KR20070105869A - Antistatic high hardness hard coating film and manufacturing method thereof - Google Patents

Abstract

It comprises a hard coating layer formed on at least one surface of the transparent base film, the hard coating layer is added to the UV curable hard coating liquid by adding polyhetero acid and / or a conductive polymer to impart antistatic properties excellent hardness, wear resistance, weather resistance and The present invention relates to a film exhibiting optical high transparency and a method of manufacturing the same. In addition, according to the present invention, not only the improvement of the antistatic performance, but also the curing speed is high at the time of manufacturing a high hardness hard coating film, the productivity is excellent, and the film produced after curing did not occur curling phenomenon.

Description

Anti-Static Hard Coating Film with High Hardness And Manufacturing Method Thereof}

1 is a cross-sectional view of a high hardness hard coating film according to an embodiment of the present invention,

Figure 2 is a cross-sectional view of a high hardness hard coating film according to another embodiment of the present invention,

Figure 3 is a flow chart of the manufacturing method of a high hardness hard coating film according to an embodiment of the present invention,

Figure 4 is a flow chart of the manufacturing method of a high hardness hard coating film according to another embodiment of the present invention.

** Description of the main symbols in the drawings **

1: transparent base film 2: hard coating layer

3: first hard coat layer 4: second hard coat layer

The present invention relates to an antistatic high hardness hard coating film and a method of manufacturing the same, and more particularly, to a hard coating film for protecting various displays, having high hardness, abrasion resistance, and weather resistance, and having excellent antistatic performance. The present invention relates to a hard coating film and a method for producing the same which are very suitable for protection.

Background Art Conventionally, hard coating films are used for various surface protection panels such as liquid crystal displays (LCDs), plasma displays (PDPs), CRTs, electroluminescent displays (EL), and the like. Since the display panel employing the glass substrate has a weak impact resistance and a problem in weight reduction, a hard coating film layer having a high hardness is formed on the surface of the plastic transparent substrate to replace or supplement the disadvantages.

As a material for forming a hard coating film, UV curable acrylic hard coating materials such as polyester, acrylate, urethane acrylate, and epoxy acrylate have sufficient surface protection properties to have as a hard coating film when the organic material alone is used. It did not represent.

Therefore, various organic-inorganic coating compositions including colloidal silica particles as inorganic materials have been used to improve the high hardness and wear resistance of hard coating films. However, the problems of stability due to precipitation and gel generation of colloidal silica particles whose silica surface is modified with organic material or silane, and the degree of curing, optical transparency and adhesion still do not meet the requirements of the hard coating film for display protection. have.

In addition, in recent years, in addition to the surface protection function of the display device, such as resistance to the display of fingerprints, markers and the like and easy to remove (that is, antifouling) and antistatic properties for the protection of the impact of the liquid crystal by static electricity, prevention of adhesion of foreign matters, etc. It is required.

As an antistatic agent for antistatic, metal oxide particles, conductive polymers, surfactants, hydrophilic monomers, ion conductive monomers, and the like can be considered. Metal oxide particles such as ATO or ITO may be manufactured by vacuum deposition. However, the high temperature process and expensive equipment are required, and thus the use of the metal oxide particles is very limited. Depending on the blending amount, the transmittance and the antistatic performance are largely affected, and thus the manufacturing is not easy.

Surfactants, hydrophilic monomers, and ion conductive monomers are sensitive to moisture in the atmosphere, have a large temperature dependency, and have a low persistence or durability, and may contaminate other substances, resulting in poor practicality.

In recent years, conductive polymers have been strengthened to shield electromagnetic waves generated from home, office, industrial, and electronic products such as computers, cordless phones, automobiles, medical devices, and multimedia. Increasing interest as an antistatic coating material that can be applied to plastic housings, polyethylene terephthalate films, etc., and typical conductive polymers include polyaniline, polypyrrole and polythiophene, and are easy to polymerize, and have excellent conductivity and oxidative stability. It can be applied as a conductive material, attracting much attention. In the case of the polythiophene-based polyethylenedioxythiophene, there is an advantage of excellent water solubility, solubility and thermal and UV stability compared to other conductive polymers.

 However, the biggest problem of the conductive polymer has its own color, which is difficult to apply to a transparent substrate, but is applied as a thin film. However, the hardness of the formed coating layer is reduced after application, resulting in a large amount of scratches, antistatic performance is also reduced. There is this.

The present invention is to solve the above problems, polyheteroacid and / or conductivity in the UV-curable hard coating liquid containing reactive silica particles chemically bonded to the polyfunctional organic material having a polymerizable unsaturated group to the siloxy group on the surface of the nano-silica particles It is an object of the present invention to provide a hard coat film having excellent properties of coating and scratch resistance, high hardness and excellent optical properties, and adding excellent antistatic performance using a coating composition to which a polymer is added, and a method of manufacturing the same.

The present invention for achieving the above object, comprising a hard coating layer formed on at least one surface of the transparent base film, the hard coating layer comprises an antistatic high hardness hard coating film made by applying a hard coating solution containing polyhetero acid to provide.

The present invention also includes a hard coating layer formed on at least one surface of the transparent substrate film, the hard coating layer is a first hard coating layer formed by applying a hard coating solution containing a hard coating solution or polyhetero acid, and the first hard It provides an antistatic high hardness hard coating film comprising a second hard coating layer formed by applying a hard coating solution containing polyhetero acid on the coating layer.

In addition, there is provided an antistatic high hardness hard coating film, characterized in that cross-linking is formed partially between the first hard coating layer and the second hard coating layer.

In addition, the hard coating solution provides an antistatic high hardness hard coating film comprising a polyfunctional organic material having a polymerizable unsaturated group and reactive silica particles chemically bonded to the siloxy group on the surface of the silica particles.

In addition, the polyhetero acid is selected from at least one selected from the group consisting of tungstophosphoric acid, tungstosilonic acid, and molybdate phosphoric acid, characterized in that 1 to 30% by weight based on 100% by weight of the hard coating solution It provides an antistatic high hardness hard coating film.

In addition, the hard coating solution or the hard coating solution containing polyhetero acid provides an antistatic high hardness hard coating film, characterized in that the conductive polymer further comprises.

In addition, the conductive polymer is polyaniline, polypyrrole or polythiophene, and provides an antistatic high hardness hard coating film, characterized in that 0.05 to 30% by weight based on 100% by weight of the hard coating solution.

In addition, 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, polyester, polystyrene, Polyamide, polyetherimide, polyacryl, polyimide, polyethersulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, At least one selected from the group consisting of polyether ether ketone, polyether sulfone, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyurethane, and epoxy; God(延伸), antistatic property, high hardness, it characterized in that a uniaxial or biaxial oriented film also provides a hard coat film.

The present invention also provides a method for forming a hard coating layer on at least one surface of a transparent base film by applying a hard coating solution containing polyhetero acid; It provides a method for producing an antistatic high hardness hard coating film comprising a; and a step of completely curing the hard coating layer.

The present invention also provides a method for forming a first hard coating layer on at least one surface of a transparent base film by applying a hard coating liquid or a hard coating liquid containing polyhetero acid; Semi-curing the first hard coating layer; Forming a second hard coat layer by applying a hard coating solution including polyhetero acid on the first hard coat layer; And completely curing the crosslinking between the first hard coat layer and the second hard coat layer so as to form an antistatic high hardness hard coat film.

In addition, the hard coating solution or the hard coating solution containing polyhetero acid provides a method for producing an antistatic high hardness hard coating film further comprises a conductive polymer.

Hereinafter, with reference to the drawings and embodiments will be described the present invention in detail.

1 is a cross-sectional view of a high-hardness hard coating film according to an embodiment of the present invention. As shown, it comprises a hard coating layer (2) formed on at least one surface of the transparent base film (1), the hard coating layer (2) is characterized by applying a hard coating solution containing polyhetero acid . The meaning that the hard coating layer is formed on at least one surface of the transparent base film includes forming a specific layer as needed on the transparent base film and then additionally forming a hard coating layer on the specific layer. In FIG. 1, only one surface of the hard coating layer is formed, but the present invention is not limited thereto. The hard coating layer may be formed on both sides, and a specific layer may be further added to the upper and lower portions of each component.

The hard coating solution is characterized in that the polyfunctional organic material having a polymeric unsaturated group and the reactive silica particles chemically bonded to the siloxy group on the surface of the silica particles.

Reactive silica particles can be prepared by chemical bonding by mixing the silica particles with a hydrolyzable silane having a polymeric unsaturated group. The amount of hydrolyzable silane having a polymeric unsaturated group bonded to the reactive silica particles is about 0.05 to 99% by weight, preferably 5 to 85% by weight. Less than 0.05% by weight affects the transparency and wear resistance of the cured film, while more than 99% by weight only slightly improves the wear resistance. Hydrolyzable silyl groups may be carboxylate silyl groups such as acetoxy silyl groups, alkoxy silyl groups such as methoxy or ethoxy silyl groups, halogen silyl groups such as chloro silyl groups, amino and hydride silyl groups, and the like, preferably alkoxy Silyl is best to use. The polymerizable unsaturated group may be carboxy, hydroxy, acryloxy, methacryloxy, vinyl, propenyl, butadienyl, styryl, cinnamoyl, maleate, acrylamide, and the like. Among these, unsaturated aliphatic carboxylic acid and methacrylate compound containing a hydroxyl group are preferable.

The average particle diameter of the reactive silica particles is not limited, but may be used in the range of 0.0001 ~ 20㎛, when used in the cured transparent film is preferably 0.001 ~ 0.01㎛.

In addition, silica particles are not limited but preferably nano-sized, specific surface area is not limited, but within the range of 0.001 ~ 2m ² / g, more preferably 0.001 ~ 0.1m ² / g, and most preferably 0.001 ~ 0.01 m ² / g. The silica particles may be a colloidal silica dispersed in an organic solvent such as a dry powder or a silica sol of methanol. The production of the reactive silica particles is carried out at 20 to 150 ° C, and is performed in a range of 5 minutes to 24 hours.

The hard coating solution may contain an unsaturated organic material, for example, dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, hexanediol diacrylate, urethane acrylate oligomer, acryloloyl morpholine, 2 -Acryloxypropylhexahydro phthalate and the like can be used.

The hard coating solution may include a photoinitiator, for example, diphenyl ketone benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-1-one, 4-hydroxy cyclo phenyl ketone, dimethoxy-2 -Phenylacetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3-methylacetophenone, 4-knoloacetophenone, 4,4-dimethoxyacetophenone, 4,4-diaminobenzophenone, etc. 0.1 to 10 wt% may be used alone or in combination. If less than 0.1% by weight, the curing speed is slow and more than 10% by weight is uneconomical. Photo stimulants can be used together with photoinitiators, for example triethylamine, diethylamine, methyldiethanolamine, ethanolamine, 4-dimethylamino-benzoic acid, isoamyl-4-dimethylaminobenzoate and the like can be used. Can be.

In addition to the above materials, antioxidants, UV absorbers, light stabilizers, thermal polymerization inhibitors, leveling agents, surfactants, lubricants and the like may be used together in the hard coating solution.

In the present invention, polyheteroic acid for imparting high hardness, antistatic property, and transparency is a complex of protonic acid, and metal isotopes such as molybdenum, vanadium, and tungsten have a certain regularity around the cation, which is a central element. It has a condensed structure, and is generally a water-soluble substance, soluble in alcoholic and polar organic solvents.

Polyheteroacids used in the present invention are 12- tungstophosphoric acid (H3PW12O40), 12- tungstosilonic acid (H4SiW12O40), 12- molybdophosphoric acid (H3PWMo12O40), 12- molybdo tungstophosphoric acid (H3PMo12-xWxO40) , X = 0 ~ 12), or 12-molybdobanadophosphoric acid (H3PMo12-xVxO46, where X = 0 ~ 12) may be used alone or in combination, including but not limited to tungsto as polyhetero acid. It is preferred to select at least one from the group consisting of phosphoric acid, tungstosilonic acid or molybdophosphoric acid, with 12- tungstophosphoric acid (H3PW12O40) being most preferred for use. The content of polyhetero acid added to the hard coating solution is not limited, but is 1 to 30% by weight, preferably 5 to 25% by weight based on 100% by weight of the hard coating solution. If it is added less than 1% by weight, the surface conductivity is weak, so that the antistatic performance cannot be exhibited. If the content is more than 30% by weight, the surface conductivity is improved, the antistatic performance is excellent, but the coating hardness is weakened, and scratches occur.

The hard coating layer 2 may further include a conductive polymer. Examples of the conductive polymer added to improve antistatic properties include polyaniline, polypyrrole and polythiophene, and these polymers are easy to polymerize and have excellent conductivity and oxidative stability. Preferably, polyethylenedioxythiophene, which is a polythiophene-based polymer having excellent water solubility, solubility and thermal and UV stability, is used. Conductive polymers such as polyethylenedioxythiophene are preferably doped with polystyrenesulfonic acid because of excellent water solubility and solubility, excellent thermal and atmospheric stability.

The content of the conductive polymer mixed with the hard coating solution is 0.05 to 30% by weight, preferably 5 to 25% by weight, and most preferably 7-20% by weight based on 100% by weight of the hard coating solution. If it is added less than 0.05% by weight, there is little improvement of antistatic performance. If it contains more than 30% by weight, the surface conductivity is improved, and the antistatic performance is excellent, but the coating hardness is weakened, and the transparency and optical performance of the coating film are reduced.

As the transparent base film 1, any film can be used as long as it is a plastic film having transparency. For example, cellulose derivatives such as diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, isobutyl ester cellulose, and ethylene- Vinyl acetate copolymer, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose or polyester, polystyrene, polyamide, polyetherimide, polyacryl, polyimide, polyethersulfone, polysulfone, polyethylene, polypropylene, poly Methyl pentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, polyether sulfone, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene Naphthalate, Paul At least one selected from thermoplastic polymers such as ricarbonate, polyurethane, and epoxy may be selected, and an unstretched, uniaxial or biaxially oriented film may be used. Among them, preferably a uniaxial 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. The thickness of a transparent base film is about 8-1000 micrometers, Preferably 40-100 micrometers is used.

Figure 2 is a cross-sectional view of a high hardness hard coating film according to another embodiment of the present invention. It comprises a hard coating layer formed on at least one surface of the transparent base film (1), wherein the hard coating layer is formed by applying a hard coating solution containing a hard coating solution or polyhetero acid and the first hard coating layer (3) It further comprises a second hard coating layer 4 formed by applying a hard coating solution containing polyhetero acid on the coating layer (3). In addition, after the first hard coating layer 3 is semi-cured, a hard coating solution containing polyheteroic acid is coated on the first hard coating layer 3 to form a second hard coating layer 4 so that crosslinking is formed. It is characterized by complete curing. 2, the hard coating layer may be formed on both sides of the transparent base film, and a specific layer may be further added to the upper and lower portions of each layer, and both are included in the present invention.

A hard coating solution or a polycoating acid-containing hard coating solution to form the hard coating layer may be formed by further comprising a conductive polymer.

Descriptions of the transparent base film, the hard coating layer, the polyhetero acid, the hard coating liquid, the conductive polymer, and the like are dedicated to the above description and will not be described. However, after the first hard coat layer 3 is semi-cured, the second hard coat layer 4 is coated and completely cured so that the unreacted reactive functional groups remaining on the surface of the first hard coat layer 3 and the first agent The reactive functional group of the 2 hard coat layer 4 causes chemical crosslinking to be formed by ultraviolet curing. Since crosslinking is formed between these layers, stronger adhesive performance can be obtained, thereby improving the strength. The semi-curing means hardening to a state before being fully cured (unreacted reactive functional groups remaining less than 5%). Preferably, it is preferable to cure at a light amount of 0.1 ~ 0.2J / cm 2 having a mechanical strength capable of applying the second hard coating layer (4).

Hereinafter, a method of manufacturing a high hardness hard coat film will be described. The same configuration as that of the high-hardness hard coat film described above is similar to that described above, and detailed descriptions thereof will be omitted.

Figure 3 is a schematic diagram illustrating a method for manufacturing a high hardness hard coat film according to an embodiment of the present invention. As shown, it comprises a step of forming a hard coating layer by applying a hard coating liquid containing polyheteroic acid on at least one surface of the transparent base film, and the step of completely curing the hard coating layer. After applying the hard coating solution, it may be dried first and then cured, and included in the present invention. The hard coating solution may further include a conductive polymer, and the hard coating solution may include a polyfunctional organic material having a polymerizable unsaturated group and reactive silica particles chemically bonded to siloxy groups on the surface of the silica particles.

Figure 4 is a schematic diagram illustrating a method for manufacturing a high-hardness hard coating film according to another embodiment of the present invention. As shown, forming a first hard coating layer by applying a hard coating liquid or a hard coating liquid containing polyheteroacid to at least one surface of the transparent substrate film, semi-curing the first hard coating layer, the first hard coating layer Forming a second hard coat layer by applying a hard coating solution containing polyhetero acid on the upper portion of the second hard coat layer, and completely curing the first hard coat layer and the second hard coat layer. The hard coating solution or the hard coating solution containing polyhetero acid may further include a conductive polymer.

After the first hard coat layer is semi-cured, the second hard coat layer is coated and completely cured so that crosslinking is formed between the first hard coat layer and the second hard coat layer. As crosslinking is formed between these layers, stronger adhesion performance can be obtained. The semi-curing means to harden to a state before complete curing (the state where there is no further progress in the degree of hardening). Preferably, it is preferable to cure to the minimum having a mechanical strength capable of applying the second hard coat layer. In order to semi-harden, it is possible to simply adjust the amount of ultraviolet radiation by reducing light energy, irradiation time and the like.

In the present invention, the coating of the hard coat film can be coated in a suitable manner such as die coating, casting, gravure and spin coating.

The coating thickness is usually about 0.1 to 200 mu m, and preferably about 1 to 50 mu m. After application, the composition is dried by evaporation of volatiles for 1 second to 2 hours, preferably 5 seconds to 1 hour at a temperature of 30-150 ° C. The irradiation amount of UV light is about 0.01-10 J / cm <^2> , Preferably it is 0.1-2 J / cm <^2> .

The antistatic high hardness hard coat film prepared as described above has excellent high hardness, antistatic property, abrasion resistance, weather resistance, and optical high transparency, and has excellent productivity due to fast curing speed during its manufacture, and is produced after curing. The film did not generate a curling phenomenon.

The present invention also provides a polarizing plate and a liquid crystal display device provided with the antistatic high hardness hard coating film or the antistatic high hardness hard coating film manufactured by the above-described manufacturing method.

Which configuration of the antistatic high hardness hard coating film is applied to the polarizing plate and the liquid crystal display device is not limited, and may be preferably applied as long as a film having high hardness and antistatic properties can be used. Examples thereof include a protective film of a polarizing plate, a protective film of an image display part of a liquid crystal display, and the like, and are well known in the art.

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

<Example 1>

Hard coating solution (product name: DN-0081.manufacturer: DSM Desotech Inc.) Apply the coating composition mixed with 85 wt% to 12 wt% of tungsteric acid to 15 μm on the transparent substrate film (TAC) Meyer bar) and dried for 1 minute at 70 ℃, then cured to 1J / cm ² to prepare a hard coating film.

<Example 2>

Hard coating solution (product name: DN-0081.manufacturer: DSM Desotech Inc.) Myerba on the transparent substrate film (TAC) to the coating composition mixed with 85% by weight of 12- tungstosilic acid 15% by weight (Meyer bar) and then dried at 70 ℃ for 1 minute, and then cured to 1J / cm ² to prepare a hard coating film of high hardness.

<Example 3>

Hard coating solution (product name: DN-0081.manufacturer: DSM Desotech Inc.) A coating composition obtained by mixing 85% by weight of 5% by weight of polyethylenedioxythiophene and 10% by weight of 12-tungstoic acid on a transparent substrate film (TAC) Was applied to a Meyer bar (Meyer bar) and dried for 1 minute at 70 ℃, and then cured to 1J / cm ² to prepare a hard coating film.

<Example 4>

Hard coating solution (Product name: DN-0081. Manufacturer: DSM Desotech Inc.) The coating composition was mixed with 85% by weight of 5% by weight of polypyrrole and 10% by weight of 12- tungstoic acid on the transparent substrate film (TAC). It was applied to a meyer bar (Meyer bar) and dried for 1 minute at 70 ℃, then cured to 1J / cm ² to prepare a hard coating film.

<Example 5>

Hard coating solution (Product name: DN-0081. Manufacturer: DSM Desotech Inc.) was applied on a transparent substrate film (TAC) with a Meyer bar to a thickness of 10 ㎛ and dried at 70 ℃ for 1 minute, then the coating composition The amount of ultraviolet irradiation is adjusted to 0.2 J / cm ² so as not to be completely cured, and semi-cured so that the reactive functional groups remain. On the semi-cured film, a coating composition obtained by mixing a hard coating solution (product name: DN-0081, manufactured by DSM Desotech Inc.) with 15 wt% of 12-tungstoic acid was mixed in a thickness of 5 μm. bar) and dried at 70 ° C. for 1 minute and then completely cured to 1 J / cm ² to prepare a hard coating film.

<Example 6>

Hard coating solution (Product name: DN-0081. Manufacturer: DSM Desotech Inc.) was applied on a transparent substrate film (TAC) with a Meyer bar to a thickness of 10 ㎛ and dried at 70 ℃ for 1 minute, then the coating composition The amount of ultraviolet irradiation is adjusted to 0.2 J / cm ² so as not to be completely cured, and semi-cured so that the reactive functional groups remain. On the semi-cured film, a coating composition obtained by mixing 5% by weight of polyethylenedioxythiophene and 10% by weight of 12-tungstoic acid in 85% by weight of the hard coating solution (product name: DN-0081, manufacturer: DSM Desotech Inc.) It was applied to a Meyer bar (Meyer bar) and dried for 1 minute at 70 ℃, and then completely cured to 1J / cm ² to prepare a high-hardness hard coating film to 5㎛.

<Example 7>

Hard coating solution (product name: DN-0081.manufacturer: DSM Desotech Inc.) Apply the coating composition of 12 wt% of 12- tungstoic acid to 85 wt% of Myerba (10 μm) on a transparent substrate film (TAC). Meyer bar) and dried at 70 ° C. for 1 minute, and then the amount of ultraviolet radiation is adjusted to 0.2 J / cm ² so that the coating composition does not fully cure, and is semi-cured so as to leave reactive functional groups. On the semi-cured film, a coating composition obtained by mixing 5% by weight of polyethylene dioxythiophene and 10% by weight of 12-tungstoic acid was mixed with 85% by weight of the hard coating solution (product name: DN-0081, manufacturer: DSM Desotech Inc.). It was applied to a Meyer bar (Meyer bar) and dried for 1 minute at 70 ℃, and then completely cured to 1J / cm ² to prepare a high-hardness hard coating film to 5㎛.

When the polarizing film was manufactured using the hard-coating film of each said Example as a protective layer of an iodine type absorption dichroic polarizing plate, the polarization which has the high practical practical surface protection function which maintained the characteristic of the said antistatic high hardness hard-coating film A film was obtained.

Comparative Example 1

Hard coating solution (Product name: DN-0081. Manufacturer: DSM Desotech Inc.) was applied on a transparent substrate film (TAC) with a Meyer bar to a thickness of 15㎛ and dried for 1 minute at 70 ℃, 1J / It was cured to cm ² to prepare a high hardness hard coat film.

Comparative Example 2

Hard coating solution (Product name: DN-0081. Manufacturer: DSM Desotech Inc.) was applied on a transparent substrate film (TAC) to a thickness of 10㎛ with a Meyer bar and dried at 70 ℃ for 1 minute, then 1J / Completely harden to cm ² . On this fully cured film, a coating composition containing 5% by weight of polyethylenedioxythiophene and 10% by weight of 12-tungstoic acid was mixed with 85% by weight of the hard coating solution (product name: DN-0081. Manufacturer: DSM Desotech Inc.). It was applied to a Meyer bar (Meyer bar) and dried for 1 minute at 70 ℃, and then completely cured to 1J / cm ² to prepare a high-hardness hard coating film to 5㎛.

Comparative Example 3

Hard coating solution (Product name: DN-0081. Manufacturer: DSM Desotech Inc.) The coating composition of 15 wt% polyethylenedioxythiophene mixed with 85 wt% of Meyer Bar on the transparent substrate film (TAC) to have a thickness of 15 μm bar) and dried at 70 ° C. for 1 minute and then cured at 1 J / cm ² to prepare a hard coating film.

<Comparative Example 4>

Dipentaerythritol pentaacrylate (Japanese gunpowder) 25.5 weight%, colloidal silica (MEK-ST, Ilsan Chemical) 8.5 weight%, 1-hydroxy cyclohexyl phenyl ketone (Chiba gauge) 0.80 weight%, methyl isobutyl ketone 50.1% by weight of fluorine-based surfactant (FC430, 3M Co. Ltd) to the 15% by weight of 12- tungstoic acid mixed with 0.1% by weight on the transparent substrate film (TAC) Meyer bar (Meyer bar) ) And dried at 70 ° C. for 1 minute, and then cured at 1 J / cm ² to prepare a hard coating film.

Comparative Example 5

Hard coating solution (Product name: DN-0081. Manufacturer: DSM Desotech Inc.) was applied on a transparent substrate film (TAC) with a Meyer bar to a thickness of 10 ㎛ and dried at 70 ℃ for 1 minute, then the coating composition The amount of ultraviolet irradiation is adjusted to 0.2 J / cm ² so as not to be completely cured, and semi-cured so that the reactive functional groups remain. On this semi-cured film, a coating composition obtained by mixing 10 wt% of polyethylene dioxythiophene with 90 wt% of the hard coating solution (Product Name: DN-0081. Manufacturer: DSM Desotech Inc.) ) Hardened to 1 J / cm ² and then dried at 70 ° C. for 1 minute to prepare a high hardness hard coat film.

Physical properties of the films prepared in Examples 1 to 7 and Comparative Examples 1 to 5 were measured by the following methods, and the results are shown in Tables 1 and 2 below.

(1) transmittance and haze

Total transmittance and haze were measured by using a spectrophotometer (HZ-1, manufactured by Suga Japan) as the TAC plane toward the light source D65.

(2) pencil hardness

The pencil hardness is measured using a pencil hardness tester (PHT, manufactured by Seokbo Science, Korea) under a 500g load. The pencil is made with Mitsubishi products and is used five times per pencil hardness. If there were two or more gases, it was determined to be defective.

Kiss: 0 OK

Kiss: 1 OK

Ges: 2 or more NG

(3) scratch resistance

The scratch resistance was tested by using a steel wool tester (WT-LCM100, manufactured by Protec Korea) for 10 reciprocations at 1 kg / (2 cm × 2 cm).

Steel wool uses # 0000.

A: 0 scratches

A ': 1 to 10 scratches

B: 11 to 20 scratches

C: 21 to 30 scratches

D: 31 or more scratches

(4) adhesion

After eleven straight lines are drawn on the coated surface of the film at intervals of 1 mm each to make 100 squares, three peel tests are performed using a tape (CT-24, Nichi Nippon Co., Ltd.). Three 100 squares were tested and averaged.

The adhesion is recorded as follows.

Adhesion = n / 100

n: number of rectangles that do not peel out of the entire rectangle

100: total number of squares

Therefore, if none were peeled off, record 100/100.

(5) surface resistance

The surface resistance is measured on the coated surface of the film using a surface resistance measuring instrument (MCP-HT450, manufactured by Mitsubishi Chemical, Japan). The voltage starts at 10V and when the surface resistance is over, the voltage is measured in the order of 100V, 250V, 500V, and 1000V.

(6) curling

The sample cut into the square shape of A4 size (29.7 X 21.0 cm) was placed on a flat glass plate with the coated surface of the film facing up, and the distance from the square glass plate was measured at 25 ° C. and 50% RH, and then averaged. Was taken as a measured value.

Very good: 0 to 15 mm, Good: 15 to 30 mm, Bad: 30 to 50 mm, Very poor: More than 50 mm

TABLE 1

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Total light transmittance (%) 91.7 91.4 91.2 90.5 91.1 90.9 90.5 Haze 0.3 0.3 0.4 0.6 0.4 0.4 0.5 Pencil hardness 5H 5H 4H 4H 6H 5H 6H Scratch resistance A A A ' A ' A A ' A ' Adhesion 100/100 100/100 100/100 100/100 100/100 100/100 100/100 Surface resistance (Ω / □) 109 1011 107 109 109 107 107 curling Very good Very good Very good Good Very good Very good Very good

TABLE 2

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Total light transmittance (%) 92.1 91.0 90.1 90.3 89.9 Haze 0.3 0.4 0.5 0.5 0.5 Pencil hardness 5H 3H 3H 2H 3H Scratch resistance A B B C B Adhesion 100/100 90/100 100/100 95/100 100/100 Surface resistance (Ω / □) 1015 107 1012 1010 1011 curling Very good Very good Very good Bad Bad

The antistatic high hardness hard coat film produced according to the present invention has excellent high hardness, antistatic property, abrasion resistance, weather resistance and optical high transparency. In addition, according to the present invention, the curing rate is high at the time of manufacturing a high hardness hard coating film, and the productivity is excellent, and the film produced after curing does not generate a curling phenomenon.

Claims (13)

And a hard coating layer formed on at least one surface of the transparent base film, wherein the hard coating layer is formed by applying a hard coating liquid containing polyhetero acid. It comprises a hard coating layer formed on at least one surface of the transparent substrate film, the hard coating layer is a first hard coating layer formed by applying a hard coating solution containing a hard coating solution or polyhetero acid, and a polyhetero on the first hard coating layer An antistatic high hardness hard coating film comprising a second hard coating layer formed by applying a hard coating solution containing an acid. The antistatic high hardness hard coat film of claim 2, wherein crosslinking is partially formed between the first hard coat layer and the second hard coat layer. The antistatic method according to any one of claims 1 to 3, wherein the hard coating solution comprises a polyfunctional organic material having a polymerizable unsaturated group and reactive silica particles chemically bonded to siloxy groups on the surface of the silica particles. Hardened hard coating film. The polyhetero acid according to any one of claims 1 to 3, wherein at least one selected from the group consisting of a tungstophosphoric acid system, a tungstosilonic acid system, and a molybdophosphoric acid system, wherein the hard coating solution is 100 wt Antistatic high hardness hard coating film, characterized in that contained 1 to 30% by weight relative to%. The antistatic high hardness hard coat film according to any one of claims 1 to 3, wherein the hard coating liquid or the hard coating liquid containing polyhetero acid further comprises a conductive polymer. The method of claim 6, wherein the conductive polymer is polyaniline, polypyrrole or polythiophene, antistatic high hardness hard coating film, characterized in that 0.05 to 30% by weight based on 100% by weight of the hard coating liquid. According to any one of claims 1 to 3, 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, polyester, polystyrene, polyamide, polyetherimide, polyacryl, polyimide, polyethersulfone, 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, and epoxy At least one in the county It comprises a selected, non-stretched (未 延伸), antistatic, characterized in that a uniaxial or biaxial oriented film sex hardness hard coat film. Forming a hard coating layer on at least one surface of the transparent base film by applying a hard coating solution containing polyhetero acid; And Full hardening of the hard coating layer; Method of producing an antistatic high hardness hard coating film comprising a. Forming a first hard coating layer on at least one surface of the transparent base film by applying a hard coating liquid or a hard coating liquid containing polyhetero acid; Semi-curing the first hard coating layer; Forming a second hard coat layer by applying a hard coating solution including polyhetero acid on the first hard coat layer; And And completely curing the crosslinking between the first hard coat layer and the second hard coat layer to form an antistatic high hardness hard coat film. The method of claim 9 or 10, wherein the hard coating solution or the hard coating solution containing polyhetero acid further comprises a conductive polymer antistatic high hardness hard coating film production method. A polarizing plate having an antistatic high hardness hard coating film of any one of claims 1 to 3 or an antistatic high hardness hard coating film prepared by the manufacturing method of claim 9. A liquid crystal display device comprising the antistatic high hardness hard coat film of any one of claims 1 to 3 or the antistatic high hardness hard coat film manufactured by the manufacturing method of claim 9.

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