyl acrylate, 2-methoxyethyl acrylate, Monomers having monofunctional groups such as 2-hydroxyethyl methacrylate, isooctyl acrylate and urethane acrylate; 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A-ethylene glycol diacrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) Acrylate, dicyclopentanyldi (meth) acrylate, caprolactone modified dicyclopentenyldi (meth) acrylate, ethylene oxide modified phosphate di (meth) acrylate, di (acryloxyethyl) isocyanurate, allyl Cyclohexyldi (meth) acrylate, dimethyloldicyclopentanediacrylate, ethylene oxide modified hexahydrophthalic acid diacrylate, tricyclodecane dimethanol acrylate, neopentyl glycol modified trimethylolpropanediacrylate and adamantanedi Difunctional monomers such as acrylate; Trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane Trifunctional monomers such as tri (meth) acrylate and tris (acryloxyethyl) isocyanurate; Tetrafunctional monomers such as diglycerin tetra (meth) acrylate and pentaerythritol tetra (meth) acrylate; Pentafunctional monomers such as propionic acid-modified dipentaerythritol penta (meth) acrylate; And six-functional monomers such as caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like, and among these, 1-3 functional monomers are preferable. These can be used individually or in combination of 2 or more types.

The ultraviolet curable acrylic monomer may be included in 10 to 50% by weight based on the total content (100% by weight) of the hard coating agent composition. If the content is less than 10% by weight, the hardness of the coating film is weakened. If the content exceeds 50% by weight, the hardness of the coating film is too high and the electrical conductivity of the surface is lowered.

Reactive silica particles are chemically bonded to a polyfunctional organic material having a polymerizable unsaturated group and a siloxy group on the surface of the silica particle, and more specifically, the silica particles are prepared by chemical bonding by mixing the silica particles with a hydrolyzable silane having a polymerizable unsaturated group. will be. In this case, the preparation of the reactive silica particles may be performed at 20 to 150 ℃ for 5 minutes to 24 hours.

The average particle diameter of the silica particles is not particularly limited, but is preferably nano size, and the specific surface area is not limited, but is preferably 0.001 to 2 m 2 / g, preferably 0.001 to 0.1 m 2 / g. As the silica particles, colloidal silica dispersed in an organic solvent such as a dry powder or a silica sol of methanol may be used.

The hydrolyzable silane may be a carboxylate silyl group such as acetoxy silyl group; Alkoxy silyl groups such as methoxy or ethoxy silyl groups; Halogen silyl groups such as chloro silyl groups; Compounds containing amino and hydride silyl groups and the like can be used, and among these, compounds containing alkoxy silyl groups are preferred.

The polymerizable unsaturated group may include a carboxyl group, a hydroxy group, an acryloxy group, a methacryloxy group, a vinyl group, a propenyl group, a butadienyl group, a styryl group, a cinnamoyl group, a maleate group, an acrylamide group, and the like, and among these, a hydroxy group Preferred are compounds of unsaturated aliphatic carboxylic acids and methacrylates containing.

The content of the hydrolyzable silane having a polymerizable unsaturated group bonded to the reactive silica particles is about 0.05 to 99.0% by weight, preferably 5.0 to 85.0% by weight. If the content is less than 0.05% by weight, it affects the transparency and wear resistance of the cured coating film, and when it exceeds 99.0% by weight, the wear resistance is no longer improved and is inefficient.

The average particle diameter of the reactive silica particles is not particularly limited, but may be used from 0.0001 to 20㎛, preferably 0.001 to 0.1㎛.

The reactive silica particles may be included in 1 to 40% by weight based on the total content (100% by weight) of the hard coating agent composition of the present invention. If the content is less than 1% by weight, there is a problem that the scratch resistance of the coating film is insufficient, and when the content exceeds 40% by weight, there is a problem of fragile.

The organic solvent is used to control the thickness of the coating film and to maintain good coating properties, and any organic solvent having no problem in compatibility with an ultraviolet curing acrylic monomer may be used. Specific examples include methanol, ethanol, isopropanol, propanol, butanol, isobutanol, ethyl cellosolve, methyl cellosolve, butyl acetate, dimethylformamide, diacetone alcohol, ethylene glycol isopropyl alcohol, propylene glycol isopropyl alcohol, Methyl ethyl ketone, N-methylpyrrolidone, etc. are mentioned, These can be used individually or in combination of 2 or more types.

The organic solvent may be included in 30 to 80% by weight relative to the total content of the hard coating agent composition (100% by weight). If the content is less than 30% by weight, there is a problem in coating property, so that a uniform coating film cannot be formed. When the content is more than 80% by weight, the thickness of the coating film is too thin to reduce the surface conductivity.

The photopolymerization initiator is used to sufficiently advance the internal and surface curing of the coating film, and specific examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, and benzoin Isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 4-chronolacetophenone, 4,4- Dimethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2- Morpholino-propane-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethyl Aminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2- Chlorothioc Santon, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylamino benzoic acid ester, 2, 4, 6- trimethyl benzoyl- diphenyl-force Fin oxide, fluorene, triphenylamine, carbazole, etc. are mentioned, These can be used individually or in combination of 2 or more types.

The photopolymerization initiator may be included in 0.1 to 10% by weight based on the total content (100% by weight) of the hard coating agent composition. If the content is less than 0.1% by weight, the curing rate is slow, and if it is more than 10% by weight, it is uneconomical.

In addition, the photopolymerization initiator may be further used together with the photopolymerization initiator. Triethylamine, diethylamine, methyl diethanolamine, ethanolamine, 4-dimethylamino-benzoic acid, isoamyl-4-dimethylaminobenzoate, etc. can be used as a photoinitiator adjuvant.

It is preferable to use an ionic solid as an antistatic agent. The term "ionic solid" refers to a salt formed by an ion combination of an organic cation and an anion, which is a cation containing one or more carbon atoms in a molecule, and a solid state at room temperature (25 ° C). The organic cations and anions may be of the kind described below, and salts of ionic liquids or ionic solids may be generated by combinations thereof. In the present invention, salts which are liquid at room temperature are excluded from salts by ion combination of organic cations and anions.

Examples of the organic cation of the antistatic agent include pyridinium cation, piperidinium cation, pyrrolidinium cation, cation having a pyrroline skeleton, cation having a pyrrole skeleton, imidazolium cation, tetrahydropyrimidinium cation, and dihydropyri. Midium cation, pyrazolium cation, pyrazolinium cation, tetraalkylammonium cation, trialkylsulfonium cation, tetraalkylphosphonium cation, and a cation in which a portion of the alkyl group is substituted with an alkenyl group, alkoxyl group or epoxy group. Can be mentioned. Of these, pyridinium or pyrrolidinium cations are preferred.

Specific examples of the pyridinium cation include 1-ethylpyridinium, 1-butylpyridinium, 1-hexylpyridinium, 1-butyl-3-methylpyridinium, 1-butyl-4-methylpyridinium, 1- Hexyl-3-methylpyridinium, 1-butyl-3,4-dimethylpyridinium, 1-octyl-4-methylpyridinium cation and the like.

Specific examples of the pyrrolidinium cation include 1,1-dimethylpyrrolidinium, 1-ethyl-1-methylpyrrolidinium, 1-methyl-1-propylpyrrolidinium cation and the like.

Specific examples of the cation having a pyrroline skeleton include 2-methyl-1-pyrroline cation, and specific examples of the cation having the pyrroline skeleton include 1-ethyl-2-phenylindole and 1,2-dimethylindole. And 1-ethylcarbazole cation.

Specific examples of the imidazolium cation include 1,3-dimethylimidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium , 1-hexyl-3-methylimidazolium, 1-octyl-3-methylimidazolium, 1-decyl-3-methylimidazolium, 1-dodecyl-3-methylimidazolium, 1-tetradecyl 3-methylimidazolium, 1,2-dimethyl-3-propylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1-butyl-2,3-dimethylimidazolium, 1-hexyl -2,3-dimethylimidazolium cation etc. are mentioned.

Specific examples of the tetrahydropyrimidinium cation include 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3-trimethyl-1,4,5,6-tetrahydro Pyrimidinium, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydro Pyrimidinium cation etc. are mentioned.

Specific examples of the dihydropyrimidinium cation include 1,3-dimethyl-1,4-dihydropyrimidinium, 1,3-dimethyl-1,6-dihydropyrimidinium, and 1,2,3- Trimethyl-1,4-dihydropyrimidinium, 1,2,3-tramethyl-1,6-dihydropyrimidinium, 1,2,3,4-tetramethyl-1,4-dihydropyrimididi Nium, 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium cation, etc. are mentioned.

Specific examples of the pyrazolium cation include 1-methylpyrazolium, 3-methylpyrazolium cation, and the like, and specific examples of the pyrazolium cation include 1-ethyl-2-methylpyrazolium cation. .

Specific examples of the tetraalkylammonium cation include tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, tetraheptylammonium, triethylmethylammonium, tributylethylammonium and trimeth Tildecylammonium, trioctylmethylammonium, tripentylbutylammonium, trihexylmethylammonium, trihexylpentylammonium, triheptylmethylammonium, tripentylbutylammonium, triheptylhexylammonium, dimethyldihexylammonium, dipropyldihexylammonium, Heptyldimethylhexylammonium, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium, glycidyltrimethylammonium, N, N-dimethyl-N-ethyl-N-propylammonium, N, N-dimethyl-N-ethyl-N-butylammonium, N, N-dimethyl-N-ethyl-N-pentylammonium, N, N-dimethyl-N-ethyl-N-hexylammonium, N, N-dimethyl-N -Ethyl-N-heptylammonium, N, N-dimethyl-N-ethyl-N-nonylammonium, N, N-dimethyl-N- Propyl-N-butylammonium, N, N-dimethyl-N-propyl-N-pentylammonium, N, N-dimethyl-N-propyl-N-hexylammonium, N, N-dimethyl-N-propyl-N-heptyl Ammonium, N, N-dimethyl-N-butyl-N-hexylammonium, N, N-dimethyl-N-butyl-N-heptylammonium, N, N-dimethyl-N-pentyl-N-hexylammonium, trimethylheptylammonium , N, N-diethyl-N-methyl-N-propylammonium, N, N-diethyl-N-methyl-N-pentylammonium, N, N-diethyl-N-methyl-N-heptylammonium, N , N-diethyl-N-propyl-N-pentylammonium, triethylmethylammonium, triethylpropylammonium, triethylpentylammonium, triethylheptylammonium, N, N-dipropyl-N-methyl-N-ethylammonium , N, N-dipropyl-N-methyl-N-pentylammonium, N, N-dipropyl-N-butyl-N-hexylammonium, N, N-dibutyl-N-methyl-N-pentylammonium, N , N-dibutyl-N-methyl-N-hexylammonium, trioctylmethylammonium, N-methyl-N-ethyl-N-propyl-N-pentylammonium cation, etc. are mentioned.

Specific examples of the trialkylsulfonium cation include trimethylsulfonium, triethylsulfonium, tributylsulfonium, trihexylsulfonium, diethylmethylsulfonium, dibutylethylsulfonium, and dimethyldecylsulfonium cation. Can be.

Specific examples of the tetraylalkylphosphonium cation include tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrapentylphosphonium, tetrahexylphosphonium, tetraheptylphosphonium, tetraoctylphosphonium and triethyl Methyl phosphonium, tributyl ethyl phosphonium, tributyl ethyl phosphonium, a trimethyldecyl phosphonium cation, etc. are mentioned.

As the anion of the antistatic agent is OTf ^- (trifluoromethyl sulfonate), OTs ^- (toluene-4-sulfonate), OMs ^{- (sulfonate), Cl -, Br -,} I -, AlCl 4 -, _{^{Al 2 Cl 7 -, BF 4}} -, PF 6 -, ClO 4 -, NO 3 -, CH 3 COO -, CF 3 COO -, CH 3 SO 3 -, CF 3 SO 3 -, (CF 3 SO 2) _{^{2 n -, (CF 3 SO}} 2) 3 C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, F (HF) n -, (CN) 2 n -, C 4 F 9 SO 3 _{^{-, (C 2 F 5 SO}} 2) 2 N -, C 3 F 7 COO - or _{(CF 3 SO 2) (CF} 3 CO) N - , and the like. Among these, BF ₄ ^- or PF ₆ ^- is preferable.

Most preferred examples of the antistatic agent include 1-octyl-4-methylpyridinium hexafluorophosphate, 1-butyl-4-methylpyridinium hexafluorophosphate, and hexylpyridinium hexafluorophosphate. These can be used individually or in combination of 2 or more types.

The antistatic agent may be included in an amount of 1.0 to 25% by weight, preferably 10 to 15% by weight, based on the total content (100% by weight) of the hard coating agent composition of the present invention. If the content is less than 1.0% by weight, the surface conductivity becomes weak, so that it is difficult to obtain a desired antistatic property. If the content exceeds 25% by weight, the surface conductivity is improved, but the hardness of the coating film is lowered.

In addition to the above components, it may further include additives such as antioxidants, ultraviolet absorbers, light stabilizers, leveling agents, surfactants, lubricants.

The antistatic hard coating layer is formed by applying an antistatic hard coating agent composition on the first polarizer protective film and then curing. The coating method is not particularly limited as long as it is commonly used in the art, and specifically, an air knife, gravure, reverse roll, kiss roll, spray, or A blade method can be used. More specifically, the antistatic hard coating agent composition on the first polarizer protective film is usually applied directly after drying to have a thickness of 0.1 to 200 μm, preferably about 1 to 50 μm, and from 1 second to 30 to 150 ° C. Dry for 2 hours, preferably 5 seconds to 1 hour. Subsequently, the hard coat layer may be laminated by completely curing by irradiating with an ultraviolet irradiation dose of about 0.01 to 10 J / cm 2, preferably 0.1 to 2 J / cm 2.

The antistatic hard coating layer preferably has a surface resistivity of 1 × 10 ¹¹ to 1 × 10 ¹³ Ω / □. In the above range, it is possible to solve the electrostatic problem that occurs during peeling removal of the surface protection film, and at the same time, the electrostatic problem that occurs during peeling removal of the separator film may be solved to some extent.

The antistatic pressure sensitive adhesive layer is laminated on the second polarizer protective film and is a layer for solving an electrostatic problem generated during peeling removal of the separator film that is difficult to solve only by the antistatic hard coating layer, and is made of an antistatic pressure sensitive adhesive composition. As used herein, the term "pressure-sensitive adhesive" means an adhesive that can be adhered to the surface of the adherend only by applying pressure, and can be removed from the adherend without leaving any traces on the adhered surface when an appropriate strength is applied.

The antistatic pressure-sensitive adhesive composition includes an alkyl (meth) acrylate copolymer, an antistatic agent, a crosslinking agent and a silane coupling agent.

Alkyl (meth) acrylate type copolymer is an alkyl (meth) acrylate type copolymer which has a crosslinkable functional group in a side chain, For example, the alkyl (meth) acrylate monomer which has 4-12 carbon atoms of an alkyl group, bridge | crosslinking to a side chain The copolymer of the polymerizable monomer which has a possible functional group, and the monomer copolymerizable as needed can be used. In this case, (meth) acrylate means that includes both acrylate and methacrylate.

Specific examples of the alkyl (meth) acrylate having 4 to 12 carbon atoms include n-butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, and pentyl (meth) acryl. Acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, and the like, and these may be used alone or in combination. It can be used in combination of two or more kinds. Among them, n-butyl acrylate, 2-ethylhexyl acrylate or a mixture thereof can be preferably used.

Specific examples of the polymerizable monomer having a crosslinkable functional group in the side chain include (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid and their monoalkyl esters, 3- (meth) acryloylpropionic acid, and alkyl groups. 2-hydroxyalkyl (meth) acrylate having 2 to 3 carbon atoms, polyoxyalkylene glycol mono (meth) acrylate having 2 to 4 carbon atoms of an alkyl group, and (meth) acryl having 2 to 3 carbon atoms of an alkyl group Monomers having a carboxyl group such as a compound obtained by ring-opening addition of amber anhydride to a caprolactone adduct to a rate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, polyoxyalkylene glycol mono (meth) having 2 to 4 carbon atoms of an alkyl group Monomers having a hydroxy group such as acrylate; Monomers having an amide group such as (meth) acrylamide; And monomers having tertiary amine groups such as N, N-dimethylamineethyl (meth) acrylate and the like.

Specific examples of the copolymer of the monomer copolymerizable as necessary include (meth) of alcohols having 1 to 3 carbon atoms of alkyl groups such as methyl (meth) acrylate, ethyl (meth) acrylate, and isopropyl (meth) acrylate. ) Acrylic acid ester; (Meth) acrylic acid esters of alcohols having 13 to 18 carbon atoms of alkyl groups such as tridecyl (meth) acrylate and stearyl (meth) acrylate; (Meth) acrylic acid ester of cyclic alcohols, such as cyclohexyl (meth) acrylate; (Meth) acrylates of aromatic alcohols such as benzyl (meth) acrylate; Aromatic monomers such as styrene and vinyltoluene; Allyl compounds such as allyl acetate; Monomers having nitrile groups such as (meth) acrylonitrile and α-chloro (meth) acrylonitrile; Halogen-containing monomers such as vinyl chloride and vinylidene chloride; Vinyl ester monomers such as vinyl acetate, vinyl propionate and vinyl butyrate; Or vinyl ether monomers such as vinyl ethyl ether, vinyl propyl ether, vinyl isobutyl ether, and the like, and methyl (meth) acrylate is preferable.

The weight ratio of the alkyl (meth) acrylate monomer having 4 to 12 carbon atoms of the alkyl group, the polymerizable monomer having a crosslinkable functional group in the side chain, and the copolymerizable monomer as necessary is usually (80 to 99.0): (1.0 to 20): (0-10), Preferably it is (90-99.9): (1.0-10): (0-5). When the weight ratio of the alkyl (meth) acrylate having 4 to 12 carbon atoms corresponding to the main chain in the alkyl (meth) acrylate-based copolymer is less than 80, the adhesive force is insufficient, and when it exceeds 99.0, the cohesive force is lowered. Cohesion force falls when the weight ratio of the polymerizable monomer which has a crosslinkable functional group in a side chain is less than 1.0, and when it exceeds 20, adhesive force falls. Moreover, when the weight ratio of the copolymerizable monomer exceeds 10 as needed, adhesive force falls.

The alkyl (meth) acrylate-based copolymer having a crosslinkable functional group in the side chain has a weight average molecular weight (polystyrene equivalent) measured by gel permeation chromatography (GPC) method is usually 50,000 to 2,000,000, preferably Is 100,000 to 1,800,000, more preferably 500,000 to 1,500,000.

The silane coupling agent is generally used to improve the adhesion between the glass substrate and the adhesive, or the adhesive strength and the heat-and-moisture resistance in the adhesive for liquid crystal display devices, and specific examples thereof include 3-glycidoxypropyltrimethoxysilane and 3-glyco. Cidoxypropyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like, and these may be used alone or in combination of two or more thereof. Can be.

The silane coupling agent is preferably included in an amount of 0.01 to 5.0 parts by weight based on 100 parts by weight of the alkyl (meth) acrylate copolymer. In the content range, it improves the adhesion stability of the pressure-sensitive adhesive composition and further improves the heat and moisture resistance, and in particular, serves to improve the adhesion reliability when left for a long time under high temperature and high humidity.

An ionic compound can be used as an antistatic agent.

The ionic compound is composed of an ion combination of an alkali metal or an organic cation and an anion.

The alkali metal may include one cation selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, barium and cesium.

The anion of said is ^{Cl -, Br -, I -} , AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, CH 3 COO -, CF 3 COO -, _{^{CH 3 SO 3 -, CF 3}} SO 3 -, (CF 3 SO 2) 2 N -, (CF 3 SO 2) 3 C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, F ( ^{_{HF) n -, (CN)}} 2 N -, C 4 F 9 SO 3 -, (C 2 F 5 SO 2) 2 N -, C 3 F 7 COO - , and _{(CF 3 SO 2) (CF} 3 CO) N 1 selected from the group consisting of N ⁻ is mentioned.

In particular, the ionic compound can be used by the same ion combination of the same cation and anion used in the antistatic hard coating agent composition, an ionic liquid which is a solid ionic solid or liquid at room temperature (25 ℃) Can be used.

The antistatic agent is preferably included in 0.05 to 5.0 parts by weight based on 100 parts by weight of the alkyl (meth) acrylate copolymer. More preferably, it is 0.1-2.0 weight part, Especially preferably, it is 0.1-1.0 weight part. In the above content range, the antistatic property is improved while the durability of the pressure-sensitive adhesive composition is practically not impaired.

A crosslinking agent is used in order to strengthen the cohesion force of an adhesive, A well-known crosslinking agent can be used. For example, Melamine derivatives, such as hexamethylol melamine, hexamethoxymethyl melamine, and hexabutoxymethyl melamine; Diisocyanate compounds such as tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, and trimethyrol propane of diisocyanate Polyisocyanate compounds such as adducts to polyhydric alcohol compounds; Polyepoxy compounds such as an epoxy compound of bisphenol A epichlorohydrin condensate type, polyglycidyl ether of polyoxyalkylene polyol, glycerin diglycidyl ether, glycerin triglycidyl ether, and tetraglycidyl xylenediamine; Or an aziridine-based compound such as trimethylolpropane tri-β-aziridinylpropionate, and the like, and preferably a polyisocyanate compound or a polyepoxy compound can be used. These can be used individually or in combination of 2 or more types.

The crosslinking agent is preferably included in 0.1 to 5 parts by weight based on 100 parts by weight of the alkyl (meth) acrylate copolymer. When the content is less than 0.1 parts by weight, the cohesion force becomes small due to insufficient crosslinking degree, thereby impairing the adhesive durability and the cutting property, and when the content exceeds 5 parts by weight, there is a problem in reducing residual stress due to excessive crosslinking reaction.

The antistatic pressure-sensitive adhesive composition comprising the above components may further include a known gun gun additive in a range that does not reduce the adhesive properties, optical properties and antistatic properties, such as durability, re-peelability, and the like. As an example of an additive, tackifying resin, a plasticizer, an ultraviolet inhibitor, a mildew agent, an antifoamer, etc. are mentioned.

The antistatic adhesive layer is formed by a direct coating method or a transfer method commonly used in the art. Specifically, in the case of the direct coating method, the pressure-sensitive adhesive composition is flow casted on a second polarizer protective film using a conventional coating apparatus, and an air knife, gravure, reverse roll, The pressure-sensitive adhesive layer can be formed by directly applying and drying by a kiss roll, spray or blade method. In the transfer method, silicone or fluorinated release film on a film or resin plate of various plastics such as polyethylene, polypropylene, polyethylene terephthalate, soft polyvinyl chloride or the like, preferably silicone release on polyethylene terephthalate By using the obtained film as a base material, and applying and drying in the same coating method as described above can form an adhesive layer, it can be transferred to the polarizer protective film using a roll pressing device.

It is preferable that the antistatic pressure-sensitive adhesive layer has a surface specific resistance of 1 × 10 ¹¹ to 1 × 10 ¹² Ω / □. In the above range, it is possible to solve the problem of static electricity generated when peeling and removing the separator film that the antistatic hard coating layer does not solve.

The polarizing plate may be applied to the upper polarizing plate of the liquid crystal display device.

1 is a cross-sectional view of the upper polarizing plate according to an embodiment of the present invention. As shown in FIG. 1, the polarizing plate 100 of the present invention has a polarizer 114 and a pressure-sensitive adhesive layer for bonding to the liquid crystal cell and the first polarizer protective film 113 disposed on the viewer side as a film for protecting the same. It has a basic structure including a second polarizer protective film 115 is laminated. The antistatic hard coating layer 112 and the surface protection film 111 are sequentially stacked on the first polarizer protective film 113, and the antistatic pressure sensitive adhesive layer 116 and the separator are disposed on the second polarizer protective film 115. The film 117 has a multilayer structure in which the films are sequentially stacked.

In addition, on the antistatic hard coating layer 112, one or more functional coating layers selected from the group consisting of antireflection, low reflection, non-reflection, anti-glare, low refractive index, high refractive index, and electromagnetic shielding layer may be further stacked.

Surface protective film 111 is to be laminated on the antistatic hard coating layer 112 to protect the surface of the polarizing plate and other optical film, if the type is normally used in the art is not particularly limited. For example, polycarbonate film; Polyester film; Polyether sulfone-based film; Alternatively, a film having a structure in which an adhesive layer is laminated on a transparent base film such as polyolefin-based film such as polyethylene, polypropylene, cyclo-based or norbornene-structured polyolefin, and ethylene propylene copolymer can be used.

The separate film 117 is a film for protecting the antistatic pressure-sensitive adhesive layer 116, and the type is not particularly limited as long as it is a film commonly used in the art. Specific examples include polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethylacrylic Polyolefin-based films such as a late copolymer and an ethylene-vinyl alcohol copolymer; Polyester-based films such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate; Polyamide films such as polyacrylate, polystyrene, nylon 6 and partially aromatic polyamide; Polyvinyl chloride film; Polyvinylidene chloride film; Or a polycarbonate film, and the like, and preferably a silicone release coated polyester film may be used. The thickness of the separator film is not particularly limited, and a conventional thickness can be used.

Polarizing plate of the present invention having a multi-layered structure as described above can solve the electrostatic problem that occurs during the peeling removal of the separator film, which is difficult to solve only by the conventional hard coating layer, as well as the electrostatic problem generated during the peeling removal of the surface protection film.

The liquid crystal display device of the present invention is characterized in that the polarizing plate is laminated with the antistatic hard coating layer and the antistatic pressure-sensitive adhesive layer.

In the present invention, since the liquid crystal display is well known to those skilled in the art, detailed description of each configuration except for the antistatic polarizing plate is omitted.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and various changes and modifications within the scope and spirit of the present invention are apparent to those skilled in the art. Naturally, such modifications and variations fall within the scope of the appended claims.

In the following Examples and Comparative Examples, "%" and "parts" indicating contents are by weight unless otherwise specified.

Example  One

(1) 2.8 parts of trimethylolpropane triacrylate, 3.8 parts of bisphenol A-ethylene glycol diacrylate, 13.4 parts of polyethylene glycol diacrylate, reactive silica particles (content of hydrolyzable silane having a hydroxyl group is about 80%, average particle diameter) 0.005 μm) 13 parts, 64 parts of an organic solvent in which isopropanol and methyl cellosolve were mixed at a ratio of 1: 1, 1 part of 1-hydroxycyclohexylphenyl ketone, and 1-octyl-4 as solid at room temperature with an antistatic agent. -1 part of methylpyridinium hexafluorophosphate was added to a small amount of a light stabilizer propylene wax and a UV absorber to prepare a hard coating composition.

(2) CORONATE-L, a polyisocyanate-based crosslinking agent, in 100 parts (based on solids content) of 126 parts of n-butyl acrylate, 0.5 part of acrylic acid, and 1.3 parts of # 2-hydroxyethyl acrylate. Product TDI ADDUCT) 0.65 parts, 3-glycidoxypropyltrimethoxysilane [Shin-Etsu Co., Ltd. KBM-403] as silane coupling agent and 1-octyl-4-methylpyridinium hexafluoro solid at room temperature as antistatic agent 2 parts of phosphate was added and stirred for 20 minutes to prepare an adhesive composition. The prepared pressure-sensitive adhesive composition was applied on a polyethylene terephthalate film (41 cm x 34 cm) coated with a silicone release agent to have a dry film thickness of 25 μm, and dried at 100 ° C. for 1 minute to form a pressure-sensitive adhesive layer. Another layer of the release film was laminated thereon and cured at 23 ° C. for 7 days to prepare an adhesive sheet.

(3) TAC films having a thickness of 40 μm with first and second polarizer protective films on both sides of the polarizer made of a 25 μm thick film in which iodine is adsorbed and oriented on a polyvinyl alcohol-based film, It laminated using the adhesive containing water-soluble epoxy resin. Subsequently, the hard coating composition prepared on the first polarizer protective film was directly applied to have a thickness of 15 μm after drying, dried at 70 ° C. for 1 minute, and then completely cured by irradiating with an ultraviolet irradiation amount of 1J / cm 2. After the hard coating layer was laminated, a polyester-based surface protective film was laminated thereto. Next, after removing the release film on one side of the pressure-sensitive adhesive sheet prepared by laminating using a roll pressing device on the second polarizer protective film to prepare a polarizing plate laminated an antistatic pressure-sensitive adhesive layer.

Example 2

10 parts of 1-octyl-4-methylpyridinium hexafluorophosphate is used in the preparation of the antistatic hard coating agent composition, and 0.8 parts of 1-octyl-4-methylpyridinium hexafluorophosphate is used in the preparation of the antistatic adhesive composition. The same procedure as in Example 1 was carried out except for use.

Example 3

15 parts of 1-octyl-4-methylpyridinium hexafluorophosphate was used in the preparation of the antistatic hard coating agent composition, and 0.6 parts of 1-octyl-4-methylpyridinium hexafluorophosphate in the preparation of the antistatic adhesive composition. The same procedure as in Example 1 was carried out except for use.

Example 4

25 parts of 1-octyl-4-methylpyridinium hexafluorophosphate was used in the preparation of the antistatic hard coating agent composition, and 1-octyl-4-methylpyridinium hexafluoro was used as the antistatic agent in the preparation of the antistatic adhesive composition. The same procedure as in Example 1 was carried out except that 0.3 part of phosphate was used.

Example 5

25 parts of 1-butyl-4-methylpyridinium hexafluorophosphate was used in the preparation of the antistatic hard coating agent composition, and 0.8 parts of 1-butyl-4-methylpyridinium hexafluorophosphate was used in the preparation of the antistatic adhesive composition. The same procedure as in Example 1 was carried out except for use.

Example  6

Example 1 except that 25 parts of hexylpyridinium hexafluorophosphate was used in the preparation of the antistatic hard coating agent composition and 2.0 parts of hexylpyridinium hexafluorophosphate was used in the preparation of the antistatic adhesive composition. It carried out in the same way.

Example 7

Except that 25 parts of 1-octyl-4-methylpyridinium hexafluorophosphate was used in the preparation of the antistatic hard coating agent composition, and 0.3 parts of lithium iodide was used as the antistatic agent in the preparation of the antistatic adhesive composition. It carried out by the same method as 1.

Comparative Example 1

25 parts of 1-octyl-4-methylpyridinium hexafluorophosphate was used in the preparation of the antistatic hard coating agent composition, and 0.05 parts of 1-octyl-4-methylpyridinium hexafluorophosphate in the preparation of the antistatic adhesive composition. Except that was used in the same manner as in Example 1.

Comparative Example 2

0.5 part of 1-octyl-4-methylpyridinium hexafluorophosphate in the preparation of an antistatic hard coating agent composition, and 0.8 part of 1-octyl-4-methylpyridinium hexafluorophosphate in the preparation of an antistatic adhesive composition. The same procedure as in Example 1 was carried out except for use.

Comparative Example 3

0.5 part of 1-octyl-4-methylpyridinium hexafluorophosphate in the preparation of an antistatic hard coating agent composition, and 10 parts of 1-octyl-4-methylpyridinium hexafluorophosphate in the preparation of an antistatic adhesive composition The same procedure as in Example 1 was carried out except for use.

Comparative Example 4

30 parts of 1-octyl-4-methylpyridinium hexafluorophosphate was used in the preparation of the antistatic hard coating agent composition, and 0.8 parts of 1-octyl-4-methylpyridinium hexafluorophosphate was used in the preparation of the antistatic adhesive composition. The same procedure as in Example 1 was carried out except for use.

Comparative Example 5

In preparing the antistatic hard coating composition, 10 parts of an ITO (average particle size 0.3 µm, solid content of 30%) dispersed in methyl isobutyl ketone was used instead of 1-octyl-4-methylpyridinium hexafluorophosphate. The same procedure as in Example 1 was carried out except that 1-octyl-4-methylpyridinium hexafluorophosphate was not used in the preparation of the antistatic adhesive composition.

The components and compositions of the hard coating agent composition and the adhesive composition prepared in Examples and Comparative Examples are shown in Table 1 below.

division Hard coating agent composition (part) Adhesive composition (part) Acrylic monomer Silica Organic solvent Photopolymerization initiator Antistatic Copolymer Silane coupling agent Crosslinking agent Antistatic Example 1 20 13 64 3 A, 1 100 0.15 0.6 A, 2 Example 2 20 13 64 3 A, 10 100 0.15 0.6 A, 0.8 Example 3 20 13 64 3 A, 15 100 0.15 0.6 A, 0.6 Example 4 20 13 64 3 A, 25 100 0.15 0.6 A, 0.3 Example 5 20 13 64 3 B, 25 100 0.15 0.6 B, 0.8 Example 6 20 13 64 3 C, 25 100 0.15 0.6 C, 2.0 Example 7 20 13 64 3 A, 25 100 0.15 0.6 D, 0.3 Comparative Example 1 20 13 64 3 A, 25 100 0.15 0.6 A, 0.05 Comparative Example 2 20 13 64 3 A, 0.5 100 0.15 0.6 A, 0.8 Comparative Example 3 20 13 64 3 A, 0.5 100 0.15 0.6 A, 10 Comparative Example 4 20 13 64 3 A, 30 100 0.15 0.6 A, 0.8 Comparative Example 5 20 13 64 3 E, 10 100 0.15 0.6 -

The type of antistatic agent used in Table 1 is as follows.

* A: 1-octyl-4-methylpyridinium hexafluorophosphate

* B: 1-butyl-4-methylpyridinium hexafluorophosphate

* C: Hexylpyridinium hexafluorophosphate

* D: lithium iodide

* E: ITO solution (average particle size 0.3㎛, solid content 30%, solvent: methyl isobutyl ketone)

Test Example

The physical properties of the polarizing plates prepared in Examples and Comparative Examples were measured by the following method, and the results are shown in Tables 2 and 3 below.

(1) surface resistivity

Using a surface resistance measuring instrument (MCP-HT450, manufactured by Mitsubishi Chemical Co., Ltd.), the three points of the antistatic hard coating layer without the surface protective film and the antistatic pressure-sensitive adhesive layer without the release film laminated thereon were measured 10 times each. And the average value.

division Surface Specific Resistance of Hard Coating Layer (Ω / □) Surface Specific Resistance of Adhesive Layer (Ω / □) Example 1 9 x 10 ¹² 1 x 10 ¹¹ Example 2 3 x 10 ¹² 3 x 10 ¹¹ Example 3 7 x 10 ¹¹ 6 x 10 ¹¹ Example 4 2 x 10 ¹¹ 8 x 10 ¹¹ Example 5 2 x 10 ¹¹ 3 x 10 ¹¹ Example 6 2 x 10 ¹¹ 1 x 10 ¹¹ Example 7 2 x 10 ¹¹ 3 x 10 ¹¹ Comparative Example 1 2 x 10 ¹¹ 3 x 10 ¹² Comparative Example 2 2 x 10 ¹³ 3 x 10 ¹¹ Comparative Example 3 2 x 10 ¹³ 3 x 10 ¹⁰ Comparative Example 4 7 x 10 ¹³ 3 x 10 ¹¹ Comparative Example 5 8 x 10 ⁷ 7 x 10 ¹³

(2) scratch resistance

Test the scratch resistance of the surface of the antistatic hard coating layer by reciprocating 10 times under 1 kg / (2 cm x 2 cm) using a steel wool tester (WT-LCM100, manufactured by Korea Protec Co., Ltd.) Evaluated. At this time, steel wool used # 0000.

◎: 0 scratches

○: 1 to 10 scratches

△: 11 to 20 scratches

X: 21-30 scratches

XX: more than 30 scratches

(3) adhesion durability

The polarizing plate was cut to 15 inches and then bonded to Corning's # 1737 glass to prepare a specimen. The prepared specimens were treated in an autoclave for 5 minutes at 50 ° C. for 20 minutes and then left in an oven at 60 ° C. and 90% relative humidity for 300 hours. Peeling phenomenon such as lifting and peeling of the specimen left undisturbed and bubbles were observed visually, and evaluated based on the following criteria.

○: No peeling phenomenon or bubbles (good)

△: peeling phenomenon and bubbles are somewhat generated

X: Peeling phenomenon and bubbles are generated (defect)

(4) luminance mura measurement

After fabricating a specimen by cutting the polarizing plate to 15 inches, the polarizing plate was bonded to the TFT glass surface of the 15 inch IPS mode monitor panel (manufactured by LG Philips), and then mounted to face the backlight unit. Subsequently, the separator of the cut polarizing plate specimen was peeled off and bonded to the glass surface on the viewer side, and then the surface protective film was removed immediately. At this time, the luminance mura by peeling electrostatic force was measured and evaluated based on the following criteria.

(Double-circle): It is difficult to distinguish a luminosity difference between ducts (very good)

○: shows uniform brightness overall (good)

(Triangle | delta): A partly bright part is observed (usually)

X: The bright and dark parts are clearly distinguished (bad)

division Scratch resistance Adhesive durability Luminance Village Example 1 ○ ○ ○ Example 2 ○ ○ ○ Example 3 ○ ○ ○ Example 4 ○ ○ ○ Example 5 ○ ◎ ○ Example 6 ○ ◎ ○ Example 7 ○ ○ ○ Comparative Example 1 ○ ○ X Comparative Example 2 ○ ○ X Comparative Example 3 ○ X ○ Comparative Example 4 X ○ ○ Comparative Example 5 ◎ ○ X

As shown in Tables 2 and 3 above, the surface specific resistance of the hard coat layer is 1 x 10 ¹¹ to 1 x 10 ¹³ Ω / □ according to the present invention, and the surface specific resistance of the pressure-sensitive adhesive layer is 1 x 10 ¹¹ to 1 x 10 ^12. The polarizing plates of Examples 1 to 7, which are Ω / □, can solve the electrostatic problem generated when peeling and removing not only the surface protective film but also the separator film due to the antistatic interaction between the hard coating layer and the pressure-sensitive adhesive layer. It was confirmed that the durability and luminance-mura characteristics were excellent overall.

On the other hand, the polarizing plates of Comparative Examples 1 to 4 in which the surface specific resistance of any one or two of the hard coating layer and the pressure-sensitive adhesive layer are not included in the scope of the present invention lack the antistatic property, and provide the scratch resistance, the adhesion durability and the luminance-mura characteristics. Could not satisfy evenly. In addition, the polarizing plate of Comparative Example 5, in which ITO was applied to the hard coating layer, had excellent surface resistivity characteristics, but the luminance mura characteristics were not good.

1 is a cross-sectional view showing an example of an upper polarizing plate according to the present invention.

Explanation of symbols on the main parts of the drawings

100: polarizing plate 111: surface protection film

112: antistatic hard coating layer 113: first polarizer protective film

114: polarizer 115: second polarizer protective film

116: antistatic pressure-sensitive adhesive layer 117: separator film

Claims (14)

As a polarizing plate comprising an antistatic hard coating layer and an antistatic pressure-sensitive adhesive layer, The surface resistivity of the antistatic hard coating layer is 1 x 10 ¹¹ to 1 x 10 ¹³ Ω / □, and the surface resistivity of the antistatic pressure-sensitive adhesive layer is 1 x 10 ¹¹ to 1 x 10 ¹² Ω / □. The method of claim 1, wherein the antistatic hard coating layer is an antistatic hard coating composition comprising an ionic solid as an antistatic agent in a hard coating composition comprising an ultraviolet curable acrylic monomer, reactive silica particles, an organic solvent and a photopolymerization initiator. Made of polarizing plate. The polarizing plate of claim 2, wherein the ionic solid is formed by an ion combination of an organic cation and an anion, which is a cation containing one or more carbon atoms in a molecule, and is a salt in a solid state at room temperature (25 ° C.). The cation according to claim 3, wherein the cation is a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a cation having a pyrroline skeleton, a cation having a pyrrole skeleton, an imidazolium cation, a tetrahydropyrimidinium cation, dihydro It is 1 type selected from the group which consists of a pyrimidium cation, a pyrazolium cation, a pyrazolinium cation tetraalkylammonium cation, a trialkylsulfonium cation, and a tetraalkyl phosphonium cation, The anion is ^{OTf -, OTs -, OMs -} , Cl -, Br -, I -, AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, CH 3 COO _{^{-, CF 3 COO -, CH}} 3 SO 3 -, CF 3 SO 3 -, (CF 3 SO 2) 2 N -, (CF 3 SO 2) 3 C -, AsF 6 -, SbF 6 -, NbF 6 - ^{_{, TaF 6 -, F (HF}} ) n -, (CN) 2 n -, C 4 F 9 SO 3 -, (C 2 F 5 SO 2) 2 n -, C 3 F 7 COO - , and (CF ₃ SO ₂ ) (CF ₃ CO) N ^- A polarizing plate which is one kind selected from the group consisting of. 4. The method of claim 3 wherein the cation is a pyridinium cation or pyrrolidine pyridinium cation, the anion is BF ₄ ^- and PF ₆ ^- prevent one member selected from the group consisting of antistatic property polarizer. 5. The ionic solid according to claim 2, wherein the ionic solid is 1-octyl-4-methylpyridinium hexafluorophosphate, 1-butyl-4-methylpyridinium hexafluorophosphate and hexylpyridi. A polarizing plate which is at least one member selected from the group consisting of aluminum hexafluorophosphate. The polarizing plate of claim 2, wherein the ionic solid is present in an amount of 1.0 to 25 wt% based on the total content of the hard coating agent composition (100 wt%). The polarizing plate of claim 1, wherein the antistatic pressure sensitive adhesive layer comprises an antistatic adhesive composition comprising an alkyl (meth) acrylate copolymer, an antistatic agent, a crosslinking agent, and a silane coupling agent. The polarizing plate according to claim 8, wherein the antistatic agent is one selected from the group consisting of alkali metal salts and ionic compounds. The method of claim 9 wherein the alkali metal salt of one selected from lithium, sodium, potassium, magnesium, calcium, and the group consisting of barium and cesium ^{cations, Cl -, Br -, I} -, AlCl 4 -, Al 2 Cl _{^{7 -, BF 4 -, PF}} 6 -, ClO 4 -, NO 3 -, CH 3 COO -, CF 3 COO -, CH 3 SO 3 -, CF 3 SO 3 -, (CF 3 SO 2) 2 N - _{, (CF 3 SO 2) 3} C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, F (HF) n -, (CN) 2 n -, C 4 F 9 SO 3 -, ( _{C 2 F 5 SO 2) 2} N -, C 3 F 7 COO - , and _{(CF 3 SO 2) (CF} 3 CO) N - salt polarizing plate made by combining an ion of the anion of one member selected from the group consisting of. The method of claim 9, wherein the ionic compound is a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a cation having a pyrroline skeleton, a cation having a pyrrole skeleton, an imidazolium cation, a tetrahydropyrimidinium cation, dihydro-pyrimidinyl cation, pyrazolium cation, pyrazolyl Jolly cation tetraalkylammonium cation, a trialkyl sulfonium cation, and tetra-one kind of cations selected from alkyl phosphonium group consisting of cationic and, OTf ^-, OTs ^-, OMs ^{- , Cl -, Br -, I} -, AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, CH 3 COO -, CF 3 COO -, CH 3 SO 3 _{^{-, CF 3 SO 3 -,}} (CF 3 SO 2) 2 N -, (CF 3 SO 2) 3 C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, F (HF) n - ^{_{, (CN) 2 N -,}} C 4 F 9 SO 3 -, (C 2 F 5 SO 2) 2 N -, C 3 F 7 COO - , and _{(CF 3 SO 2) (CF} 3 CO) N - consisting of By ion combination of one anion selected from the group Polar salt is a salt. The polarizing plate of claim 8, wherein the antistatic agent is included in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the alkyl (meth) acrylate copolymer. The polarizing plate of claim 1, further comprising at least one functional coating layer selected from the group consisting of antireflection, low reflection, non-reflection, anti-glare, low refractive index, high refractive index, and electromagnetic shielding layer on the hard coating layer. A liquid crystal display device comprising a polarizing plate according to claim 1 on at least one side of a liquid crystal cell.

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