KR20110060038A - Anti static hard coating composition, hard coating film, polarizing plate and display device using the same - Google Patents

Abstract

PURPOSE: An antistatic hard coating composition is provided to ensure excellent antistatic property, transparency and high transmittance and to enable use for an antistatic hard coating film, a polarizing plate and a display device. CONSTITUTION: An antistatic hard coating composition includes a polymer obtained by polymerizing a compound including an ionic monomer having a (meth)acrylate group represented by chemical formula 1. In chemical formula 1, R1 and R2 are independently C1-50 aliphatic hydrocarbon; R3 is hydrogen atom or methyl group; n is an integer of 1-100; and X is atom or compounds capable of using monovalent anions.

Description

Anti-static hard coating composition, anti-static hard coating film, polarizing plate and display device including the same {Anti Static Hard Coating Composition, Hard Coating Film, Polarizing Plate and Display Device Using The Same}

The present invention relates to an antistatic hard coating composition, an antistatic hard coating film, a polarizing plate and a display device including the same.

In general, a hard coating layer having a hard coating layer having excellent anti-scratch on a base film as a surface protective material is used for display devices such as a cathode ray tube (CRT), a liquid crystal display (LCD), and a plasma display panel (PDP). Film is used. However, since the conventional hard coating film has a surface resistance of 10 ¹³ Pa / sq or more, there is a disadvantage that surrounding dust or the like is easily attached to the surface.

Accordingly, an antistatic hard coating film having imparted antistatic property to a hard coating layer is used. In order to impart antistatic property to the hard coating layer, an antistatic agent is generally added or an antistatic layer may be separately formed. Recently, an antistatic hard coating composition using a metal oxide-based conductive sol such as antimontinoxide (ATO) or indiumtinoxide (ITO) has been developed. Such an antistatic hard coating composition has excellent antistatic persistence by free electron charge transfer and is very active in commercial applications because of its generally excellent transparency.

However, when the antistatic hard coating composition is coated on the transparent plastic, the transmittance is very low, such as 80% to 85%, and has a predetermined color, thereby damaging the appearance of the transparent plastic, and the price is very expensive, thereby reducing the cost of the product. There is a disadvantage to increase.

Accordingly, an object of the present invention is to provide an antistatic hard coating composition excellent in antistatic performance and excellent transmittance when applied to the production of an antistatic hard coating film.

Another object of the present invention is to provide an antistatic hard coating film having excellent antistatic performance and transmittance.

Still another object of the present invention is to provide a polarizing plate provided with the antistatic hard coating film.

Still another object of the present invention is to provide a display device provided with the antistatic hard coating film.

The present invention for achieving the above object provides an antistatic hard coating composition comprising a polymer obtained by polymerizing a compound containing an ionic monomer having a (meth) acrylate group represented by the following formula (1). .

[Formula 1]

In Formula 1, R ₁ and R ₂ are each independently an aliphatic hydrocarbon having 1 to 50 carbon atoms, R ₃ is a hydrogen atom or a methyl group, n is an integer of 1 to 100, X is a monovalent anion Atoms or compounds.)

The polymer is preferably obtained by using a polyethylene oxide unsaturated compound represented by the following formula (2) or (3) as a crosslinking agent.

[Formula 2]

(In Formula 2, m is an integer of 1 to 500.)

(3)

(In Formula 3, R ₄ is independently of each other a hydrogen atom or a methyl group, p is an integer from 1 to 500.)

The antistatic hard coating composition may include a urethane (meth) acrylate, a (meth) acrylate monomer, a photoinitiator and a solvent.

It is preferable that the said urethane (meth) acrylate contains the urethane (meth) acrylate more than 5-functional.

5 to 45 parts by weight of the polymer, 10 to 60 parts by weight of the urethane (meth) acrylate, 5 to 50 parts by weight of the (meth) acrylate monomer, and the photoinitiator, based on 100 parts by weight of the antistatic hard coating composition. The 0.1 to 10 parts by weight and the solvent provides an antistatic hard coating composition characterized in that it comprises 0.1 to 75 parts by weight.

In order to achieve another object of the present invention, the present invention provides an antistatic hard coating film comprising a hard coating layer formed using the antistatic hard coating composition according to the present invention.

The surface resistance of the antistatic hard coating film is preferably 5 × 10 ¹⁰ Pa / sq or less.

In order to achieve another object of the present invention, the present invention provides a polarizing plate comprising the antistatic hard coating film according to the present invention described above.

In order to achieve another object of the present invention, the present invention provides a display device comprising the antistatic hard coating film according to the present invention described above.

The antistatic hard coating composition according to the present invention exhibits excellent antistatic performance and transparency when applied to the production of hard coating films. Accordingly, the antistatic hard coating composition may be usefully applied to an antistatic hard coating film, a polarizing plate, and a display device.

Hereinafter, the present invention will be described in more detail.

The antistatic hard coating composition according to the present invention includes a polymer obtained by polymerizing a compound containing an ionic monomer having a (meth) acrylate group represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ and R ₂ are each independently an aliphatic hydrocarbon having 1 to 50 carbon atoms, R ₃ is a hydrogen atom or a methyl group, n is an integer of 1 to 100, X is a monovalent anion Atoms or compounds.)

The polymer, when included in the hard coating composition, exhibits excellent antistatic properties as well as high transmittance as compared to other conventional antistatic agents.

The monomer represented by Formula 1 reacts halogen alkyl alcohol and (meth) acrylochloride in the presence of an amine such as triethylamine to produce a halogen alkyl (meth) acrylate, which is reacted with an N-alkyl imidazole compound. It can be manufactured easily.

Specific examples of the halogen alkyl alcohol include 2-chloroethanol, 2-bromoethanol, 2-iodoethanol, 3-chloro-1-propanol, 3-bromo-1-propanol, 4-chloro-1-butanol, 6-chloro-1-hexanol, 6-bromo-1-hexanol, 7-bromo-1-heptanol, 8-chloro-1-octanol, 8-bromo-1-octanol, 9- Bromo-1-nonanol, 10-chloro-1-decanol, 10-bromo-1-decanol, 11-bromo-1-undecanol or 12-bromo-1-dodecanol have.

Specific examples of the N-alkylimidazole compound include N-methylimidazole, N-ethyl-2-methylimidazole, 1,2-dimethylimidazole, N-decyl-2-methylimidazole, N-vinylimidazole, N-arylimidazole, N-butylimidazole, etc. are mentioned.

In Formula 1, X is not particularly limited as an atom or a compound that may be used as a monovalent anion. Wherein X ^- is for example, ^{Cl -, Br -, I -} , AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, SbF 6 -, NO 3 -, ClO 4 -, CH 3 COO -, CF _{^{3 COO -, CH 3 SO 3}} -, CF 3 SO 3 -, (CF 3 SO 2) 2 N -, (C 2 F 5 SO 2) 2 N -, C 3 F 7 COO -, (CF 3 SO 2 ) (CF ₃ CO) N ^{-and the} like.

The polymer is preferably a polyethylene oxide unsaturated compound represented by the following formula (2) or (3) as a crosslinking agent for polymerizing a compound containing an ionic monomer having a (meth) acrylate group represented by the following formula (1)

[Formula 2]

(In Formula 2, m is an integer of 1 to 500.)

 (3)

(In Formula 3, R ₄ is independently of each other a hydrogen atom or a methyl group, p is an integer from 1 to 500.)

When the polyethylene oxide unsaturated compound represented by the formula (2) or (3) is used as the crosslinking agent, it provides flexibility to the inside of the polymer to improve the electrical conductivity.

The polyethylene oxide vinyl ether compound represented by Formula 2 is specifically a group consisting of ethylene glycol divinyl ether, di (ethylene glycol) divinyl ether, tri (ethylene glycol) divinyl ether, tetra (ethylene glycol) divinyl ether, and the like. At least one selected from can be used.

In addition, the polyethylene oxide (meth) acrylate compound represented by the formula (3) is specifically ethylene glycol dimethacrylate, ethylene glycol diacrylate, di (ethylene glycol) diacrylate, polyethylene glycol diacrylate, polyethylene glycol di At least 1 sort (s) chosen from the group which consists of methacrylate etc. can be used.

The production method of the polymer is not particularly limited, and may be prepared by a solution polymerization method, a photopolymerization method, a bulk polymerization method, a suspension polymerization method or an emulsion polymerization method. Preferably, the polymer is prepared using a solution polymerization method, and the polymerization temperature is preferably 50 to 110 ° C, and the polymerization initiator is preferably added in a state where the monomers are uniformly mixed. As the polymerization initiator, those used in the art may be applied. Specifically, azo-based polymerization initiators such as azobisisobutyronitrile and azobisisovaleronitrile, benzoyl peroxide, di-t-butyl peroxide And at least one selected from peroxide-based polymerization initiators such as lauryl peroxide.

The polymer is preferably included 5 to 45 parts by weight based on 100 parts by weight of the antistatic hard coating composition. When the content of the polymer is less than 5 parts by weight, there is a problem that the surface resistance is not sufficiently improved and the antistatic property is lowered, and when it exceeds 45 parts by weight, compatibility is reduced.

The antistatic hard coating composition according to the present invention may include a urethane (meth) acrylate, a (meth) acrylate monomer, a photoinitiator and a solvent.

It is preferable that the urethane (meth) acrylate includes a urethane (meth) acrylate of 5 or more functionalities, and particularly, the urethane (meth) acrylate of 5 or more functionalities is more preferably represented by the following formula (4).

[Formula 4]

In Formula 4, Y is an aliphatic or aromatic hydrocarbon containing or not containing 2 to 80 heteroatoms including 2 to 20 (meth) acrylate functional groups, and Q is linear or branched. Or an aliphatic or aromatic hydrocarbon containing or without a cyclic C3-C50 hetero atom, and q is an integer of 1 to 10.)

The 5-functional or more urethane (meth) acrylate represented by Formula 4 may be prepared by reacting a (meth) acrylate compound containing a hydroxyl group with a compound having two or more isocyanate groups in a molecule.

Specific examples of the compound having an isocyanate group include 4,4'-dicyclohexyl diisocyanate, hexamethylene diisocyanate trimer, 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,8-diisocyanate Natooctane, 1,12-diisocyanatodecane, 1,5-diisocyanato-2-methylpentane, trimethyl-1,6-diisocyanatohexane, 1,3-bis (isocyanatomethyl) cyclohexane, Trans-1,4-cyclohexene diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylene- 1,4-diisocyanate, tetramethylxylene-1,3-diisocyanate, 1, -chloromethyl-2,4-diisocyanate, 4,4'-methylenebis (2,6-dimethylphenylisocyanate), 4,4'-oxybis (phenylisocyanate), derived from hexamethylene diisocyanate Trifunctional isocyanate, a trimethane propanol adduct toluene diisocyanate, etc. are mentioned. These can be used individually or in combination of 2 types or more, respectively.

Specific examples of the (meth) acrylate compound containing the hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxyisopropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and capro Lactone ring-opening hydroxyacrylate, pentaerythritol tri / tetra (meth) acrylate mixture, dipentaerythritol penta / hexa (meth) acrylate mixture, and the like, and the like, each of which may be used alone or in combination of two or more thereof. have.

The urethane (meth) acrylate is not limited, but is preferably included 10 to 60 parts by weight based on 100 parts by weight of the antistatic hard coating composition. If the content of the urethane (meth) acrylate is less than 10 parts by weight based on the above-mentioned, it is difficult to improve the sufficient hardness, and if it exceeds 60 parts by weight, cracks may occur due to surface hardness improvement.

The (meth) acrylate monomer may be further added to maximize the effect of the urethane (meth) acrylate and may be preferably used in terms of shrinkage and hardness. Specific examples of the (meth) acrylate monomer include dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylolpropane tetra (meth). ) Acrylate, (meth) acrylic ester, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (Meth) acrylate, propylene glycol (meth) acrylate, 1,3-butanedioldi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate Neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl Isocyanurate di (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isooctyl (meth) acrylate, iso-decyl (Meth) acrylate, stearyl (meth) acrylate, tetrahydroperfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornol (meth) acrylate, etc. are mentioned. Said (meth) acrylate monomers can be used individually or in combination of 2 types or more, respectively.

The (meth) acrylate monomer preferably contains 5 to 50 parts by weight based on 100 parts by weight of the antistatic hard coating composition. If the content of the (meth) acrylate is less than 5 parts by weight based on the above criteria, it is difficult to control the shrinkage of the urethane (meth) acrylate, and if the content exceeds 50 parts by weight, there is a problem that the hardness is lowered.

The photoinitiator may be applied without limitation as long as it is generally used in the art. The photoinitiator may include a hydroxyketone photoinitiator or an amino ketone photoinitiator, more specifically, benzophenone, 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinepropanone-1, di Phenyl ketone benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-1-one, 4-hydroxycyclophenyl ketone, dimethoxy-2-phenylatetophenone, anthraquinone, fluorene, triphenylamine , At least one selected from the group consisting of carbazole, 3-methylacetophenone, 4-knoloacetophenone, 4,4-dimethoxyacetophenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexylphenylketone Species photoinitiators can be used.

Preferably, the photoinitiator preferably includes a hydrogen-reducing photoinitiator such as benzophenone, and in this case, surface hardness may be further improved.

The photoinitiator is preferably included 0.1 to 10 parts by weight based on 100 parts by weight of the antistatic hard coating composition. When the content of the photoinitiator is less than 0.1 parts by weight based on the above standard, the curing rate may be slow and may exceed 10 parts by weight.

The solvent can be used without limitation so long as it is known in the art.

Examples of the solvent include alcohols (methanol, ethanol, isopropanol, butanol, methylcellulose, ethyl solusorb, etc.), ketones (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, Cyclohexanone etc.), hexane type (hexane, heptane, octane etc.), benzene type (benzene, toluene, xylene etc.) etc. can be illustrated. The said solvent can be used individually or in combination of 2 or more types, respectively.

The solvent may be added 0.1 to 75 parts by weight based on 100 parts by weight of the antistatic hard coating composition. If the content of the solvent is less than 1 part by weight based on the above standard, the viscosity is high, the workability is lowered, and if it exceeds 75 parts by weight, it takes a long time in the curing process and there is a problem of low economic efficiency.

In addition to the above components, an antistatic hard coating composition according to the present invention may be used with an antioxidant, a UV absorber, a light stabilizer, a thermal polymerization inhibitor, a labelling agent, a surfactant, a lubricant, an antifouling agent, and the like.

The antistatic hard coating film according to the present invention includes a hard coating layer formed using the antistatic hard coating composition according to the present invention described above. That is, the antistatic hard coating film according to the present invention includes an antistatic hard coating layer formed by applying the antistatic hard coating composition according to the present invention to a substrate.

The substrate is preferably a transparent film, and for example, cycloolefin derivatives having a unit of a monomer containing a cycloolefin such as norbornene or a polycyclic norbornene monomer, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyl Cellulose, ethylene-vinyl acetate copolymer, polyester, polystyrene, polyamide, polyetherimide, polyacryl, polyimide, polyether sulfone, Polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, polyether sulfone, polymethyl methacrylate, polyethylene Terephthalate, Polybutylene Terephthalate , Polyethylene naphthalate, polycarbonate, polyurethane may be used, and an unoriented, uniaxial or biaxially oriented film may be used. Among them, preferably, a monoaxial or biaxially stretched polyester film having excellent transparency and heat resistance, but a triacetyl cellulose film is suitably used in view of transparency and optical anisotropy.

Although the thickness of the said base material is not restrict | limited, 8-1000 micrometers is preferable, More preferably, it is 40-100 micrometers.

The method of applying the antistatic hard coating composition to the substrate may be a method generally used in the art, for example, selected from die coater, air knife, reverse roll, spray, blade, casting, gravure and spin coating, etc. It may be carried out in a suitable manner.

The coating thickness of the antistatic hard coating composition is 0.1 to 200 µm, preferably 2 to 30 µm, and more preferably 4 to 25 µm. After applying the antistatic hard coating composition, the volatiles are dried by evaporation at a temperature of 30 to 150 ° C. for 1 second to 30 minutes, preferably 10 seconds to 10 minutes. After curing by irradiation with UV light. The irradiation amount of the UV light is preferably about 0.01 to 10 J / cm 2, more preferably 0.1 to 2 J / cm 2.

The thickness of the hard coating layer is not limited, but is preferably in the range of 1 to 30 μm, more preferably in the range of 5 to 15 μm. When the thickness of the hard coating layer is within the above range, it is possible to obtain an antistatic hard coating film having a curling property of 15 mm or less.

The antistatic hard coating film manufactured as described above has excellent surface resistance and optical high transparency, and has a high curing speed at the time of manufacture, and thus has high productivity, and the film produced after curing has an advantage of not causing a curling phenomenon. In particular, the antistatic hard coating film produced in the present invention exhibits excellent surface resistance of 10 ¹⁰ or less.

The polarizing plate according to the present invention is formed by laminating the aforementioned antistatic hard coating film on at least one surface.

The polarizing plate is not particularly limited, but various kinds may be used. The polarizing plate may be, for example, a film uniaxially stretched by adsorbing a dichroic substance such as a polyvinyl alcohol film, an ethylene-vinyl acetate copolymerized partial saponified film, iodine or a dichroic dye, a dehydrated product of polyvinyl alcohol, or Polyene type orientation films, such as the dehydrochlorination material of polyvinyl chloride, etc. can be used. Among these, the polarizing plate which consists of dichroic substances, such as a polyvinyl alcohol-type film or iodine, is preferable. Although the thickness in particular of these polarizing plates is not restrict | limited, Usually, it is about 5-80 micrometers.

The display device according to the present invention includes the antistatic hard coating film described above. That is, the display device having excellent antistatic property can be manufactured by embedding a polarizing plate on which the antistatic hard coating film of the present invention is laminated. . In particular, the antistatic hard coating film of the present invention can be preferably used in reflective, transmissive, transflective LCD or LCD of various driving methods such as TN type, STN type, OCB type, HAN type, VA type, and IPS type. . In addition, the antistatic hard coating film of the present invention is excellent in wear resistance and antifouling property, and can be preferably used in various display devices such as plasma displays, field emission displays, organic EL displays, inorganic EL displays, and electronic paper.

The present invention will be further illustrated by the following examples, which are merely illustrative of the present invention and are not intended to limit or limit the scope of the present invention.

[Haloalkyl (meth) acrylate synthesis]

 Synthesis Example 1

250 parts by weight of methylene chloride, 50 parts by weight of 2-bromoethanol (Aldrich) and 15 parts by weight of triethylamine were added to a reactor equipped with a condenser, a stirring device, and a temperature controller, and the reactor temperature was lowered to 0 ° C. 25 parts by weight of acroyl chloride was diluted with 25 parts by weight of methylene chloride and slowly added dropwise thereto. After the addition was completed, the temperature was raised to room temperature, followed by stirring for 1 hour. After completion of the reaction, the reaction was confirmed using gas chromatography. After completion of the reaction, 250 parts by weight of water was added thereto, stirred, and left to stand. The solvent layer removed the solvent using the pressure reduction apparatus, and obtained 2-bromoethyl acrylate of purity 95%.

Synthesis Example 2

250 parts by weight of methylene chloride, 65 parts by weight of 6-bromo-1-hexanol (Aldrich) and 15 parts by weight of triethylamine were added to a reactor equipped with a condenser, a stirring device, and a temperature controller. After lowering to ℃ ℃ 23 parts by weight of acroyl chloride diluted to 23 parts by weight of methylene chloride was slowly added dropwise. After the addition was completed, the temperature was raised to room temperature, followed by stirring for 1 hour. After completion of the reaction, the reaction was confirmed using gas chromatography. After completion of the reaction, 250 parts by weight of water was added thereto, stirred, and left standing to remove the water layer. The solvent layer removed the solvent using the pressure reduction apparatus, and obtained 6-bromohexyl acrylate of purity 96%.

Synthesis Example 3

250 parts by weight of methylene chloride, 65 parts by weight of 6-bromo-1-hexanol (Aldrich) and 15 parts by weight of triethylamine were added to a reactor equipped with a condenser, a stirring device, and a temperature controller. After lowering to ℃ ℃ 23 parts by weight of methacroyl chloride was diluted with 23 parts by weight of methylene chloride was slowly added dropwise. After the addition was completed, the temperature was raised to room temperature, followed by stirring for 1 hour. After completion of the reaction, the reaction was confirmed using gas chromatography. After completion of the reaction, 250 parts by weight of water was added thereto, followed by stirring. The solvent layer removed the solvent using the pressure reduction apparatus, and obtained 6-bromohexyl methacrylate of 94% purity.

Synthesis Example 4

250 parts by weight of methylene chloride, 60 parts by weight of 6-chloro-1-hexanol (Aldrich) and 15 parts by weight of triethylamine were added to a reactor equipped with a condenser, a stirring device, and a temperature controller, and the reactor temperature was 0 ° C. After lowering to 23 parts by weight of methacroyl chloride diluted to 23 parts by weight of methylene chloride was slowly added dropwise. After the addition was completed, the temperature was raised to room temperature, followed by stirring for 1 hour. After completion of the reaction, the reaction was confirmed using gas chromatography. After completion of the reaction, 250 parts by weight of water was added thereto, stirred, and left standing to remove the water layer. The solvent layer removed the solvent using the pressure reduction apparatus, and obtained 6-chlorohexyl methacrylate of 94% purity.

Synthesis of Ionic Compounds Having [(meth) acrylate (Anion: Br ^- or Cl ^- )]

Synthesis Example 5

30 parts by weight of 2-bromoethyl acrylate (as prepared in Synthesis Example 1) and 70 parts by weight of N-ethylimidazole were added to a reactor equipped with a condenser, a stirring device, and a temperature controller, and the resultant was stirred at 80 ° C. for 24 hours. Stirred. After confirming the completion of the reaction by gas chromatography, lowering the temperature to room temperature, adding 100 parts by weight of hexane, stirring and removing the solvent layer five times to remove the residual amount of N-ethylimidazole and remaining under reduced pressure. The solvent was removed to obtain 1-ethyl-3-acroylethylimidazolium bromide.

 [Synthesis Example 6]

30 parts by weight of 6-bromohexyl acrylate (prepared in Synthesis Example 2) and 80 parts by weight of N-ethylimidazole were added to a reactor equipped with a condenser, a stirring device, and a temperature controller for 24 hours at 80 ° C. Stirred. After confirming the completion of the reaction by gas chromatography, lowering the temperature to room temperature, adding 100 parts by weight of hexane, stirring and removing the solvent layer five times to remove excess N-ethylimidazole, and then remaining solvent under reduced pressure. Was removed to obtain 1-ethyl-3-acroylhexylimidazolium bromide.

[Synthesis Example 7]

30 parts by weight of 6-bromohexyl methacrylate (manufactured in Synthesis Example 3) and 75 parts by weight of N-ethylimidazole were added to a reactor equipped with a condenser, a stirring device, and a temperature controller, and the result was 24 hours at 80 ° C. Was stirred. After confirming the completion of the reaction by gas chromatography and lowering the temperature to room temperature, 100 parts by weight of hexane was added thereto, followed by stirring five times to remove the solvent layer, to remove residual N-ethylimidazole. Was removed to obtain 1-ethyl-3-methacrylohexylimidazolium bromide.

[Synthesis Example 8]

30 parts by weight of 6-chlorohexyl methacrylate (prepared in Synthesis Example 4) and 84 parts by weight of N-butylimidazole were added to a reactor equipped with a condenser, a stirring device, and a temperature control unit at 80 ° C. for 24 hours. Stirred. After confirming the completion of the reaction by gas chromatography and lowering the temperature to room temperature, 100 parts by weight of hexane was added and stirred to remove the solvent layer five times to remove excess N-butylimidazole, and then residual solvent under reduced pressure. Was removed to give 1-butyl-3-methacryloylethylimidazolium chloride.

Synthesis of Ionic Compounds Having [(meth) acrylate (Anion: NTf ₂ ^-  Or PF ₆ ^- ]

Synthesis Example 9

200 parts by weight of acetonitrile, 20 parts by weight of 1-ethyl-3-acroylethylimidazolium bromide (manufactured in Synthesis Example 5) as a solvent in a reactor equipped with a condenser, a stirring device, and a thermostat 25 parts by weight of trifluoromethanecellfonyl) imide (Aldrich) was added and stirred at 80 ° C for 48 hours. After confirming the completion of the reaction, the temperature was lowered to room temperature, and then passed through a column filled with silica gel (400 mesh, Merck) to remove the lithium bromide solid to remove 1-ethyl-3-acryloylethylimidazolium bis (trifluoromethane cell phone). Nil) imide was obtained.

Synthesis Example 10

200 parts by weight of acetonitrile, 1-ethyl-3-acylhexylimidazolium bromide (manufactured in Synthesis Example 6) as a solvent in a reactor equipped with a condenser, a stirring device, and a temperature controller, and a lithium bis ( 40 parts by weight of trifluoromethanecellfonyl) imide (Aldrich) was added and stirred at 80 ° C for 48 hours. After confirming the completion of the reaction, the temperature was lowered to room temperature, and then passed through a column filled with silica gel (400 mesh, Merck) to remove the lithium bromide solid to remove 1-ethyl-3-acrylohexylimidazolium bis (trifluoromethane cell phone). Nil) imide was obtained.

Synthesis Example 11

200 parts by weight of acetonitrile, 20 parts by weight of 1-ethyl-3-methacrohexylimidazolium bromide (manufactured in Synthesis Example 7) as a solvent in a reactor equipped with a condenser, a stirring device, and a thermostat 40 parts by weight of (trifluoromethanecellfonyl) imide (Aldrich) was added and stirred at 80 ° C for 48 hours. After confirming the completion of the reaction, the temperature was lowered to room temperature and passed through a column filled with silica gel (400 mesh, Merck) to remove the lithium bromide solid to remove 1-ethyl-3-methacroylhexylimidazolium bis (trifluoromethane). Celfonyl) imide was obtained.

Synthesis Example 12

200 parts by weight of acetonitrile, 20 parts by weight of 1-butyl-3-methacroylethylimidazolium chloride (manufactured in Synthesis Example 8) as a solvent in a reactor equipped with a condenser, a stirring device, and a thermostat, lithium bis 40 parts by weight of (trifluoromethanecellfonyl) imide (Aldrich) was added and stirred at 80 ° C for 48 hours. After confirming the completion of the reaction, the temperature was lowered to room temperature and passed through a column filled with silica gel (400 mesh, Merck) to remove the lithium chloride solid, thereby removing 1-butyl-3-methacrylohexylimidazolium bis (trifluoromethane). Celfonyl) imide was obtained.

[Synthesis Example 13]

200 parts by weight of acetonitrile, 20 parts by weight of 1-ethyl-3-methacrylohexylimidazolium bromide (prepared in Synthesis Example 7) as a solvent in a reactor equipped with a condenser, a stirring device, and a thermostat, sodium hexa 30 parts by weight of fluorophosphine (Aldrich) was added and stirred at 80 ° C. for 48 hours. After confirming the completion of the reaction, the temperature was lowered to room temperature, and then passed through a column filled with silica gel (400 mesh, Merck) to remove the lithium bromide solid to remove 1-ethyl-3-methacroylhexylimidazolium hexafluorophosphine. Got it.

[Polymer synthesis]

[Synthesis Example 14]

50 parts by weight of ethyl acetate as a solvent, 1-ethyl-3-acryloethylimidazolium bis (trifluoromethaneselfonyl) imide (manufactured in Synthesis Example 9) in a reactor equipped with a condenser, a stirring device, and a temperature controller. 25 parts by weight, 1 part by weight of tetra (ethylene glycol) divinyl ether was added, and the temperature was raised to 70 ° C., 0.1 part by weight of azobisisobutyronitrile was dissolved in 10 parts by weight of ethyl acetate as an initiator, and slowly added. Stirring was performed for a time to obtain a polymer having a solid content of 50% by weight.

Synthesis Example 15

50 parts by weight of ethyl acetate as a solvent, 1-ethyl-3-acroylhexylimidazolium bis (trifluoromethaneselfonyl) imide (manufactured in Synthesis Example 10) in a reactor equipped with a condenser, a stirring device, and a temperature controller. 25 parts by weight, 1 part by weight of tetra (ethylene glycol) divinyl ether was added, and the temperature was raised to 70 ° C., 0.1 part by weight of azobisisobutyronitrile was dissolved in 10 parts by weight of ethyl acetate as an initiator, and slowly added. Stirring was performed for a time to obtain a polymer having a solid content of 50% by weight.

Synthesis Example 16

50 parts by weight of ethyl acetate as a solvent, 1-ethyl-3-methacrylohexyl imidazolium bis (trifluoromethanecellfonyl) imide (in Synthesis Example 11) in a reactor equipped with a condenser, a stirring device, and a temperature controller. 25 parts by weight, 1 part by weight of tetra (ethylene glycol) divinyl ether is added, and the temperature is raised to 70 ° C, 0.1 part by weight of azobisisobutyronitrile is dissolved in 10 parts by weight of ethyl acetate as an initiator, and slowly added. Stirring was performed for 8 hours to obtain a polymer having a solid content of 50% by weight.

Synthesis Example 17

50 parts by weight of ethyl acetate as a solvent, 1-butyl-3-methacroylheximidazolium bis (trifluoromethanecellfonyl) imide (in Synthesis Example 12) in a reactor equipped with a condenser, a stirring device, and a temperature controller. 25 parts by weight, 1 part by weight of tetra (ethylene glycol) divinyl ether was added and the temperature was raised to 70 ° C, and 0.1 part by weight of azobisisobutyronitrile was dissolved in 10 parts by weight of ethyl acetate as an initiator, and slowly added thereto. Stirring was performed for 8 hours to obtain a polymer having a solid content of 50% by weight.

Synthesis Example 18

50 parts by weight of ethyl acetate as a solvent, 1-ethyl-3-methacrohexyl imidazolium hexafluorophosphine (manufactured in Synthesis Example 13) in a reactor equipped with a condenser, a stirring device, and a temperature controller (25 parts) 1 part by weight of tetra (ethylene glycol) divinyl ether was added, and the temperature was raised to 70 ° C., 0.1 part by weight of azobisisobutyronitrile was dissolved in 10 parts by weight of ethyl acetate as an initiator, and slowly added thereto, followed by stirring for 8 hours. To obtain a polymer having a solid content of 50% by weight.

Synthesis Example 19

50 parts by weight of ethyl acetate as a solvent, 1-ethyl-3-methacrohexyl imidazolium hexafluorophosphine (manufactured in Synthesis Example 13) in a reactor equipped with a condenser, a stirring device, and a temperature controller (25 parts) 1 part by weight of di (ethylene glycol) diacrylate was added and the temperature was raised to 70 ° C., 0.1 part by weight of azobisisobutyronitrile was dissolved in 10 parts by weight of ethyl acetate as an initiator, and slowly added thereto, followed by stirring for 8 hours. To obtain a polymer having a solid content of 50% by weight.

Synthesis Example 20

50 parts by weight of ethyl acetate as a solvent, 1-ethyl-3-methacrohexyl imidazolium hexafluorophosphine (manufactured in Synthesis Example 13) in a reactor equipped with a condenser, a stirring device, and a temperature controller (25 parts) Then, 1 part by weight of poly (ethylene glycol) dimethacrylate (p = 6) was added, and the temperature was raised to 70 ° C., 0.1 part by weight of azobisisobutyronitrile was dissolved in 10 parts by weight of ethyl acetate as an initiator, and slowly added. Stirring was performed for 8 hours to obtain a polymer having a solid content of 50% by weight.

Synthesis Example 21

50 parts by weight of ethyl acetate as a solvent, 1-ethyl-3-methacrohexyl imidazolium hexafluorophosphine (manufactured in Synthesis Example 13) in a reactor equipped with a condenser, a stirring device, and a temperature controller (25 parts) Then, 1 part by weight of poly (ethylene glycol) diacrylate (p = 12) was added and the temperature was raised to 70 ° C., 0.1 part by weight of azobisisobutyronitrile was dissolved in 10 parts by weight of ethyl acetate as an initiator, and slowly added 8 Stirring was performed for a time to obtain a polymer having a solid content of 50% by weight.

[Examples 1 to 14 and Comparative Examples 1 to 3]

To prepare the antistatic hard coating composition by mixing the components as shown in Table 1.

Urethane acrylate: 10 functional urethane acrylate (SUO-1700B, Shin ArtenC)

Acrylate monomer: pentaerythritol tree / pentaacrylate (M340, Miwon Corporation)

Antistatic Agent: ATO (Antimony Tin Oxide 30% in 2-methoxyethanol, Schemtech)

Antistatic agent: quaternary ammonium (1-methyl-3-butylimidazonium tetrafluoroborate, sea tree)

I-184: 1-hydroxycyclohexylphenyl ketone (Shiba Corporation)

I-907: 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinepropanone-1 (Shiba Corporation)

MEK: methyl ethyl ketone

MIBK: methyl isobutyl ketone

BYK-378: Silicone Modified Oil (BYK)

Experimental Example

The antistatic hard coating composition prepared in Examples and Comparative Examples was applied on one side of a transparent substrate made of a triacetyl cellulose film having a thickness of 80 μm, and then dried by heating and UV cured to form a hard coating layer having a thickness of 5 μm. The physical properties of the thus prepared film were measured as follows, and the results are shown in Table 2 below.

(1) transmittance and haze

Total transmittance and haze were measured using a spectrophotometer (HZ-1, Suga, Japan).

(2) surface resistivity

Electrical resistance was measured using Hiresta's MCP-HT450.

As shown in Table 2, in Examples 1 to 14 including the polymer of the compound containing the ionic monomer according to the present invention, the antistatic performance is very good and the transmittance is very high compared to Comparative Examples 1 to 3 not including the same. You can see the high.

Claims (9)

An antistatic hard coating composition comprising a polymer obtained by polymerizing a compound containing an ionic monomer having a (meth) acrylate group represented by the following formula (1). [Formula 1]

In Formula 1, R ₁ and R ₂ are each independently an aliphatic hydrocarbon having 1 to 50 carbon atoms, R ₃ is a hydrogen atom or a methyl group, n is an integer of 1 to 100, X is a monovalent anion Atoms or compounds.) The method of claim 1, wherein the polymer is an antistatic hard coating composition, characterized in that obtained by using a polyethylene oxide unsaturated compound represented by the formula (2) or (3) as a crosslinking agent. [Formula 2]

(In Formula 2, m is an integer of 1 to 500.) (3)

(In Formula 3, R ₄ is independently of each other a hydrogen atom or a methyl group, p is an integer from 1 to 500.) The antistatic hard coating composition of claim 1, wherein the antistatic hard coating composition comprises a urethane (meth) acrylate, a (meth) acrylate monomer, a photoinitiator, and a solvent. The antistatic hard coating composition of claim 3, wherein the urethane (meth) acrylate comprises a urethane (meth) acrylate having five or more functional groups. The method according to claim 3, wherein 5 to 45 parts by weight of the polymer, 10 to 60 parts by weight of the urethane (meth) acrylate, and 5 to 50 to the (meth) acrylate monomer based on 100 parts by weight of the antistatic hard coating composition By weight, the photoinitiator 0.1 to 10 parts by weight and the antistatic hard coating composition, characterized in that it comprises 0.1 to 75 parts by weight. An antistatic hard coating film comprising a hard coating layer formed using the antistatic hard coating composition of any one of claims 1 to 5. The antistatic hard coating film of claim 6, wherein the surface resistance of the antistatic hard coating film is 5 × 10 ¹⁰ Pa / sq or less. The antistatic hard coating film of claim 6 is provided with a polarizing plate. Display device, characterized in that the antistatic hard coating film of claim 6.