KR20100019661A - Anti-static hard coating composition and anti-static hard coating film using the same - Google Patents

Abstract

PURPOSE: An anti-static hard coating composition is provided to ensure excellent hardness and abrasion resistance, and good antistatic property and optical performance, and to be suitable for preventing the surface of various display devices. CONSTITUTION: An anti-static hard coating composition comprises a UV curable acrylic monomer, reactive silica particles, organic solvent, photopolymerization initiator and antistatic agent. The antistatic agent is an ion complex consisting of alkyl amide and alkali metal salt. The ion complex is represented by chemical formula 1. In chemical formula 1, R1 and R2 are hydrogen, C1-22 alkyl group, C1-22 unsaturated hydrocarbon group, alkylsilane group or perfluoroalkyl group; M^+ is cation of the alkali metal salt; and X^- is anion of the alkali metal salt.

Description

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

The present invention relates to an antistatic hard coating agent composition and an antistatic hard coating film using the same which are excellent in hardness, 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.

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 a 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 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 hardness, 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 addition, another object of the present invention to provide an antistatic hard coating film using the antistatic hard coating agent composition.

In addition, 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 is a hard coating agent composition comprising an ultraviolet curable acrylic monomer, a reactive silica particles, an organic solvent, a photopolymerization initiator and an antistatic agent, wherein the antistatic agent is an ion complex composed of alkylamide and an alkali metal salt An anti-hard coating composition is provided.

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 addition, 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 hardness and wear resistance to prevent scratches or scrapes caused by contact due to external impact and at the same time excellent antistatic properties can solve the electrostatic problem In addition, the optical performance is excellent, it is possible to provide an antistatic hard coating film suitable for the surface protection of various display devices. In addition, the cost of the coating solution itself and the cost of the final product can be lowered, which is economical and suitable for various commercial applications.

The present invention relates to an antistatic hard coating agent composition having excellent hardness, abrasion resistance and at the same time excellent antistatic property and optical performance, which is very suitable for surface protection of various display devices, 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 complex composed of an alkylamide and an alkali metal salt as an ultraviolet curable acrylic monomer, a reactive silica particle, 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; Or 6 functional monomers, such as caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. are mentioned, 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, and 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 0.005 to 0.03 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, a 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.

The antistatic agent is preferably an ionic complex composed of alkylamide and alkali metal salt. More specifically, the antistatic agent is an ionic complex formed by the coordinating bond of alkylamide and alkali metal salt.

The ion complex may be a compound represented by Formula 1 below.

Wherein R ₁ and R ₂ are each hydrogen, an alkyl group having 1 to 22 carbon atoms, an unsaturated hydrocarbon group having 1 to 22 carbon atoms, an alkylsilane group or a perfluoroalkyl group, and at least one of R ₁ and R ₂ is hydrogen And M ⁺ is a cation of an alkali metal salt and X ⁻ is an anion of an alkali metal salt).

Examples of the alkyl group having 1 to 22 carbon atoms include methyl group, ethyl group, propyl group, butyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tetradecyl group, cetyl group, stearyl group, oleyl group or biphenyl group Etc. can be mentioned.

Moreover, the kind is not specifically limited as said C1-C22 unsaturated hydrocarbon group, Specifically, an acryl group, benzyl group, or a phenyl group etc. are mentioned.

A cation of the alkali metal salt may be a full selected from the group consisting of lithium, sodium and potassium and the anion of the alkali metal salt is OTf ^- (trifluoromethane sulfonate), OTs ^- (toluene-4-sulfonate), OMs ^- (methane sulfonate), TfSI ^- (trifluoro methane sulfonyl ^{imide), 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 may be all selected from the group consisting of. An alkali metal salt is formed by the combination of such cations and anions, and among these combinations, those having high solubility in organic solvents are preferable.

With said alkyl amide is R ₁ is a methyl group and R ₂ is a hydrogen acetamide are preferred, and the alkali metal salt cation is lithium and the anion is I ^-, ClO ₄ ^- or TfSI ^- and in that, more preferably a cation the lithium and the anion is ClO ₄ ^- is a.

The equivalent ratio of the alkylamide and the alkali metal salt is preferably 1: 0.9 to 1: 1.2, more preferably 1: 1 to 1: 1.2. If the equivalent ratio is less than 1: 0.9, the antistatic property may be lowered due to the unreacted alkylamide compound. If the equivalent ratio is greater than 1: 1.2, the antistatic property is maintained, but the meltability at high temperature is lowered and the price is increased. It is economical.

The ion complex may be prepared by a method of melting the alkylamide and the alkali metal salt at a high temperature. Looking at the preparation method of the ion complex in detail, 0.8 to 1.2 parts by weight of the alkylamide compound is added and the temperature is heated to 60 ℃ or more and completely dissolved, 0.8 to 1.2 parts by weight of alkali metal salt is added thereto for 1 to 6 hours Prepared by stirring. At this time, the use amount is adjusted so that the equivalent ratio of alkylamide and alkali metal salt is 1: 0.9 to 1: 1.2. The reaction temperature is not particularly limited as long as it is equal to or higher than the melting point of the alkylamide compound. However, when the reaction temperature is lower than the melting point, the reaction rate is very low. The prepared ion complex may be applied by solidifying or liquidifying at room temperature.

The ion complex prepared by the above method has excellent antistatic performance and scratch resistance, and unlike metal oxides such as ITO or ATO, it can be directly applied in a dissolved state instead of dispersion at room temperature, so it is difficult to disperse in the coating solution. And there is no problem of over time instability of the coating liquid, there is a characteristic that does not lower the contrast because the haze value is low.

The content of the antistatic agent is not particularly limited, it is preferably included in 0.5 to 30% by weight, more preferably 1.0 to 25% by weight, most preferably based on the total content (100% by weight) of the hard coating agent composition of the present invention. It may be included in 5 to 20% by weight. If the content is less than 0.5% by weight, the surface conductivity may be weakened. When the content is more than 30% by weight, the surface conductivity may be improved, but the hardness of the coating may be reduced.

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, polymethyl methacrylates, polyethylene terephthalates, polybutylene terephthalates, polyethylene naphthalates, polycarbonates, polyurethanes, epoxy films and the like can be used, which are unstretched, monoaxial or biaxial; Axially stretched film The. 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 a method commonly used in the art, and specifically, a bar coater, air knife, gravure, reverse roll, kiss roll , Spray or blade methods may be used. More specifically, the antistatic hard coating agent composition on the transparent substrate film is usually applied directly after drying to a thickness of 0.1 to 200㎛, preferably about 1 to 50㎛, 1 second to 2 hours at 30 to 150 ℃ , 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.

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.

Production Example  One. Acetamide and LiClO ₄ Ion Complex  B-1 manufacturing

277.45 g of acetamide was added to a 1 L reactor equipped with a temperature controller and a heater to control the temperature, and then the temperature of the reactant was raised to 60 ° C. to completely melt the acetamide, and then slowly stirred 500 g of LiClO ₄ with alkali metal salt while stirring. Input. After adding all of LiClO ₄ , the mixture was stirred for 2 hours, and cooled to room temperature to prepare 776.2 g (yield 99.8%) of ion complex B-1 (produced by Suyang Chemtech Co., Ltd.).

Production Example  2. Acetamide and LiI Ion Complex  B-2 manufacturing

Except for using 236.3 g of acetamide and 535.4 g of LiI, 757 g (yield 98.1%) of Ion Complex B-2 (manufactured by Suyang Chemtech Co., Ltd.) was prepared in the same manner as in Preparation Example 1 above.

Preparation Example 3 Preparation of Ion Complex B-3 of Acetamide and LiTfSI

Except for using 118.1 g of acetamide and 574.2 g of LiTfSI, 690 g (yield 99.7%) of Ion Complex B-3 (manufactured by Suyang Chemtech Co., Ltd.) was prepared in the same manner as in Preparation Example 1.

Example 1

2.8 parts of trimethylolpropane triacrylate (A-1), 3.8 parts of bisphenol A-ethylene glycol diacrylate (A-2), 13.4 parts of polyethylene glycol diacrylate (A-3), reactive silica particles (having a hydroxy group About 80% of hydrolyzable silane, average particle size: 0.005㎛) 13 parts, 64 parts of organic solvent in which isopropanol and methyl cellosolve are mixed at a ratio of 1: 1, 1 part of 1-hydroxycyclohexylphenyl ketone , 1 part of Ion Complex B-1 of Preparation Example 1 was mixed with an antistatic agent. A small amount of propylene wax and an ultraviolet absorber, which are light stabilizers, were added thereto to prepare a hard coating composition.

After drying the prepared hard coating composition on a transparent substrate film (40㎛, TAC) by using a Myer bar so as to have a thickness of 14㎛, and dried for 1 minute at 70 ℃, irradiated with an ultraviolet irradiation amount of 720mJ / ㎠ by curing The film in which the hard coat layer was laminated was prepared.

Example 2

Except for using 5 parts of the ion complex B-1 of Preparation Example 1 as an antistatic agent was carried out in the same manner as in Example 1.

Example 3

Except for using 10 parts of the ion complex B-1 of Preparation Example 1 as the antistatic agent was carried out in the same manner as in Example 1.

Example 4

Except for using 15 parts of the ion complex B-1 of Preparation Example 1 as an antistatic agent was carried out in the same manner as in Example 1.

Example 5

Except for using 20 parts of the ion complex B-1 of Preparation Example 1 as an antistatic agent was carried out in the same manner as in Example 1.

Example 6

The same procedure as in Example 1 was carried out except that 25 parts of the ion complex B-1 of Preparation Example 1 was used as an antistatic agent.

Example 7

Except for using 10 parts of the ion complex B-2 of Preparation Example 2 as an antistatic agent was carried out in the same manner as in Example 1.

Example  8

Except for using 10 parts of the ion complex B-3 of Preparation Example 3 as the antistatic agent was carried out in the same manner as in Example 1.

Comparative Example 1

Except for using 10 parts of LiClO ₄ (B-4) as an antistatic agent was carried out in the same manner as in Example 1.

Comparative Example 2

The same procedure as in Example 1 was carried out except that 10 parts of 4-methyl-1hexylpyridinium hexafluorophosphate (B-5), which was a liquid at room temperature, was used as an antistatic agent.

Comparative Example 3

Except for using 10 parts of ATO (average particle diameter 0.03㎛, solid content 30%) (B-6) dispersed in methyl isobutyl ketone as an antistatic agent was carried out in the same manner as in Example 1.

The components and contents of the hard coating agent compositions prepared in the above 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 20 - - - - - Example 6 2.8 3.8 13.4 13 64 3 25 - - - - - Example 7 2.8 3.8 13.4 13 64 3 - 10 - - - - Example 8 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: Ion Complex of Acetamide and LiClO ₄

B-2: Ion Complex of Acetamide and LiI

B-3: Ion Complexes of Acetamide and LiTfSI

B-4: LiClO ₄

B-5: 4-methyl-1hexylpyridinium hexafluorophosphate (liquid at room temperature)

B-6: ATO (average particle diameter 0.03㎛, 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) transmittance (%) and haze (%)

Total light transmittance and total haze were measured using a spectrophotometer (HZ-1, manufactured by Suga Corporation, Japan).

(2) pencil hardness

Pencil hardness was measured using a pencil hardness tester (PHT, manufactured by Seokbo Science Co., Ltd.) at 500 g. The pencil used Mitsubishi 3H product, and was repeated 5 times with one pencil. At this time, when there were more than two scratches, it was determined to be defective.

(3) scratch resistance

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

◎: 0 scratches

○: 1 to 10 scratches

△: 11 to 20 scratches

×: 21 to 30 scratches

××: 31 or more scratches

(5) 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, Nichi-Nisa, Japan). After calculating by 1, the average value was shown. At this time, when no square is peeled off, it is represented as 100/100.

Adhesion = n / 100

(In formula, n represents the number of squares which do not peel.)

(6) Surface specific resistance (Ω / □)

The surface resistivity of three points on the surface of the hard coat layer laminated on the transparent base film was measured 10 times using a surface resistance measuring instrument (MCP-HT450, manufactured by Mitsubishi Chemical Co., Ltd.), and the average value was shown.

division Transmittance (%) Haze (%) Pencil hardness Scratch resistance Adhesion Surface resistivity (Ω / □) Example 1 92.3 0.3 2H ○ 100/100 3 × 10 ¹¹ Example 2 91.8 0.4 2H ○ 100/100 1 × 10 ¹¹ Example 3 91.5 0.4 2H ○ 100/100 5 × 10 ¹⁰ Example 4 90.9 0.5 2H △ 100/100 1 × 10 ¹⁰ Example 5 90.7 0.6 2H △ 100/100 8 × 10 ⁹ Example 6 90.4 0.9 2H △ 100/100 5 × 10 ⁹ Example 7 90.1 1.1 2H ○ 100/100 2 × 10 ¹⁰ Example 8 91.2 0.4 2H ○ 100/100 3 × 10 ¹⁰ Comparative Example 1 91.3 0.4 2H × 98/100 7 × 10 ¹³ Comparative Example 2 91.6 0.3 2H ×× 100/100 2 × 10 ¹² Comparative Example 3 89.3 2.2 2H ○ 90/100 8 × 10 ⁷

As shown in Table 2, the hard coating film of Examples 1 to 8 comprising an ion complex composed of alkylamide and an alkali metal salt as an antistatic agent according to the present invention, such as transmittance, haze, pencil hardness, scratch resistance and adhesion It was confirmed that the antistatic property as well as the optical and mechanical properties.

On the other hand, Comparative Example 1 containing the ionic salt LiClO ₄ as an antistatic agent was excellent in pencil hardness, but did not have good antistatic property, scratch resistance and adhesion, 4-methyl-1hexylpyridinium hexafluoro ionic liquid Comparative Example 2 containing a low phosphate was not good antistatic properties and greatly reduced the scratch resistance, Comparative Example 3 containing ATO was excellent in antistatic properties, but the transmittance was low, the haze was high, the adhesion was greatly reduced.

Claims (11)

A hard coating composition comprising an ultraviolet curable acrylic monomer, a reactive silica particle, an organic solvent, a photopolymerization initiator, and an antistatic agent, wherein the antistatic agent is an ion complex composed of alkylamide and an alkali metal salt. The antistatic hard coating agent composition of claim 1, wherein the ion complex is represented by the following Chemical Formula 1: [Formula 1]

Wherein R ₁ and R ₂ are each hydrogen, an alkyl group having 1 to 22 carbon atoms, an unsaturated hydrocarbon group having 1 to 22 carbon atoms, an alkylsilane group or a perfluoroalkyl group, and at least one of R ₁ and R ₂ is hydrogen And M ⁺ is a cation of an alkali metal salt and X ⁻ is an anion of an alkali metal salt). The antistatic hard coating agent composition of claim 2, wherein R ₁ is a methyl group and R ₂ is hydrogen. The method of claim 2, wherein a cation of the alkali metal salt is one selected from the group consisting of lithium, sodium and potassium and anions ^{OTf -, OTs -, OMs -} , TfSI -, 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 - prevent one member charged is selected from the group consisting of sex hard Coating composition. The method of claim 4, wherein a cation of the alkali metal salt is lithium and the anion is I ^-, ClO ₄ ^- and TfSI ^- prevent one member selected from the group consisting of antistatic property hard coating composition. According to claim 1, wherein the ultraviolet curable acrylic monomer 10 to 50% by weight, reactive silica particles 1 to 40% by weight, organic solvent 30 to 80% by weight, photopolymerization initiator 0.1 to 10% by weight and antistatic agent 0.5 to 30% by weight Antistatic hard coating agent composition. 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. 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, Antistatic, which is one kind selected from the group consisting of polyetherketone, polyetheretherketone, polyethersulfone, polymethylmethacrylate, 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. The liquid crystal display device of claim 8, wherein the antistatic hard coating film is provided.