WO2007004818A1 - Anti-reflective film having high surface hardness and antistatic property and method for producing the same - Google Patents
Anti-reflective film having high surface hardness and antistatic property and method for producing the same Download PDFInfo
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- WO2007004818A1 WO2007004818A1 PCT/KR2006/002561 KR2006002561W WO2007004818A1 WO 2007004818 A1 WO2007004818 A1 WO 2007004818A1 KR 2006002561 W KR2006002561 W KR 2006002561W WO 2007004818 A1 WO2007004818 A1 WO 2007004818A1
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- WIPO (PCT)
- Prior art keywords
- refractive index
- high refractive
- layer
- electroconductive
- antireflection film
- Prior art date
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/111—Anti-reflection coatings using layers comprising organic materials
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
Definitions
- the present invention relates, in general, to an anti-reflective polymer film and, more particularly, to an anti-reflective polymer film which is superior in surface hardness and antistatic property as well as being capable of minimizing the reflection of outside light.
- An anti-reflective layer which has recently been used as the outermost layer of displays of various display devices, such as CRTs, LCDs, PDPs, etc., functions to reduce reflectivity through the principle of optical interference to prevent a decrease in contrast and mirroring of images due to the reflection of outside light.
- Such an anti-reflective layer which plays an important role in improving the view of images on displays, is formed by depositing a plurality of thin layers having different refractive indices, designed to cause the light beams reflected from the layers to destructively interfere with each other.
- a suitable combination of thicknesses and refractive indices of the thin layers leads to effective reduction in the reflection of outside light.
- a film formed on one side of a display by alternately depositing a high refractive index inorganic substance, such as TiO or ZrO , and a low refractive index inorganic substance, such as SiO or MgF , by means of a vacuum evaporation method or a sputtering method exhibits significantly decreased light reflectivity (U. S. Pat. No. 6,689,479, Japanese Pat. Laid-Open Publication No. 9-197102).
- a dry coating method such as vacuum evaporation or sputtering, suffers from the drawback of having a very slow process rate, being difficult to use to form a coating on a large area display, and being very limitedly applicable to heat-susceptible polymeric base films due to the high process temperature thereof.
- an anti-reflection film formed through a wet-coating method featuring the application of a fluorine -based compound having a low refractive index to one side of a transparent polymer film and the application of the resulting antireflective transparent polymer film to a display (U. S. Pat. No. 6,502,943, Japanese Pat. Publication No. 9-203801).
- antireflection film means a film, which is formed not integrally with but separately from, a display and is applied to the display.
- an antireflection film comprises a base polymeric film coated on one side with an an- tireflective layer and on the other wide with an adhesive for direct attachment to a display.
- This type of antireflection film can be produced on a mass scale thanks to the high process rate and relatively moderate process temperatures, and thus is in increasing demand.
- an antireflection film that overcomes the problems encountered in the prior art, e.g, an antireflection film that has superb surface hardness and does not permit the occurrence of defects, such as cracks, and is also highly antistatic.
- poly- thiophene a conducting polymer.
- Polythiophene exhibits high transparency and elec- troconductivity and has mechanical flexibility, so that a film made therefrom is transparent, retains stable antistatic properties and does not undergo cracking.
- antireflection films made of conducting polymers are not widely used because of the following problems.
- an antireflection film having an outermost layer made of an electroconductive polymer exhibits high antistatic properties, but is apt to be scratched during use because the surface hardness of the electroconductive polymer layer is not high.
- an electro- conductive polymer layer may be used as an intermediate layer with a low refractive index layer having high surface hardness deposited thereon.
- the resulting film has improved surface hardness compared to the film having an electroconductive polymer as an outermost layer.
- the formation of one more layer makes the fabrication process complicated.
- the antireflective property of the film is not sufficient to effectively prevent decreased contrast and mirroring of images due to the reflection of outside light, since most electroconductive polymers range in refractive index from as low as 1.48 to 1.57, which is insufficient for use as high refractive index materials.
- an antistatic, an- tireflection film which comprises a transparent base polymer film on which a high refractive index electroconductive layer based on an electroconductive polymer, ranging in refractive index from 1.60 to 2.20, and a low refractive index electroconductive layer, based on fluoroorganic compound, having a high surface hardness and a refractive index of 1.25 to 1.55, are formed in the order.
- the present invention provides an antireflection film, showing excellent transparency, antistatic property, antifouling property, and surface hardness, comprising: a transparent base polymer film; a high refractive index electroconductive layer; having a refractive index of 1.60 to 2.20, a thickness of 0.01-1 microns and a surface resistance of 10E3-10E10 ohms/square, formed by layering a composition containing an electroconductive polymer and high refractive inorganic particles on one side of the transparent base polymer film; and a low refractive index layer, having a refractive index of 1.25 to 1.55 and a thickness of 0.01-1 microns, formed by layering a composition of a fluoroorganic compound or by layering a composition of a fluoroorganic compound and conductive polymer on the high refractive index electroconductive layer.
- the present invention provides a method for producing an antireflection film, showing excellent transparency, antistatic property, antifouling property, and surface hardness, comprising: providing a transparent base polymer film; forming a high refractive index electroconductive layer having a refractive index of 1.60 to 2.20, a thickness of 0.01-1 microns and a surface resistance of 10E3-10E10 ohms/square, by layering a composition containing an electroconductive polymer and high refractive inorganic particles on one side of the transparent base polymer film; and forming a low refractive index layer, having a refractive index of 1.25 to 1.55 and a thickness of 0.01-1 microns, by layering a composition comprising a fluoroorganic compound or by layering a composition comprising a fluoroorganic compound on the high refractive index electroconductive layer.
- the antireflection film of the present invention is composed of a transparent base polymer film, a high refractive index electroconductive layer formed by layering a resin composition comprising an electroconductive polymer and high refractive inorganic particles on one side of the transparent film, and a low refractive index layer formed by layering a heat- or UV-curable fluorine-modified resin on the high refractive index electroconductive layer.
- the antireflection film prepared according to the present invention can effectively reduce the reflection of outside light, ensuring clear contrast and mirroring of images. Also, the film is highly antistatic, thereby preventing the pollution of display due to the attachment of dust thereon.
- the high refractive index layer itself shows an antistatic property thus requiring no additional antistatic layers, which leads to the simplification of the fabrication process thereof.
- the antireflection film is superior in surface hardness and thus is prevented from being scratched during use. Consequently, the antireflection film of the present invention is very effective for use in various display devices.
- FIG. 1 is a cross sectional view showing a bilayer structure of an antireflection film according to an embodiment of the present invention.
- FIG. 2 is a cross sectional view showing a trilayer structure of an antireflection film according to another embodiment of the present invention. Mode for the Invention
- an antireflection film is shown in a cross sectional view in accordance with an embodiment of the present invention.
- an antireflection film 100 according to an embodiment of the present invention comprises a transparent polymer film 110 on one side of which a high refractive index layer 130, based on an electroconductive polymer and including high refractive index inorganic particles therein, and a low refractive index layer 140, based on a fluoroorganic compound, are formed in that order.
- any film can be used as the polymer film 110.
- the transparent polymer film 110 useful in the present invention include films made from polyesters, such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, etc., cellulose derivatives, such as diacetyl cellulose, triacetyl cellulose, etc., polyolefins, such as polypropylene, poly- methylpentene, etc., polycarbonates, polystyrenes, polyacrylate, polymethylmethacrylate, polysulfones, poly ethersulf ones, polyimides, polyetherimides, polyetherketones, and cyclic olefin resins.
- the antireflection film of the present invention When the antireflection film of the present invention is applied to a polarizer film for LCD, it preferably comprises a base film made from triacetyl cellulose.
- the antireflection film For the application of the antireflection film to flat CRT or PDP, it is preferable that the antireflection film comprise a transparent polymer film having a light transmittance of 80% or higher at 550 nm.
- the transparent polymer film is subjected to surface treatment, such as corona discharge treatment, glow discharge treatment, UV treatment, plasma treatment and the like, so that it provides an excellent adhesive condition for the layer to be formed thereon.
- the high refractive index electroconductive layer 130 may be formed by coating one side of the base film with a resin composition comprising an electroconductive pol ymer and high refractive index inorganic particles, and drying or curing the coating.
- the high refractive index electroconductive layer 130 plays a role as a high refractive index layer as well as an antistatic layer thanks to its high refractive index, which is in the range from 1.60 to 2.2.
- the formation of the high refractive index electroconductive layer may be largely divided into two steps: preparation of a resin composition comprising an electroconductive polymer and inorganic fine particles; and application and drying or curing of the resin composition.
- the preparation of the resin composition for the high refractive electroconductive layer starts with mixing an electroconductive polymer and high refractive index inorganic fine particles in an organic solvent, followed by uniformly dispersing the high refractive index inorganic fine particles with the aid of an apparatus, such as a sand grinder, a roll mill or a sonicator.
- the resin composition comprises an electroconductive polymer in an amount from 0.5 to 99.5 weight parts and high refractive index inorganic fine particles in an amount from 0.5 to 99.5 weight parts, with the optional addition of additives.
- the resin composition useful in the present invention comprises an electroconductive polymer in an amount from 0.5 to 24.5 weight parts, high refractive index inorganic fine particles in an amount from 10 to 70 weight parts, a heat- or UV-curable organic binder in an amount from 5 to 25 weight parts, and a heat curing agent or a photoinitiator in an amount from 0.05 to 10 weight parts.
- a coupling agent, a curing accelerator, a UV stabilizer, an anti-coloring agent, a leveling agent, a lubricant, and/or an adhesion promoter may be employed.
- the electroconductive polymer used in the high refractive index electroconductive layer is selected from a group consisting of polyaniline, polypyrrole, polythiophene, and derivatives thereof. Being superior in electroconductivity, transmittance of visual light, and thermal stability compared to other electroconductive polymers, polyethylenedioxythiophene, a polythiophene derivative, is particularly suitable for use as an antistatic material for the antireflection film. Despite the excellent antistatic property and transparency, most of the electroconductive polymers, such as polyethylenedioxythiophene, are of limited use because their refractive indices are as low as 1.48 to 1.57. In accordance with the present invention, accordingly, inorganic fine particles having a high refractive index are mixed with the electroconductive polymer so as to increase the overall refractive index of the resulting composition.
- any type of inorganic fine particle may be used in the resin composition for the high refractive index electroconductive layer.
- the inorganic fine particles may be particles of a metal oxide, such as titan dioxide (rutile, rutile/anatase mix crystal, anatase type), tin oxide, indium oxide, zirconium oxide, aluminum oxide, or a metal sulfide, such as zinc oxide.
- a metal oxide such as titan dioxide (rutile, rutile/anatase mix crystal, anatase type)
- tin oxide indium oxide, zirconium oxide, aluminum oxide, or a metal sulfide, such as zinc oxide.
- particle sizes are important factors in determining the physical properties of the antireflection film. Greater particle size results in lower transparency to visible light.
- the inorganic fine particles have a mean particle size from 1 to 300 nm.
- the inorganic fine particles are preferably used in an amount from 10 to 70 weight parts based on 100 weight parts of the resin composition for the high refractive electroconductive layer.
- the amount of inorganic fine particles is less than 10 weight parts, only an insignificant increase in refractive index can be obtained.
- an amount greater than 70 weight parts of the inorganic fine particles leads to a reduction in transparency and physical properties.
- the surfaces of the inorganic fine particles are preferably treated with an inorganic or an organic compound.
- the inorganic fine particles When treated with an inorganic compound, such as alumina or zirconium oxide, or when used in combination with organic compounds, such as stearic acid or stearate, and/or a silane- or titanate-based coupling agent, the inorganic fine particles, such as titan dioxide, can be uniformly dispersed, thereby preventing a decrease in transparency attributable to the aggregation thereof. It is preferred that the inorganic or organic compound be used in an amount from 0.01 to 5 weight parts based on 100 weight parts of the inorganic fine particles.
- the organic binder useful in the resin composition for the high refractive index electroconductive layer is an organic compound which is heat or UV curable. As long as it contains a functional group necessary for crosslinking, such as ester, ether, epoxy, urethane, alkyd, etc., and has a higher surface hardness than that of the electroconductive polymer after being cured, any organic binder may be used.
- a high refractive index electroconductive layer showing a high antistatic property and refractive index, may be formed of a resin composition prepared from a mixture of an electroconductive polymer and inorganic fine particles in the absence of the organic binder.
- the organic binder plays a role in complementing the mechanical strength of the high refractive index electroconductive layer.
- the organic binder is an organic compound which contains a sulfur atom or a benzene ring therein, and ranges in refractive index from 1.55 to 1.70.
- an organic binder having a low refractive index decreases the refractive index of the high refractive index electroconductive layer.
- the resin composition used for the formation of the high refractive index electroconductive layer is prepared in the form of a dispersion of the electroconductive polymer, the inorganic fine particles and an organic binder in an organic solvent.
- Useful is a solvent which has a boiling point from 50 to 200 0 C.
- Various organic solvents may be used depending on the electroconductive polymer and organic binder.
- organic solvent useful in the present invention examples include, but not are limited to, water, alcohols (methanol, ethanol, isopropanol, and isobutanol), amides (2-pyrrolidone, N-methyl-2-pyrrolidone, N-methylformamide and N, N- dimethylformamide), ethers and ether alcohols (ethyleneglycol, glycerol, ethyleneglycol monomethylether, ethyleneglycol monoethylether, l-methoxy-2-propanol and diethylether), and combinations thereof.
- alcohols methanol, ethanol, isopropanol, and isobutanol
- amides (2-pyrrolidone, N-methyl-2-pyrrolidone, N-methylformamide and N, N- dimethylformamide
- ethers and ether alcohols ethyleneglycol, glycerol, ethyleneglycol monomethylether, ethyleneglycol monoethylether, l-meth
- the resin composition prepared as described above is applied to one side of a base film and dried or cured to form a high refractive index electroconductive layer 0.01 to 1 micron thick.
- various wet coating methods known in the art such as a wire-bar coating method, a roll coating method, a spraying method, a gravure coating method, a reverse-gravure coating method, etc., may be used depending on the method of forming the electroconductive polymer of the resin composition.
- a wet coating method is conducted to apply the composition to the base film.
- a high refractive index electroconductive layer can be formed using a gas phase polymerization method, in which a polymerization initiator and a dopant are mixed with the organic binder and the inorganic fine particles and applied to the base film, and polymerizable electroconductive monomers in a gas phase are directly polymerized on the surface of the film.
- the high refractive index electroconductive layer formed using the method described above is 0.01 to 1 micron thick and has a refractive index from 1.60 to 2.20 and a surface resistance from 10E3 to 1OE 10 ohm/square and a transmittance of visible light from 65.0 to 99.5%.
- the low refractive index layer 140 it can be formed by applying a fluorine- modified resin composition on the high refractive index electroconductive layer 130 and curing the resin solution.
- the fluorine-modified resin composition according to the present invention comprises a heat- or UV-curable fluorine-modified resin in an amount from 90-99.9 weight parts and a heat curing agent or a photoinitiator in an amount from 0.01 to 10 weight parts, and optionally a curing accelerator, a UV stabilizer, an anti-colorant, a surface smoothing agent, a lubricant, a water repellent, and/or an organic solvent.
- the heat- or UV-curable fluorine-modified resin is a monomeric or oligomeric compound synthesized through the reaction of a compound having a fluorine substituent and a compound having a crosslinkable functional group.
- Preferable is a monomeric or oligomeric compound which has a refractive index from 1.25 to 1.55 and can increase in surface hardness as the curing reaction proceeds.
- fluorine substituent-containing compound useful in the present invention examples include fluoroolefins (e.g., fluoroethylene, vinylidene fluoride, tetrafluo- roethylene, hexafluoroethylene, hexafluoropropylene and perfluoro- 2,2-dimethyl-l,3-dioxol), fluoro(meth)acrylic acid ester, fluoroalkyl (meth)acryl, and fluorovinyl ether.
- the compound having a crosslinkable functional group may be exemplified by (meth)acrylates having an epoxy group, a carboxyl group, a hydroxyl group, an amino group or sulfonic acid.
- a more preferable fluorine-modified resin may be comprised of a fluorine-modified multifunctional acrylate compound synthesized by reacting a compound having perflu- oropolyether with multifunctional acrylate.
- a perfluoropolyether compound having various functional groups such as perfluoropolyether polyol having hydroxyl groups, perfluoropolyether dibasic acid having carboxylic acids, and perfluoropolyether epoxy compounds having epoxy groups, is reacted with a multifunctional acrylate compound, such as a modified acrylate compound having carboxylic acid, an epoxy group, or isocyanate, to form a monomer or oligomer having 2 to 16 functional groups.
- the fluorine-modified multifunctional acrylate compound resulting from the reaction of perfluoropolyether compound with multifunctional (meth)acrylate is used in the present invention.
- the low refractive index layer is required to have a surface hardness high enough to provide sufficient resistance to scratching and abrasion, and must also show a low refractive property.
- Most of the resins into which fluorine substituents are introduced in order to decrease the refractive index thereof are non-crosslinkable, and thus they do not increase in surface hardness or abrasion resistance.
- the perfluoropoly ether compound and the multifunctional (meth)acrylate can be mixed in an arbitrary ratio thanks to good compatibility therebetween, and therefore, the fluorine-modified multifunctional acrylate used in the present invention can be prepared by reaction therebetween, and the refractive index and surface hardness thereof can be readily controlled.
- the low refractive index layer is not limited to products prepared from the fluorine- modified resin, but may be a thin layer having a refractive index of 1.25 to 1.55 even if it is prepared using a conventional method.
- a fluorocarboxylic acid or fluoroalkyl silane compound is applied on the high refractive index electroconductive layer formed on the transparent base film, and then thermally cured.
- a silicate compound is layered on the high refractive index electroconductive layer and subjected to a sol-gel reaction to form a low refractive index layer.
- MgF which has been used conventionally, may be layered on the high refractive index electroconductive layer to produce the an- tireflection film.
- a resin composition containing low refractive index inorganic fine particles, such as silica may be used for the formation of the low refractive index layer.
- the incorporation of bubbles into a resin through a chemical or physical method can reduce the refractive index to a degree suitable for use in the low refractive index layer formed on the high refractive index electroconductive layer.
- a resin composition containing inorganic fine particles such as silica or a resin composition containing bubbles having a size of tens of microns can be applied for the formation of the low refractive index layer on the high refractive index electroconductive layer.
- the antireflection film comprises a transparent base polymer film 110 and a high refractive index electroconductive layer 130, with a hard coating layer 120 intercalated therebetween.
- the hard coating layer functions to improve the mechanical strength of the antireflection film, and may be formed of a heat- or UV-curable compound, examples of which include an acryl compound, a urethane compound, an epoxy compound, a silane compound, and a silicate compound, but are not limited thereto. As long as it has a surface hardness of IH or greater, and more preferably 2H or greater, after being cured, any compound may be used to form the hard coating layer.
- only a low refractive index layer may be formed on a transparent base polymer film, or a high refractive layer and a low refractive layer may be alternately formed on a transparent base polymer film. In either case, the high refractive index layer and the low refractive index layer in accordance with the present invention can be used.
- the low refractive index layer may further comprise an electro- conductive polymer.
- the content of the electroconductive polymer is the same as in the high refractive index layer, while the fluoro compound is reduced as much.
- a resin composition for a high refractive index electroconductive layer was prepared. 30 wt parts of titanium dioxide (mean particle size: 40 nm, refractive index: 2.70), 5 wt parts of a titanate -based coupling agent, 40 wt parts of water and 25 wt parts of ethyleneglycol monomethylether were mixed using an ultrasonic dispersing apparatus to yield a titanium dioxide dispersion. This dispersion was mixed in a volume ratio of 70:30 with a solution of the water-dispersable electroconductive polymer polyethylenedioxythiophene.
- the resulting mixture was layered on one side of a triacetylcellulose (TAC) film having a thickness of 80 microns, and dried at 8O 0 C for 1 min to produce a 100 nm- thick high refractive index electroconductive layer 100 nm thick.
- TAC triacetylcellulose
- Example 2 [41] The same procedure as in Example 1 was conducted with the exception that a polyethyleneterephthalate (PET) film 120 microns thick was used as a transparent base polymer film.
- PET polyethyleneterephthalate
- Example 2 The same procedure as in Example 2 was conducted, with the exception that the titanium dioxide dispersion and the polyethylene dioxythiophene solution were mixed in different ratios to provide different titanium dioxide contents for the high refractive index electroconductive layer.
- the titanium dioxide dispersion was mixed with the polyethylene dioxythiophene solution in volume ratios of 60/40, 50/50, and 40/60, respectively.
- Each of the antireflection films prepared in Examples 1-5 had a bilayer structure in which the high refractive index electroconductive layer and the low refractive index layer were formed on a transparent base polymer film. Physical properties of the antireflection films are summarized in Table 1, below, in which n represents the refractive index.
- Each of the antireflection films prepared according to Examples 6 and 7 had a trilayer structure in which a hard coating layer, a high refractive index electro- conductive layer and a low refractive index layer were formed in that order on a base film.
- the physical properties of the antireflection films are summarized in Table 2, below.
- the antistatic antireflection film having a high hardness can be used in various display devices, such as CRTs, LCDs, PDPs, etc., ensuring clear contrast and mirroring of images by minimizing the reflection of outside light
Abstract
Disclosed is an antistatic antireflection film which has a high hardness and is applicable to various display devices, such as CRTs, LCDs, PDPs, etc., ensuring clear contrast and mirroring of images by minimizing the reflection of outside light. The antireflection film (100) can be prepared by applying a mixture of an electroconductive polymer and high refractive inorganic fine particles to one side of a transparent base polymer film (110). Alternatively, high refractive index fine particles coated with an electroconductive polymer are used to form a high refractive index layer 0.01-1 micron thick on one side of a transparent base polymer and a heat- or UV-curable fluorine-modified resin is used to form a low refractive index layer. The antireflection film is transparent and has a good antistatic property. The low refractive index layer made of fluorine-modified multifunctional acrylate is superior with respect to antireflective property and surface hardness. Also, the electroconductive, high refractive index layer plays a role as an antistatic layer.
Description
Description
ANTI-REFLECTIVE FILM HAVING HIGH SURFACE
HARDNESS AND ANTISTATIC PROPERTY AND METHOD
FOR PRODUCING THE SAME
Technical Field
[1] The present invention relates, in general, to an anti-reflective polymer film and, more particularly, to an anti-reflective polymer film which is superior in surface hardness and antistatic property as well as being capable of minimizing the reflection of outside light. Background Art
[2] An anti-reflective layer, which has recently been used as the outermost layer of displays of various display devices, such as CRTs, LCDs, PDPs, etc., functions to reduce reflectivity through the principle of optical interference to prevent a decrease in contrast and mirroring of images due to the reflection of outside light.
[3] Currently, such an anti-reflective layer, which plays an important role in improving the view of images on displays, is formed by depositing a plurality of thin layers having different refractive indices, designed to cause the light beams reflected from the layers to destructively interfere with each other. On the basis of such optical interference, a suitable combination of thicknesses and refractive indices of the thin layers leads to effective reduction in the reflection of outside light. For example, a film formed on one side of a display by alternately depositing a high refractive index inorganic substance, such as TiO or ZrO , and a low refractive index inorganic substance, such as SiO or MgF , by means of a vacuum evaporation method or a sputtering method exhibits significantly decreased light reflectivity (U. S. Pat. No. 6,689,479, Japanese Pat. Laid-Open Publication No. 9-197102). However, a dry coating method, such as vacuum evaporation or sputtering, suffers from the drawback of having a very slow process rate, being difficult to use to form a coating on a large area display, and being very limitedly applicable to heat-susceptible polymeric base films due to the high process temperature thereof.
[4] In order to overcome the above problems, suggested is an anti-reflection film formed through a wet-coating method featuring the application of a fluorine -based compound having a low refractive index to one side of a transparent polymer film and the application of the resulting antireflective transparent polymer film to a display (U. S. Pat. No. 6,502,943, Japanese Pat. Publication No. 9-203801).
[5] As used herein, the term antireflection film means a film, which is formed not integrally with but separately from, a display and is applied to the display. Usually, an
antireflection film comprises a base polymeric film coated on one side with an an- tireflective layer and on the other wide with an adhesive for direct attachment to a display. This type of antireflection film can be produced on a mass scale thanks to the high process rate and relatively moderate process temperatures, and thus is in increasing demand.
[6] However, most conventional anti-reflection films show good anti-reflective properties, but have poor surface hardness and abrasion resistance, and thus are vulnerable to scratching. In addition, because their antistatic property is insufficient or lacking, conventional anti-reflection films are apt to allow dust to collect on displays. Suggested as an alternative to overcome these drawbacks was an antireflection film which comprises a high refractive layer, made of highly transparent and electro- conductive ITO (indium tin oxide) having a refractive index of about 2.0, and a low refractive layer made of fluoroorganic compound, thus being imparted with antistatic properties (U. S. Pat. No. 6,899,957). An antireflection film based on ITO exhibits excellent antistatic and antireflective functions, but is economically disadvantageous and easily cracked because ITO is expensive and lacks mechanical flexibility.
[7] Therefore, there is a requirement for an antireflection film that overcomes the problems encountered in the prior art, e.g, an antireflection film that has superb surface hardness and does not permit the occurrence of defects, such as cracks, and is also highly antistatic. To meet this requirement, intensive attention is being paid to poly- thiophene, a conducting polymer. Polythiophene exhibits high transparency and elec- troconductivity and has mechanical flexibility, so that a film made therefrom is transparent, retains stable antistatic properties and does not undergo cracking. In spite of such advantages, antireflection films made of conducting polymers are not widely used because of the following problems. First, an antireflection film having an outermost layer made of an electroconductive polymer exhibits high antistatic properties, but is apt to be scratched during use because the surface hardness of the electroconductive polymer layer is not high. In order to avoid this problem, an electro- conductive polymer layer may be used as an intermediate layer with a low refractive index layer having high surface hardness deposited thereon. The resulting film has improved surface hardness compared to the film having an electroconductive polymer as an outermost layer. However, the formation of one more layer makes the fabrication process complicated. Further, the antireflective property of the film is not sufficient to effectively prevent decreased contrast and mirroring of images due to the reflection of outside light, since most electroconductive polymers range in refractive index from as low as 1.48 to 1.57, which is insufficient for use as high refractive index materials.
[8] Therefore, there is a need for a method that can impart an electroconductive layer with both a high antistatic property and a high refractive index, thereby preparing an
antireflective polymer film. Disclosure of Invention
Technical Problem
[9] It is therefore an object of the present invention to provide an antistatic, an- tireflection film which comprises a transparent base polymer film on which a high refractive index electroconductive layer based on an electroconductive polymer, ranging in refractive index from 1.60 to 2.20, and a low refractive index electroconductive layer, based on fluoroorganic compound, having a high surface hardness and a refractive index of 1.25 to 1.55, are formed in the order. Technical Solution
[10] In accordance with an aspect, the present invention provides an antireflection film, showing excellent transparency, antistatic property, antifouling property, and surface hardness, comprising: a transparent base polymer film; a high refractive index electroconductive layer; having a refractive index of 1.60 to 2.20, a thickness of 0.01-1 microns and a surface resistance of 10E3-10E10 ohms/square, formed by layering a composition containing an electroconductive polymer and high refractive inorganic particles on one side of the transparent base polymer film; and a low refractive index layer, having a refractive index of 1.25 to 1.55 and a thickness of 0.01-1 microns, formed by layering a composition of a fluoroorganic compound or by layering a composition of a fluoroorganic compound and conductive polymer on the high refractive index electroconductive layer.
[11] In accordance with another aspect, the present invention provides a method for producing an antireflection film, showing excellent transparency, antistatic property, antifouling property, and surface hardness, comprising: providing a transparent base polymer film; forming a high refractive index electroconductive layer having a refractive index of 1.60 to 2.20, a thickness of 0.01-1 microns and a surface resistance of 10E3-10E10 ohms/square, by layering a composition containing an electroconductive polymer and high refractive inorganic particles on one side of the transparent base polymer film; and forming a low refractive index layer, having a refractive index of 1.25 to 1.55 and a thickness of 0.01-1 microns, by layering a composition comprising a fluoroorganic compound or by layering a composition comprising a fluoroorganic compound on the high refractive index electroconductive layer.
[12] The antireflection film of the present invention is composed of a transparent base polymer film, a high refractive index electroconductive layer formed by layering a resin composition comprising an electroconductive polymer and high refractive inorganic particles on one side of the transparent film, and a low refractive index layer
formed by layering a heat- or UV-curable fluorine-modified resin on the high refractive index electroconductive layer.
Advantageous Effects
[13] The antireflection film prepared according to the present invention can effectively reduce the reflection of outside light, ensuring clear contrast and mirroring of images. Also, the film is highly antistatic, thereby preventing the pollution of display due to the attachment of dust thereon. The high refractive index layer itself shows an antistatic property thus requiring no additional antistatic layers, which leads to the simplification of the fabrication process thereof. In addition, the antireflection film is superior in surface hardness and thus is prevented from being scratched during use. Consequently, the antireflection film of the present invention is very effective for use in various display devices. Brief Description of the Drawings
[14] FIG. 1 is a cross sectional view showing a bilayer structure of an antireflection film according to an embodiment of the present invention.
[15] FIG. 2 is a cross sectional view showing a trilayer structure of an antireflection film according to another embodiment of the present invention. Mode for the Invention
[16] A detailed description is given of resin compositions used for each layer of an antireflection film according to the present invention and of a preparation method thereof in conjunction with the drawings, below.
[17] With reference to FIG. 1, an antireflection film is shown in a cross sectional view in accordance with an embodiment of the present invention. As shown in FIG. 1, an antireflection film 100 according to an embodiment of the present invention comprises a transparent polymer film 110 on one side of which a high refractive index layer 130, based on an electroconductive polymer and including high refractive index inorganic particles therein, and a low refractive index layer 140, based on a fluoroorganic compound, are formed in that order.
[18] As long as it is highly transparent to visible light, any film can be used as the polymer film 110. Examples of the transparent polymer film 110 useful in the present invention include films made from polyesters, such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, etc., cellulose derivatives, such as diacetyl cellulose, triacetyl cellulose, etc., polyolefins, such as polypropylene, poly- methylpentene, etc., polycarbonates, polystyrenes, polyacrylate, polymethylmethacrylate, polysulfones, poly ethersulf ones, polyimides, polyetherimides, polyetherketones, and cyclic olefin resins. When the antireflection film of the present invention is applied to a polarizer film for LCD, it preferably comprises a base film
made from triacetyl cellulose. For the application of the antireflection film to flat CRT or PDP, it is preferable that the antireflection film comprise a transparent polymer film having a light transmittance of 80% or higher at 550 nm. Preferably, the transparent polymer film is subjected to surface treatment, such as corona discharge treatment, glow discharge treatment, UV treatment, plasma treatment and the like, so that it provides an excellent adhesive condition for the layer to be formed thereon.
[19] The high refractive index electroconductive layer 130 may be formed by coating one side of the base film with a resin composition comprising an electroconductive pol ymer and high refractive index inorganic particles, and drying or curing the coating. In the present invention, the high refractive index electroconductive layer 130 plays a role as a high refractive index layer as well as an antistatic layer thanks to its high refractive index, which is in the range from 1.60 to 2.2. The formation of the high refractive index electroconductive layer may be largely divided into two steps: preparation of a resin composition comprising an electroconductive polymer and inorganic fine particles; and application and drying or curing of the resin composition.
[20] The preparation of the resin composition for the high refractive electroconductive layer starts with mixing an electroconductive polymer and high refractive index inorganic fine particles in an organic solvent, followed by uniformly dispersing the high refractive index inorganic fine particles with the aid of an apparatus, such as a sand grinder, a roll mill or a sonicator. In accordance with the present invention, the resin composition comprises an electroconductive polymer in an amount from 0.5 to 99.5 weight parts and high refractive index inorganic fine particles in an amount from 0.5 to 99.5 weight parts, with the optional addition of additives. Preferably, the resin composition useful in the present invention comprises an electroconductive polymer in an amount from 0.5 to 24.5 weight parts, high refractive index inorganic fine particles in an amount from 10 to 70 weight parts, a heat- or UV-curable organic binder in an amount from 5 to 25 weight parts, and a heat curing agent or a photoinitiator in an amount from 0.05 to 10 weight parts. In addition to these ingredients, a coupling agent, a curing accelerator, a UV stabilizer, an anti-coloring agent, a leveling agent, a lubricant, and/or an adhesion promoter may be employed.
[21] The electroconductive polymer used in the high refractive index electroconductive layer is selected from a group consisting of polyaniline, polypyrrole, polythiophene, and derivatives thereof. Being superior in electroconductivity, transmittance of visual light, and thermal stability compared to other electroconductive polymers, polyethylenedioxythiophene, a polythiophene derivative, is particularly suitable for use as an antistatic material for the antireflection film. Despite the excellent antistatic property and transparency, most of the electroconductive polymers, such as polyethylenedioxythiophene, are of limited use because their refractive indices are as
low as 1.48 to 1.57. In accordance with the present invention, accordingly, inorganic fine particles having a high refractive index are mixed with the electroconductive polymer so as to increase the overall refractive index of the resulting composition.
[22] As long as its refractive index falls within the range of 1.60 to 2.90, any type of inorganic fine particle may be used in the resin composition for the high refractive index electroconductive layer. For example, the inorganic fine particles may be particles of a metal oxide, such as titan dioxide (rutile, rutile/anatase mix crystal, anatase type), tin oxide, indium oxide, zirconium oxide, aluminum oxide, or a metal sulfide, such as zinc oxide. Besides refractive index, particle sizes are important factors in determining the physical properties of the antireflection film. Greater particle size results in lower transparency to visible light. Preferably, the inorganic fine particles have a mean particle size from 1 to 300 nm. In consideration of the refractive index and transparency of the final composition, the inorganic fine particles are preferably used in an amount from 10 to 70 weight parts based on 100 weight parts of the resin composition for the high refractive electroconductive layer. When the amount of inorganic fine particles is less than 10 weight parts, only an insignificant increase in refractive index can be obtained. On the other hand, an amount greater than 70 weight parts of the inorganic fine particles leads to a reduction in transparency and physical properties. In order to form a uniform dispersion, the surfaces of the inorganic fine particles are preferably treated with an inorganic or an organic compound. When treated with an inorganic compound, such as alumina or zirconium oxide, or when used in combination with organic compounds, such as stearic acid or stearate, and/or a silane- or titanate-based coupling agent, the inorganic fine particles, such as titan dioxide, can be uniformly dispersed, thereby preventing a decrease in transparency attributable to the aggregation thereof. It is preferred that the inorganic or organic compound be used in an amount from 0.01 to 5 weight parts based on 100 weight parts of the inorganic fine particles.
[23] The organic binder useful in the resin composition for the high refractive index electroconductive layer is an organic compound which is heat or UV curable. As long as it contains a functional group necessary for crosslinking, such as ester, ether, epoxy, urethane, alkyd, etc., and has a higher surface hardness than that of the electroconductive polymer after being cured, any organic binder may be used. A high refractive index electroconductive layer, showing a high antistatic property and refractive index, may be formed of a resin composition prepared from a mixture of an electroconductive polymer and inorganic fine particles in the absence of the organic binder. However, this high refractive index electroconductive layer is highly likely to be scratched during the fabrication process because the electroconductive polymer itself has a low surface hardness. Thus, it is more effective to use the organic binder in
combination with a mixture of the electroconductive polymer and the inorganic fine particles. In this regard, the organic binder plays a role in complementing the mechanical strength of the high refractive index electroconductive layer. Preferably, the organic binder is an organic compound which contains a sulfur atom or a benzene ring therein, and ranges in refractive index from 1.55 to 1.70. For example, an organic binder having a low refractive index decreases the refractive index of the high refractive index electroconductive layer.
[24] The resin composition used for the formation of the high refractive index electroconductive layer is prepared in the form of a dispersion of the electroconductive polymer, the inorganic fine particles and an organic binder in an organic solvent. Useful is a solvent which has a boiling point from 50 to 2000C. Various organic solvents may be used depending on the electroconductive polymer and organic binder. Examples of the organic solvent useful in the present invention include, but not are limited to, water, alcohols (methanol, ethanol, isopropanol, and isobutanol), amides (2-pyrrolidone, N-methyl-2-pyrrolidone, N-methylformamide and N, N- dimethylformamide), ethers and ether alcohols (ethyleneglycol, glycerol, ethyleneglycol monomethylether, ethyleneglycol monoethylether, l-methoxy-2-propanol and diethylether), and combinations thereof.
[25] The resin composition prepared as described above is applied to one side of a base film and dried or cured to form a high refractive index electroconductive layer 0.01 to 1 micron thick. For coating the base film with the resin composition, various wet coating methods known in the art, such as a wire-bar coating method, a roll coating method, a spraying method, a gravure coating method, a reverse-gravure coating method, etc., may be used depending on the method of forming the electroconductive polymer of the resin composition. For example, when an electroconductive polymer, already polymerized, is mixed with the organic binder and the inorganic fine particles to prepare a resin composition, a wet coating method is conducted to apply the composition to the base film. Alternatively, a high refractive index electroconductive layer can be formed using a gas phase polymerization method, in which a polymerization initiator and a dopant are mixed with the organic binder and the inorganic fine particles and applied to the base film, and polymerizable electroconductive monomers in a gas phase are directly polymerized on the surface of the film.
[26] The method described above features mixing high refractive index inorganic fine particles with the electroconductive polymer. However, the same effect could be obtained by coating the high refractive index inorganic fine particles with the electroconductive polymers.
[27] The high refractive index electroconductive layer formed using the method described above is 0.01 to 1 micron thick and has a refractive index from 1.60 to 2.20
and a surface resistance from 10E3 to 1OE 10 ohm/square and a transmittance of visible light from 65.0 to 99.5%.
[28] As for the low refractive index layer 140, it can be formed by applying a fluorine- modified resin composition on the high refractive index electroconductive layer 130 and curing the resin solution. The fluorine-modified resin composition according to the present invention comprises a heat- or UV-curable fluorine-modified resin in an amount from 90-99.9 weight parts and a heat curing agent or a photoinitiator in an amount from 0.01 to 10 weight parts, and optionally a curing accelerator, a UV stabilizer, an anti-colorant, a surface smoothing agent, a lubricant, a water repellent, and/or an organic solvent. The heat- or UV-curable fluorine-modified resin is a monomeric or oligomeric compound synthesized through the reaction of a compound having a fluorine substituent and a compound having a crosslinkable functional group. Preferable is a monomeric or oligomeric compound which has a refractive index from 1.25 to 1.55 and can increase in surface hardness as the curing reaction proceeds. Examples of the fluorine substituent-containing compound useful in the present invention include fluoroolefins (e.g., fluoroethylene, vinylidene fluoride, tetrafluo- roethylene, hexafluoroethylene, hexafluoropropylene and perfluoro- 2,2-dimethyl-l,3-dioxol), fluoro(meth)acrylic acid ester, fluoroalkyl (meth)acryl, and fluorovinyl ether. The compound having a crosslinkable functional group may be exemplified by (meth)acrylates having an epoxy group, a carboxyl group, a hydroxyl group, an amino group or sulfonic acid.
[29] A more preferable fluorine-modified resin may be comprised of a fluorine-modified multifunctional acrylate compound synthesized by reacting a compound having perflu- oropolyether with multifunctional acrylate. In greater detail, a perfluoropolyether compound having various functional groups, such as perfluoropolyether polyol having hydroxyl groups, perfluoropolyether dibasic acid having carboxylic acids, and perfluoropolyether epoxy compounds having epoxy groups, is reacted with a multifunctional acrylate compound, such as a modified acrylate compound having carboxylic acid, an epoxy group, or isocyanate, to form a monomer or oligomer having 2 to 16 functional groups.
[30] For the following reasons, the fluorine-modified multifunctional acrylate compound resulting from the reaction of perfluoropolyether compound with multifunctional (meth)acrylate is used in the present invention. As the outermost layer of the an- tireflection film according to the present invention, the low refractive index layer is required to have a surface hardness high enough to provide sufficient resistance to scratching and abrasion, and must also show a low refractive property. Most of the resins into which fluorine substituents are introduced in order to decrease the refractive index thereof are non-crosslinkable, and thus they do not increase in surface hardness
or abrasion resistance. Suggested in order to overcome this problem was a crosslinkable polymer which can be formed by reacting fluoro(meth)acrylic acid ester and non-fluorine multifunctional (meth)acrylic acid ester. However, the fluoro(meth)acrylic acid and the non-fluorine multifunctional (meth)acrylic acid ester are difficult to react in arbitrary mixture ratios because compatibility therebetween is poor. Accordingly, it is difficult to control the refractive index of the low refractive index layer. On the other hand, when the fluorine content of fluoro(meth)acrylate, even if compatible with non-fluorine (meth)acrylic acid ester, is increased in order to lower the refractive index, the crosslinking density is also decreased. Thus, it is difficult for the conventional low refractive index layer to satisfy both refractive index and surface hardness. In contrast, the perfluoropoly ether compound and the multifunctional (meth)acrylate can be mixed in an arbitrary ratio thanks to good compatibility therebetween, and therefore, the fluorine-modified multifunctional acrylate used in the present invention can be prepared by reaction therebetween, and the refractive index and surface hardness thereof can be readily controlled.
[31] The low refractive index layer is not limited to products prepared from the fluorine- modified resin, but may be a thin layer having a refractive index of 1.25 to 1.55 even if it is prepared using a conventional method. For example, a fluorocarboxylic acid or fluoroalkyl silane compound is applied on the high refractive index electroconductive layer formed on the transparent base film, and then thermally cured. Alternatively, a silicate compound is layered on the high refractive index electroconductive layer and subjected to a sol-gel reaction to form a low refractive index layer. In another implementation of the present invention, MgF , which has been used conventionally, may be layered on the high refractive index electroconductive layer to produce the an- tireflection film. In a further implementation of the present invention, a resin composition containing low refractive index inorganic fine particles, such as silica, may be used for the formation of the low refractive index layer. In addition, the incorporation of bubbles into a resin through a chemical or physical method can reduce the refractive index to a degree suitable for use in the low refractive index layer formed on the high refractive index electroconductive layer. Further, a resin composition containing inorganic fine particles such as silica or a resin composition containing bubbles having a size of tens of microns can be applied for the formation of the low refractive index layer on the high refractive index electroconductive layer.
[32] With reference to FIG. 2, a more preferable form of the antireflection film in accordance with the present invention is shown. As shown in FIG. 2, the antireflection film comprises a transparent base polymer film 110 and a high refractive index electroconductive layer 130, with a hard coating layer 120 intercalated therebetween. The hard coating layer functions to improve the mechanical strength of the antireflection
film, and may be formed of a heat- or UV-curable compound, examples of which include an acryl compound, a urethane compound, an epoxy compound, a silane compound, and a silicate compound, but are not limited thereto. As long as it has a surface hardness of IH or greater, and more preferably 2H or greater, after being cured, any compound may be used to form the hard coating layer.
[33] In another embodiment of the present invention, only a low refractive index layer may be formed on a transparent base polymer film, or a high refractive layer and a low refractive layer may be alternately formed on a transparent base polymer film. In either case, the high refractive index layer and the low refractive index layer in accordance with the present invention can be used.
[34] When used alone, the low refractive index layer may further comprise an electro- conductive polymer. In this regard, the content of the electroconductive polymer is the same as in the high refractive index layer, while the fluoro compound is reduced as much.
[35] A better understanding of the present invention may be obtained through the following examples which are set forth to illustrate, but are not to be construed as the limit of the present invention
[36]
[37] <EXAMPLE 1>
[38] A resin composition for a high refractive index electroconductive layer was prepared. 30 wt parts of titanium dioxide (mean particle size: 40 nm, refractive index: 2.70), 5 wt parts of a titanate -based coupling agent, 40 wt parts of water and 25 wt parts of ethyleneglycol monomethylether were mixed using an ultrasonic dispersing apparatus to yield a titanium dioxide dispersion. This dispersion was mixed in a volume ratio of 70:30 with a solution of the water-dispersable electroconductive polymer polyethylenedioxythiophene. The resulting mixture was layered on one side of a triacetylcellulose (TAC) film having a thickness of 80 microns, and dried at 8O0C for 1 min to produce a 100 nm- thick high refractive index electroconductive layer 100 nm thick.
[39] 29.5 wt parts of perfluoro polyether polyol, 70 wt parts of isocyanate modified triac rylate, and 0.5 wt. parts of hydroquinone and dibutyltin dilaurate were mixed with stirring to give hexafunctional fluorine-modified acrylate. 100 wt parts of this acrylate was mixed with 5 wt parts of a photoinitiator and 0.5 wt. parts of a UV stabilizer to prepare a resin composition for a low refractive index layer. This resin composition was applied onto the high refractive index electroconductive layer, dried, and cured under a UV lamp at an energy of 200 mJ/m to form a low refractive index layer about 100 nm thick.
[40] <EXAMPLE 2>
[41] The same procedure as in Example 1 was conduced with the exception that a polyethyleneterephthalate (PET) film 120 microns thick was used as a transparent base polymer film.
[42] <EXAMPLES 3-5> [43] The same procedure as in Example 2 was conducted, with the exception that the titanium dioxide dispersion and the polyethylene dioxythiophene solution were mixed in different ratios to provide different titanium dioxide contents for the high refractive index electroconductive layer. In Examples 3 to 5, the titanium dioxide dispersion was mixed with the polyethylene dioxythiophene solution in volume ratios of 60/40, 50/50, and 40/60, respectively.
[44] [45] Each of the antireflection films prepared in Examples 1-5 had a bilayer structure in which the high refractive index electroconductive layer and the low refractive index layer were formed on a transparent base polymer film. Physical properties of the antireflection films are summarized in Table 1, below, in which n represents the refractive index.
[46] Table 1
[47] [48] <EXAMPLE 6> [49] The same procedure as in Example 1 was conducted with the exception that a hard coating layer 3 microns thick was formed between a triacetylcellulose film and the high refractive index electroconductive layer.
[50] <EXMAPLE 7> [51] The same procedure as in Example 1 was conducted with the exception that a solution containing 35 wt parts of fluoroalkylsilane, 13 wt. parts of water, 50 wt. parts of isopropyl alcohol, and 2 wt. parts of a hydrochloric acid solution was layered on the
high refractive index electroconductive layer and thermally cured at 1000C for 10 min.
[52] Each of the antireflection films prepared according to Examples 6 and 7 had a trilayer structure in which a hard coating layer, a high refractive index electro- conductive layer and a low refractive index layer were formed in that order on a base film. The physical properties of the antireflection films are summarized in Table 2, below.
[53] Table 2
[54]
Industrial Applicability [55] As described in the foregoing, the antistatic antireflection film having a high hardness can be used in various display devices, such as CRTs, LCDs, PDPs, etc., ensuring clear contrast and mirroring of images by minimizing the reflection of outside light
[56]
Claims
[1] An antireflection film, showing excellent transparency, antistatic property, an- tifouling property, and surface hardness, comprising: a transparent base polymer film; a high refractive index electroconductive layer; having a refractive index of 1.60 to 2.20, a thickness of 0.01-1 microns and a surface resistance of 10E3-10E10 ohms/square, formed by layering a composition containing an electroconductive polymer and high refractive inorganic particles on one side of the transparent base polymer film; and a low refractive index layer, having a refractive index of 1.25 to 1.55 and a thickness of 0.01-1 microns, formed by layering a composition of a fluoroorganic compound on the high refractive index electroconductive layer.
[2] An antireflection film according to claim 1, further comprising a hard coating layer 3-15 microns thick, between the transparent base polymer film and the high refractive index electroconductive layer.
[3] The antireflection film according to claim 1 or 2, wherein the electroconductive polymer of the high refractive index electroconductive layer is made from a compound selected from a group consisting of polyaniline, polypyrrole, poly- thiophene and derivatives thereof.
[4] The antireflection film according to one of claims 1 to 3, wherein the high refractive inorganic particles of the high refractive index electroconductive layer range in refractive index from 1.60 to 2.90 and in mean particle size from 0.5 to 200 nm.
[5] The antireflection film according to one of claims 1 to 4, wherein the high refractive index electroconductive layer is made of a composition containing the electroconductive polymer and the high refractive index inorganic fine particles, optionally in combination with an agent selected from a group consisting of a heat- or UV-curable organic binder, a curing agent or a photoinitiator, a coupling agent, a curing accelerator, a UV stabilizer, an anti-colorant, a leveling agent, a lubricant, an adhesion promoter, and combinations thereof.
[6] The antireflection film according to one of claims 1 to 5, wherein the low refractive index layer is formed by curing a fluorine-modified multifunctional (meth)acrylate compound having both a fluorine substituent and a crosslinkable functional group.
[7] The antireflection film according to one of claims 1 to 6, wherein the transparent base polymer film is made of a compound selected from a group consisting of polyesters including polyethylene terephthalate, polyethylene naphthalate, and
polybutylene terephthalate, cellulose derivatives including diacetyl cellulose and triacetyl cellulose, polyolefins including polypropylene and polymethylpentene, polycarbonates, polystyrenes, polyacrylates, polymethylmethacrylate, poly sulf ones, poly ethersulf ones, polyimides, polyetherimides, polyetherketones, cyclic olefin resins, and copolymers and blends thereof.
[8] A method for producing an antireflection film, showing excellent transparency, antistatic property, antifouling property, and surface hardness, comprising: providing a transparent base polymer film; forming a high refractive index electroconductive layer having a refractive index of 1.60 to 2.20, a thickness of 0.01-1 microns and a surface resistance of 10E3-10E10 ohms/square, by layering a composition containing an electro- conductive polymer and high refractive inorganic particles on one side of the transparent base polymer film; and forming a low refractive index layer, having a refractive index of 1.25 to 1.55 and a thickness of 0.01-1 microns, by layering a composition comprising a fluo- roorganic compound on the high refractive index electroconductive layer.
[9] The method according to claim 8, further comprising forming a hard coating layer 3-15 microns thick before the formation of the high refractive index electroconductive layer.
[10] The method according to claim 8 or 9, wherein the transparent base polymer film is surface treated to provide an adhesive condition for the layer to be formed thereon.
[11] The method according to one of claims 8 to 10, wherein the high refractive inorganic particles of the high refractive index electroconductive layer range in refractive index from 1.60 to 2.90 and in mean particle size from 0.5 to 200 nm.
[12] The method according to one of 8 to 11, wherein the low refractive index layer is formed by curing a fluorine-modified multifunctional (meth)acrylate compound having both a fluorine substituent and a crosslinkable functional group.
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| KR10-2005-0058956 | 2005-06-30 | ||
| KR20050058956 | 2005-06-30 |
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| PCT/KR2006/002561 WO2007004818A1 (en) | 2005-06-30 | 2006-06-30 | Anti-reflective film having high surface hardness and antistatic property and method for producing the same |
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| WO2008101363A2 (en) * | 2007-02-23 | 2008-08-28 | Tex-A-Tec Ag | Anti-static multi-functional layer and method for use of the same |
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| US8362353B2 (en) | 2008-12-22 | 2013-01-29 | E I Du Pont De Nemours And Company | Photovoltaic module with multi-layer fluoropolymeric film |
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| KR100886039B1 (en) | 2009-02-26 |
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