KR20090110662A - Anti-static hard coating composition and anti-static hard coating film using the same - Google Patents

Abstract

PURPOSE: A composition of antistatic hard coating agent is provided to ensure excellent mechanical property such as high hardness and abrasion resistance and prevent scratch or scrape. CONSTITUTION: A composition of antistatic hard coating agent comprises a hard coating agent composition and ionic solid as an antistatic agent. The hard coating agent composition contains 10-50 weight% of UV curable acrylic monomer; 1-40 weight% of reactivity silica particle; 30-80 weight% of organic solvent; 0.1-10 weight% of photopolymerization initiator and 1.0-25 weight% of antistatic agent.

Description

ANTI-STATIC HARD COATING COMPOSITION AND ANTI-STATIC HARD COATING FILM USING THE SAME}

The present invention relates to an antistatic hard coating composition and an antistatic hard coating film using the same which are excellent in high hardness, wear resistance, and at the same time, excellent in antistatic property and optical performance.

Liquid crystal display devices (LCDs) are used in various applications such as notebooks, mobile phones, liquid crystal TVs, etc., and generally require liquid crystal cells and polarizing plates containing liquid crystals. In addition, the polarizing plate is provided with a polarizer protective film on both sides of the polarizer, the anti-reflective, anti-glare, high hardness, antistatic functional coating layer is further added on the polarizer protective film, the protective film is attached thereon. In addition to the polarizing plate, the use of optical films such as retardation plates, brightness enhancement films, etc., as optical elements for improving the quality of display devices in liquid crystal panels is increasing.

However, the optical film as described above has high surface resistance and is easy to attach foreign substances to the surface due to the occurrence of static electricity. In particular, as the liquid crystal display device is enlarged in recent years, the problem of liquid crystals being broken by static electricity due to external charges is increasing. For example, static electricity is generated by the film adhesive in the protective film removal step of the LCD polarizer during production of a large LCD substrate, and the generated static electricity may cause fatal damage to the LCD module. In addition, the optical film has a problem that scratches or scrapes are easily generated due to contact due to external impact due to low surface hardness, and thus transparency is impaired.

In order to solve this problem, a method of using a conductive coating such as a metal such as aluminum or carbon black and an additive such as a surfactant that exhibits ion conductivity by reacting with water has been proposed for the hard coating composition. There is a problem in lowering, the surfactant is sensitive to moisture in the air and temperature dependence is large, so there is a problem of poor durability or durability and polluting other materials.

In addition, a method of preparing a hard coating composition using a hydrophilic monomer and an ion conductive monomer has also been proposed, but the compositions are often not antistatic, and even if they are antistatic, they are often degraded over time. (Japanese Laid-Open Patent Nos. 1993-214044, 1993-214045, 193-186534, and Korean Laid-Open Patent No. 2001-0058446).

Alternatively, a method of using a conductive polymer such as polyaniline, polypyrrole, polythiophene, or the like in a hard coating agent composition has been proposed. They are easy to polymerize and have excellent conductivity and oxidative stability, so they can be applied as various conductive materials. However, they have a drawback of their own color and are difficult to apply to transparent substrates. Therefore, although it is applied as a thin film, the hardness of the coating layer formed after application is low, a large amount of scratches occur, there is a disadvantage that the antistatic performance is also reduced (Japanese Patent Publication Nos. 1995-292081, 1994-295016).

Recently, an antistatic hard coating agent using a metal oxide-based conductive sol such as ATO (antimontinoxide) or ITO (indiumtinoxide) has been developed as a hard coating agent. In such coatings, excellent antistatic persistence by free electron charge transfer and excellent transparency have been generally applied to commercial applications. However, these metal oxides are not very economical and are not suitable for commercial applications because the price of the coating solution itself is very expensive and increases the cost of the final product.

An object of the present invention is to provide an antistatic hard coating agent composition which is excellent in high hardness and wear resistance and at the same time excellent in antistatic property and optical performance, which is very suitable for surface protection of various display devices.

In another aspect, the present invention is to provide an antistatic hard coating film using the antistatic hard coating agent composition.

Another object of the present invention is to provide a polarizing plate and a liquid crystal display device having the antistatic hard coating film.

In order to achieve the above object, the present invention provides an antistatic hard coating agent composition comprising an ionic solid as an antistatic agent in a hard coating agent composition comprising an ultraviolet curable acrylic monomer, a reactive silica particles, an organic solvent and a photopolymerization initiator.

The present invention also provides an antistatic hard coating film in which a hard coating layer made of the antistatic hard coating composition is laminated on a transparent base film.

In another aspect, the present invention provides a polarizing plate and a liquid crystal display device provided with the antistatic hard coating film.

According to the present invention, it is excellent in mechanical properties such as high hardness and wear resistance to prevent scratches or scrapes caused by contact due to external impact and at the same time excellent antistatic properties to solve the electrostatic problem It is possible to provide an antistatic hard coating film suitable for the surface protection of various display devices with excellent optical performance. It also lowers the cost of the coating solution itself and the cost of the final product, making it economical and suitable for a variety of commercial applications.

The present invention relates to an antistatic hard coating agent composition suitable for the surface protection of various display devices having excellent hardness, wear resistance, and excellent antistatic property and optical performance, and an antistatic hard coating film using the same.

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

The antistatic hard coating agent composition of the present invention is characterized in that it comprises an ionic solid as an ultraviolet curing acrylic monomer, reactive silica particles, an organic solvent, a photopolymerization initiator and an antistatic agent.

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 UV 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 of the present invention. 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, more 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 ineffective.

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, when the content exceeds 40% by weight there is a problem that the coating film is easily broken.

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 (100% by weight) of the hard coating agent composition of the present invention. 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-dime Oxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-mor Polyno-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylamino Benzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chloro Tio Ton, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoic acid ester, 2,4,6-trimethylbenzoyl-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 relative to the total content (100% by weight) of the hard coating agent composition of the present invention. 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.

Such ionic solids are characterized by excellent scratch resistance when applied to the coating film compared to the ionic liquid, and compared to the metal oxides such as ITO or ATO, so that the ionic solid is present in a dissolved state rather than dispersed in the coating agent. There is no problem of dispersion of the resin and the instability of the coating during application, and the haze is low so that the contrast is not lowered. Therefore, it is more preferably used in the present invention.

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-diethylimidazolium, 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, 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 trimethyldecyl Ammonium, Trioctylmethylammonium, Tripentylbutylammonium, Trihexylmethylammonium, Trihexylpentylammonium, Triheptylmethylammonium, Tripentylbutylammonium, Triheptylhexylammonium, Dimethyldihexylammonium, Dipropyldihexylammonium, Heptyldimethyl Hexylammonium, 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- Lofil-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 triethylmethyl Phosphonium, tributylethylphosphonium, tributylethylphosphonium, trimethyldecylphosphonium cation, and the like.

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 content of the antistatic agent is not particularly limited, it is preferably included in 1.0 to 25% by weight, more preferably 10 to 15% by weight relative to the total content (100% by weight) of the hard coating agent composition of the present invention. have. If the content is less than 1.0% by weight, the surface conductivity may be weakened. If the content exceeds 25% by weight, the surface conductivity may be improved, but the hardness of the coating film may be 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 film of the present invention is characterized in that a hard coating layer made of the antistatic hard coating agent composition is laminated on a transparent base film.

The transparent base film is not particularly limited as long as it is a transparent plastic film. Specific examples include cellulose derivatives such as diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, isobutyl ester cellulose, ethylene-vinyl acetate copolymer, propionyl cellulose, butyryl cellulose and acetyl propionyl cellulose, and polyester , Polystyrene, polyamide, polyetherimide, polyacryl, polyimide, polyethersulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, poly Ether ketones, polyether ether ketones, polyether sulfones, polymethyl methacrylates, polyethylene terephthalates, polybutylene terephthalates, polyethylene naphthalates, polycarbonates, polyurethanes, epoxy films, and the like, and these may be unstretched, 1 or 2 axes It may be a film. Among them, a uniaxial or biaxially stretched polyester film having excellent transparency and heat resistance, but a triacetyl cellulose film is preferable in view of transparency and optically anisotropy.

The transparent base film has a thickness of about 8 to 1000 μm, preferably 40 to 100 μm.

The hard coat layer is formed by applying an antistatic hard coat agent composition on a transparent base 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 is applied directly onto the transparent substrate film to have a thickness of usually 0.1 to 200 탆, preferably about 1 to 50 탆, after drying, for 1 second to 2 hours at 30 to 150 ° C. , Preferably for 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.

In addition, 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, electromagnetic wave shielding layer, and the like may be laminated on the hard coating layer of the antistatic hard coating film.

The antistatic hard coating film is used for the surface protection of various image display devices such as a protective film of an optical film, a liquid crystal display, a plasma display, a CRT, an electroluminescent display, and the like.

The present invention also provides a polarizing plate and a liquid crystal display device having the antistatic hard coating film.

In the polarizing plate and the liquid crystal display of the present invention, which configuration the antistatic hard coating film is applied to is not particularly limited, and may be preferably applied as long as a film having excellent mechanical properties and antistatic properties can be used at the same time. For example, the protective film of a polarizing plate, the image display part protective film of a liquid crystal display device, etc. are mentioned.

In the present invention, since the polarizing plate and the liquid crystal display are well known to those skilled in the art, detailed descriptions of the respective components except for the antistatic hard coating film are 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 it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications 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

2.8 parts of trimethylolpropanetriacrylate, 3.8 parts of bisphenol A-ethylene glycol diacrylate, 13.4 parts of polyethylene glycol diacrylate, reactive silica particles (about 80% of hydrolyzable silane having a hydroxyl group, average particle size of 0.005 탆) 13 parts, 64 parts of an organic solvent in which isopropanol and methyl cellosolve are mixed at a ratio of 1: 1, 1 part of 1-hydroxycyclohexylphenyl ketone, and 1-octyl-4-methylpyri as solid at room temperature as an antistatic agent. 1 part of dinium hexafluorophosphate was mixed. A small amount of propylene wax and an ultraviolet absorber, which are light stabilizers, were added thereto to prepare a hard coating composition.

The prepared hard coating agent composition was dried on a triacetyl cellulose (TAC) transparent substrate film having a thickness of 50 μm, and then directly applied to have a thickness of 15 μm, and dried at 70 ° C. for 1 minute. Subsequently, the film on which the hard coat layer was laminated | stacked was produced by irradiating with the ultraviolet irradiation amount of 1J / cm <2> and fully hardening.

Example  2

The same procedure as in Example 1 was conducted except that 5 parts of 1-octyl-4-methylpyridinium hexafluorophosphate was used as an antistatic agent.

Example  3

 The same procedure as in Example 1 was carried out except that 10 parts of 1-octyl-4-methylpyridinium hexafluorophosphate was used as an antistatic agent.

Example  4

 The same procedure as in Example 1 was carried out except that 15 parts of 1-octyl-4-methylpyridinium hexafluorophosphate was used as an antistatic agent.

Example  5

 The same procedure as in Example 1 was conducted except that 25 parts of 1-octyl-4-methylpyridinium hexafluorophosphate was used as an antistatic agent.

Example  6

 The same procedure as in Example 1 was carried out except that 0.5 part of 1-octyl-4-methylpyridinium hexafluorophosphate was used as an antistatic agent.

Example  7

 The same procedure as in Example 1 was carried out except that 30 parts of 1-octyl-4-methylpyridinium hexafluorophosphate was used as an antistatic agent.

Example  8

 The same procedure as in Example 1 was conducted except that 10 parts of 1-butyl-4-methylpyridinium hexafluorophosphate was used as an antistatic agent.

Example  9

 The same procedure as in Example 1 was conducted except that 10 parts of hexylpyridinium hexafluorophosphate was used as an antistatic agent.

Comparative example  One

Except for using 10 parts of 4-methyl-1-hexylpyrimidinium hexafluorophosphate liquid at room temperature as an antistatic agent was carried out in the same manner as in Example 1.

Comparative example  2

Except for using 10 parts of NaPF ₆ as the antistatic agent was carried out in the same manner as in Example 1.

Comparative example  3

Except for using 10 parts of ITO (average particle size 0.3㎛, solid content 30%) dispersed in methyl isobutyl ketone as an antistatic agent was carried out in the same manner as in Example 1.

The components and compositions of the hard coating agent compositions prepared in Examples and Comparative Examples are shown in Table 1 below. At this time, the content of each component represents parts by weight.

division Acrylic monomer Reactive silica Organic solvent Photopolymerization Initiator Antistatic agent A-1 A-2 A-3 B-1 B-2 B-3 B-4 B-5 B-6 Example 1 2.8 3.8 13.4 13 64 3 One - - - - - Example 2 2.8 3.8 13.4 13 64 3 5 - - - - - Example 3 2.8 3.8 13.4 13 64 3 10 - - - - - Example 4 2.8 3.8 13.4 13 64 3 15 - - - - - Example 5 2.8 3.8 13.4 13 64 3 25 - - - - - Example 6 2.8 3.8 13.4 13 64 3 0.5 - - - - - Example 7 2.8 3.8 13.4 13 64 3 30 - - - - - Example 8 2.8 3.8 13.4 13 64 3 - 10 - - - - Example 9 2.8 3.8 13.4 13 64 3 - - 10 - - - Comparative Example 1 2.8 3.8 13.4 13 64 3 - - - 10 - - Comparative Example 2 2.8 3.8 13.4 13 64 3 - - - - 10 - Comparative Example 3 2.8 3.8 13.4 13 64 3 - - - - - 10

In Table 1, the components of the acrylic monomer and the antistatic agent are as follows.

A-1: trimethylol propane triacrylate

A-2: Bisphenol A-ethylene glycol diacrylate

A-3: polyethylene glycol diacrylate

B-1: 1-octyl-4-methylpyridinium hexafluorophosphate

B-2: 1-butyl-4-methylpyridinium hexafluorophosphate

B-3: Hexylpyridinium hexafluorophosphate

B-4: 4-methyl-1-hexylpyridinium (liquid at room temperature)

B-5: NaPF ₆

B-6: ITO (average particle size 0.3㎛, solid content 30%, solvent; methyl isobutyl ketone)

Test Example

The physical properties of the antistatic hard coating film prepared in Examples and Comparative Examples were measured by the following method, and the results are shown in Table 2 below.

(1) haze

Haze was measured with the spectrophotometer (HZ-1, the Japan Corporation make) facing the transparent base film surface toward the light source D65.

(2) pencil hardness

Pencil hardness was measured using a pencil hardness tester (PHT, manufactured by Seokbo Science Co., Ltd.) at 500 g. The pencil was performed 5 times using Mitsubishi 3H product, and evaluated based on the following criteria. At this time, if there were two or more scratches, it was judged as defective.

О: 1 or less scratches (good)

X: 2 or more scratches (bad)

(3) scratch resistance

Using a steel wool tester (WT-LCM100, manufactured by Protec Co., Ltd.) for 10 reciprocating motions under 1 kg / (2 cm × 2 cm), the scratch resistance was tested and evaluated based on the following criteria. At this time, steel wool used # 0000.

◎: 0 scratches

○: 1 to 10 scratches

△: 11 to 20 scratches

X: 21-30 scratches

(4) adhesion

After drawing 11 straight lines each at 1 mm intervals on the coated surface of the film to make 100 squares, a peel test was performed three times using a tape (CT-24, manufactured by Nichi Nippon Co., Ltd.). The average value is shown after the calculation.

Adhesion = n / 100

In the formula, n represents the number of squares not peeled off.

(5) surface resistivity

Three points of the antistatic pressure-sensitive adhesive layer were measured 10 times each using a surface resistance measuring instrument (MCP-HT450, manufactured by Mitsubishi Chemical Co., Ltd.), and the average values were represented.

division Haze (%) Pencil hardness Scratch resistance Adhesion Surface resistivity (Ω / □) Example 1 0.3 ○ ◎ 100/100 9 × 10 ¹² Example 2 0.4 ○ ○ 100/100 7 × 10 ¹² Example 3 0.4 ○ ○ 100/100 5 × 10 ¹² Example 4 0.6 ○ ○ 100/100 7 × 10 ¹¹ Example 5 0.9 ○ △ 100/100 3 × 10 ¹¹ Example 6 0.5 ○ △ 99/100 3 × 10 ¹³ Example 7 1.1 ○ △ 100/100 7 × 10 ¹² Example 8 0.4 ○ ○ 100/100 5 × 10 ¹² Example 9 0.4 ○ ○ 100/100 5 × 10 ¹² Comparative Example 1 0.3 ○ X 100/100 4 × 10 ¹² Comparative Example 2 1.2 X X 98/100 6 × 10 ¹¹ Comparative Example 3 2.2 ○ ○ 90/100 8 × 10 ⁷

As shown in Table 2, the hard coating film of Examples 1 to 9 including an ionic solid as an antistatic agent in accordance with the present invention is excellent in mechanical properties such as haze, hardness, scratch resistance and adhesion at the same time I could confirm that. In particular, in Examples 1 to 6 containing the ionic solid at 1.0 to 25% by weight it was confirmed that the mechanical properties and antistatic properties are more preferable.

On the other hand, Comparative Example 1 containing an ionic liquid as an antistatic agent was excellent in antistatic properties, so scratch resistance was not very good, Comparative Example 2 containing an ionic salt was confirmed that the mechanical properties of pencil hardness and scratch resistance is not good Could. In addition, Comparative Example 3 including ITO was excellent in antistatic properties, but it was not economical considering that the haze was high, the adhesion was not good, and the price of the coating solution itself was expensive.

Claims (13)

An antistatic hard coating composition comprising an ionic solid as an antistatic agent in a hard coating composition comprising an ultraviolet curable acrylic monomer, a reactive silica particle, an organic solvent, and a photopolymerization initiator. The method according to claim 1, wherein 10 to 50% by weight of the ultraviolet curable acrylic monomer, 1 to 40% by weight of reactive silica particles, 30 to 80% by weight of an organic solvent, 0.1 to 10% by weight of a photopolymerization initiator and 1.0 to 25% by weight of an antistatic agent. Antistatic hard coating agent composition comprising. The antistatic hard coating agent composition of claim 1, wherein the 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 particles. The antistatic hard coating agent composition of claim 1, 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 method according to claim 4, wherein the cation is pyridinium cation, piperidinium cation, pyrrolidinium cation, cation having a pyrroline skeleton, cation having a pyrrole skeleton, imidazolium cation, 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 ^- Antistatic hard coating agent composition is one selected from the group consisting of. The method of claim 4, wherein the cation is a pyridinium cation or pyrrolidine pyridinium cation, the anion is BF ₄ ^- or PF ₆ ^- the antistatic hard coating composition. The group of claim 1, wherein the ionic solid consists of 1-octyl-4-methylpyridinium hexafluorophosphate, 1-butyl-4-methylpyridinium hexafluorophosphate, and hexylpyridinium hexafluorophosphate. At least one antistatic hard coating agent composition selected from. An antistatic hard coating film comprising a hard coating layer comprising the antistatic hard coating agent composition of claim 1 on a transparent base film. The method of claim 8, wherein the transparent substrate film is diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, isobutyl ester cellulose, ethylene-vinyl acetate copolymer, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, poly Ester, polystyrene, polyamide, polyetherimide, polyacryl, polyimide, polyethersulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, Anti-static, one kind selected from the group consisting of polyether ketone, polyether ether ketone, polyether sulfone, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyurethane and epoxy film Castle hard coating Name. The polarizing plate of claim 8 is provided with an antistatic hard coating film. 11. The method of claim 10, wherein 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 wave shielding layer on the hard coating layer of the antistatic hard coating film Two more laminated polarizers. The liquid crystal display device of claim 8, wherein the antistatic hard coating film is provided. A liquid crystal display device comprising the polarizing plate of claim 10.