KR101405076B1 - Index matching film and method of manufacturing the same - Google Patents

Abstract

More particularly, the present invention relates to an index matching film and a method for producing the index matching film, and more particularly, to a method for producing an index matching film and a method for producing the index matching film by laminating a hard coating layer, a high refractive index coating layer and a hollow silica low refractive index coating layer on a transparent base film, The present invention relates to an index matching film having improved visibility and a manufacturing method thereof.

Description

[0001] INDEX MATCHING FILM AND METHOD OF MANUFACTURING THE SAME [0002]

More particularly, the present invention relates to an index matching film and a method for producing the index matching film, and more particularly, to a method for producing an index matching film and a method for producing the index matching film by laminating a hard coating layer, a high refractive index coating layer and a hollow silica low refractive index coating layer on a transparent base film, The present invention relates to an index matching film having improved visibility and a manufacturing method thereof.

Generally, a touch device is an input / output device of an electronic device that detects a contact position of a user on a display screen and performs overall control of the electronic device including the display screen control using the sensed information.

These touch devices are especially used in smart phones, and their technology importance is increasing due to the recent surge in demand for smart phones. The touch sensor detects the touch by resistive membrane type, capacitive type, electromagnetic induction type, and the representative capacitive type uses the principle of detecting the static electricity generated in the human body.

The electrostatic capacitive type has strong durability, good permeability, and fast reaction time. However, the touch screen which realizes this is inevitable to use the sensing and operation sensor by patterning the conductive transparent electrode, and the conductive layer and the base layer The pattern was visually recognized due to the difference in reflectance.

To solve this problem, a transparent conductive film, a transparent conductive laminate, a touch panel, and a method for manufacturing a transparent conductive film in Korean Patent Publication Nos. 2010-0008758, 2008-0068552 and 2012-0047828 have.

In order to improve the visibility of the pattern portion and the pattern opening in the transparent polyethylene terephthalate (PET) film, the undercoat layer and the conductive layer are formed by two layers having different refractive indexes, and the two layers are laminated on the back surface thereof with a transparent adhesive.

However, when the conductive layer is patterned, the low refractive index layer on the lower base surface is etched to cause bleaching phenomenon, and the transmittance is decreased. In the formation of the wiring electrode using the silver paste, There is a limitation in decreasing the transmittance by increasing the pattern line width or increasing the thickness of the conductive layer to realize a low resistance.

In addition, there are transparent electrodes of JP-A 2003-080624, JP-A 2008-152767, JP-A-2012-025066 and JP-A-2013-008099.

This is because the transparent conductive material and the touch panel are made of a low refractive index layer composed of a fluorine compound to remove the hard coating layer to improve the transmittance. However, such a configuration has a problem that the interlayer adhesion of the conductive film is remarkably low.

In order to improve this, there is a method of further forming an underlayer below the conductive layer or forming irregularities on the surface of the hard coat layer to strengthen the interlayer adhesion, but there is a problem that the transmittance is lowered and a method of forming an intermediate layer between the conductive layer and the hard coat layer However, this has a limitation that the reflectivity after the conductive layer pattern is low and the visibility is not improved.

Accordingly, there is a need for a new technique for a film having a high adhesive force between the respective layers and having improved visibility of a pattern having a low haze while maintaining a high transmittance.

An object of the present invention is to provide an index matching film having improved visibility with low haze while maintaining a high transmittance with a high contact force between the respective layers by laminating a hard coating layer, a high refractive index coating layer and a hollow silica low refractive index coating layer on a transparent base film, And a method for manufacturing the same.

In order to achieve the above object, the index matching film of the present invention comprises a base film, a first hard coating layer formed by reacting an ionic antistatic compound and an organic-inorganic hybrid nano-metal oxide on the bottom surface of the base film, A second hard coating layer formed by reacting an ionic antistatic compound with an organic-inorganic hybrid nano-metal oxide; a second hard coating layer formed by reacting a fluorene compound having an acrylic group on the upper surface of a second hard coat layer with a nano- And a hollow silica low refraction coating layer formed by reacting a lithium compound with a UV-curable organic-inorganic hybrid type hollow silica on the high refractive index coating layer and the high refractive index coating layer.

At this time, a conductive layer may further be formed on the upper surface of the hollow silica low refractive coating layer.

At this time, the ionic antistatic compound may be a compound represented by the following formula (1).

[Chemical Formula 1]

Wherein R ₁ -N is a heterocyclic compound selected from the group consisting of imidazole, pyridine, pyrrole, benzopyrrole, pyrazole, isothiazole, thiazole, indole, indazole, isoindole, indolizine and carbazole, R ₂ is a straight chain alkyl group having 1 to 18 carbon atoms and X is CF ₃ SO ₃ , CF ₃ CO ₂ , FPO ₃ , CF ₂ ═CFCO ₂ , PF ₆ , BF ₄ , N (CN) ₂ , ₂ CF ₃ ) ₂ .

At this time, the fluorene compound may be a compound represented by the following formula (2).

(2)

(X is selected from CH ₂ ═CHCO-, CH ₂ ═C (CH _{3 )} CO-, Y is an aromatic ring compound selected from fluorene and xanthene, W is H, CH ₃ , It is selected from _{OH, OCH 3, Cl, Br} .)

At this time, the lithium compound may be a compound represented by the following formula (3).

(3)

Li-Z

(Z represents an anion and is a substituent selected from the group consisting of (C ₂ F ₅ SO ₂ ) N, C ₃ F ₇ CO ₂ , (CF ₃ SO ₂ ) (CF ₃ CO) N)

In this case, the first hard coating layer or the second hard coating layer may contain 3 to 70% by weight of the reaction mixture obtained by reacting the organic-inorganic hybrid nano-metal oxide and the ionic antistatic compound, 5 to 80% by weight of the photocurable resin, 90% and 1 to 10% by weight of a photoinitiator.

In this case, the organic-inorganic hybrid nano-metal oxide included in the first hard coat layer may be a hollow silica having a particle diameter of 20 to 100 nm, SiO ₂ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , Nb ₂ O ₃ , and Y ₂ O ₃ , and can be surface-treated with a silane coupling agent.

At this time, the second oil contained in the hard coat layer-inorganic hybrid nano metal oxide particle diameter 5 ~ 30nm of the hollow silica, SiO _2, TiO _2, ZrO _2, Al ₂ O _3, SnO _2, Sb ₂ O _5, Nb ₂ O ₃ , and Y ₂ O ₃ , and can be surface-treated with a silane coupling agent.

In this case, the high-refractive-index coating layer preferably contains 3 to 20% by weight of a fluorene compound, 5 to 55% by weight of a nano-metal oxide sol of an organic-inorganic hybrid type, 25 to 60% by weight of a photocurable resin, 15 to 30% by weight of a photo-curable solvent having a hydroxy group and 1 to 10% by weight of a photoinitiator.

At this time, the composition may be diluted to 0.1 to 10% of the total solids in a single solvent or a mixed solvent.

In this case, the organic-inorganic hybrid nano-metal oxide included in the high-refractive-index coating layer may be TiO ₂ , ZrO ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , Nb ₂ O ₃ , Y ₂ O ₃ , and can be surface-treated with a silane coupling agent.

At this time, the photocurable solvent is acrylamide, N-methylacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide and N-vinylpyrrolidine. Examples of the solvent having a hydroxy group include hydroxy Ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and the like.

At this time, the hollow silica low refractive coating layer may include a reaction mixture composed of 5 to 60 wt% of hollow silica, 10 to 90 wt% of a photocurable resin, and 1 to 10 wt% of a photo initiator.

At this time, the reaction mixture may be diluted to 0.1 to 10% of the total solids in the solvent alone or in a mixed solvent.

At this time, the hollow silica has a particle diameter of 10 to 60 nm, a particle porosity of 10 to 70%, a refractive index of 1.2 to 1.40, and can be surface-treated with a silane coupling agent.

At this time, the base film may be made of polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), polypropylene (PP), polyethylene (PE) , And polystyrene (PS).

At this time, the base film may have a thickness of 20 to 400 탆.

In this case, the silane coupling agent may be 3-methacryloxypropylmethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3 Aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- Ethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3- glycidoxypropyl tri Mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Propyltetrasulfide, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 2- (3,4-epoxide Ethylcyclohexyl) -ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) Methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, para-styryltrimethoxysilane, para-styryltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3- (Meth) acryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propyl Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride , 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, and the like. . ≪ / RTI >

In this case, the photo-curing resin is preferably a hydroxy or ethylene oxide-containing monomer which is added with an ethylene oxide (2 to 8 mol) phenol (meth) acrylate, ethylene (2 to 10 moles), 1,6-hexanediol diacrylate, neopentyl glycol di (meth) acrylate, propylene oxide addition (2 to 4 moles) neopentyl glycol diacrylate, tripropylene glycol di Acrylate, ethylene glycol di (meth) acrylate, dipentaerythritol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di , Silicone urethane (meth) acrylate and silicone polyester acrylate, bisphenol A (3 to 30 mol of ethylene oxide) di (meth) acrylate Acrylate, dipentaerythritol hexaacrylate, acrylate, bisphenol A epoxy acrylate, and the like.

In order to achieve the above object, a method of manufacturing an index matching film according to the present invention comprises the steps of forming a first hard coating layer by reacting an ionic antistatic compound and a metal oxide of an organic-inorganic hybrid type on a bottom surface of a base film, Forming a second hard coat layer by reacting an ionic antistatic compound and a metal oxide of an organic-inorganic hybrid type on the upper surface of the base film, forming a second hard coat layer on the upper surface of the second hard coat layer by reacting a fluorene compound and a high- Forming a high refractive index coating layer by reacting an oxide sol; and forming a hollow silica low refractive index coating layer on the upper surface of the high refractive index coating layer using a lithium compound and an ultraviolet curing type organic-inorganic hybrid type hollow silica.

In this case, the method may further include forming a conductive layer on the upper surface of the hollow silica low refractive index coating layer by a sputtering deposition method using indium-tin oxide.

At this time, the ionic antistatic compound contained in the first hard coat layer and the second hard coat layer may be a compound represented by the following formula (1).

[Chemical Formula 1]

Wherein R ₁ -N is a heterocyclic compound selected from the group consisting of imidazole, pyridine, pyrrole, benzopyrrole, pyrazole, isothiazole, thiazole, indole, indazole, isoindole, indolizine and carbazole, R ₂ is a straight chain alkyl group having 1 to 18 carbon atoms and X is CF ₃ SO ₃ , CF ₃ CO ₂ , FPO ₃ , CF ₂ ═CFCO ₂ , PF ₆ , BF ₄ , N (CN) ₂ , ₂ CF ₃ ) ₂ .

At this time, the fluorene compound contained in the high refractive index coating layer may be a compound represented by the following formula (2).

(2)

(X is selected from CH ₂ ═CHCO-, CH ₂ ═C (CH _{3 )} CO-, Y is an aromatic ring compound selected from fluorene and xanthene, W is H, CH ₃ , It is selected from _{OH, OCH 3, Cl, Br} .)

At this time, the lithium compound contained in the hollow silica low refractive coating layer may be a compound represented by the following formula (3).

(3)

Li-Z

(Z represents an anion and is a substituent selected from the group consisting of (C ₂ F ₅ SO ₂ ) N, C ₃ F ₇ CO ₂ , (CF ₃ SO ₂ ) (CF ₃ CO) N)

In this case, the step of forming the first hard coat layer may include the steps of: preparing a surface modified nano-metal oxide sol by surface-reacting a nano metal oxide with a silane coupling agent; And a step of mixing the ionic antistatic compound with the photocurable resin to synthesize the first hard coating solution and applying the first hard coating solution to the lower surface of the base film.

In this case, the first hard coating solution may contain 3 to 70% by weight of the reaction mixture obtained by reacting the ionic antistatic compound and the nano-metal oxide, 5 to 80% by weight of the photocurable resin, 15 to 90% of the solvent and 1 to 10% .

In this case, the nano-metal oxide may be selected from the group consisting of hollow silica, SiO ₂ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , Nb ₂ O ₃ and Y ₂ O ₃ having a particle diameter of 20 to 100 nm More than two metal oxides.

At this time, the step of forming the second hard coat layer may include a step of surface-reacting a nano-metal oxide with a silane coupling agent to prepare a surface modified nano-metal oxide sol of a oil-inorganic hybrid type, Compounding the ionic antistatic compound with the photocurable resin to synthesize the second hard coating solution, and applying the second hard coating solution to the upper surface of the base film.

In this case, the second hard coating solution may contain 3 to 70% by weight of the reaction mixture obtained by reacting the ionic antistatic compound and the nano-metal oxide, 5 to 80% by weight of the photocurable resin, 15 to 90% of the solvent and 1 to 10% .

At this time, the nano-metal oxide may be at least one metal selected from the group consisting of SiO ₂ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , Nb ₂ O ₃ , and Y ₂ O ₃ having a particle diameter of 5 to 30 nm Oxide. ≪ / RTI >

At this time, the step of forming a high-refractive index coating layer may include a step of preparing a surface-modified nano-metal oxide sol of a surface-modified nano-metal oxide by surface reaction with a silane coupling agent, a step of reacting a nano- Synthesizing a high refractive index coating solution by blending a photo-curable resin with the fluorene compound that has been reacted, and applying a high refractive index coating solution to the top surface of the second hard coating layer to form a high refractive index coating layer.

At this time, the high refractive index coating liquid preferably contains 3 to 20% by weight of a fluorene compound, 5 to 55% by weight of a nano metal oxide sol, 25 to 60% by weight of a photocurable resin, a photocurable solvent having an amide group or a hydroxy group having an unsaturated double bond 15 to 30% by weight of a photoinitiator and 1 to 10% by weight of a photoinitiator.

At this time, the composition may further include a step of diluting the composition solely or in a mixed solvent so that the total solid content is 0.1 to 10%, followed by coating.

At this time, the nano-metal oxide includes at least one metal oxide selected from TiO ₂ , ZrO ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , Nb ₂ O ₃ and Y ₂ O ₃ having a particle diameter of 5 to 60 nm can do.

The step of forming the hollow silica low refractive coating layer may include the steps of: preparing a hollow silica sol of a surface-modified organic-inorganic hybrid type by surface-reacting the hollow silica with a silane coupling agent; Inorganic hybrid type hollow silica low refraction coating liquid for ultraviolet curing by blending a lithium compound with a photocurable resin in the reacted lithium compound, and applying a hollow silica low refractive coating liquid to the upper surface of the high refractive index coating layer have.

At this time, the hollow silica low refraction coating liquid contains a reaction mixture composed of 5 to 60% by weight of an organic-inorganic hybrid hollow silica combined with the lithium compound, 10 to 90% by weight of the photo-curing resin, and 1 to 10% by weight of a photoinitiator can do.

At this time, the reaction mixture may further include a step of thinning the reaction mixture by itself or in a mixed solvent so that the total solid content becomes 0.1 to 10%.

In this case, the hollow silica may have a particle diameter of 10 to 60 nm, a porosity of the particles of 10 to 70%, and a refractive index of 1.2 to 1.40.

In this case, the silane coupling agent may be 3-methacryloxypropylmethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3 Aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- Ethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3- glycidoxypropyl tri Mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Propyltetrasulfide, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 2- (3,4-epoxide Ethylcyclohexyl) -ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) Methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, para-styryltrimethoxysilane, para-styryltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3- (Meth) acryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propyl Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride , 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, and the like. ≪ / RTI >

In this case, the photo-curing resin is a monomer having a hydroxy or ethylene oxide moiety and is preferably an ethylene oxide addition (2 to 8 mol) phenol (meth) acrylate, an ethylene oxide addition (2 to 10 mol) 1,6-hexane diol diacrylate, Acrylate, neopentyl glycol di (meth) acrylate, propylene oxide adduct (2 to 4 mol) neopentyl glycol diacrylate, tripropylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, ethylene oxide addition polyethylene glycol di (meth) acrylate, difunctional urethane acrylate, silicone urethane (meth) acrylate and silicone polyester acrylate, bisphenol A (3 to 30 moles of ethylene oxide) di (meth) acrylate and bisphenol A epoxy acrylate. Which may include one or more components.

In this case, the photocurable resin may be a polyfunctional acrylate, trimethylolpropane (meth) acrylate, ethylene oxide addition (3 to 15 mol) trimethylolpropane (meth) acrylate, trifunctional urethane acrylate, glycerin triacrylate, Trimethylolpropane tri (meth) acrylate, tris 2-hydroxyethyl isocyanate triacrylate, ethylene oxide-added pentaerythritol tetraacrylate (meth) acrylate, propylene oxide adduct (Meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate hexafunctional urethane (meth) acrylate, ditrimethylolpropane tetra Acrylate, and 10-functional aliphatic urethane acrylate. It may include minutes.

At this time, the photocurable solvent is acrylamide, N-methylacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide and N-vinylpyrrolidine. Examples of the solvent having a hydroxy group include hydroxy Ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and the like.

According to the present invention, a hardcoat layer having antistatic property and anti-blocking property is formed by using a metal oxide of the organic-inorganic hybrid type on the back surface of the conductive layer to prevent high electric current and resistance to metastasis by static electricity.

In addition, a high-refractive-index coating layer of an ultraviolet-curing type organic-inorganic hybrid type is formed to improve the pattern visibility of the oil-inorganic hybrid type hard coating layer.

Further, by forming a low refraction coating layer using an ultraviolet curing type organic-inorganic hybrid type hollow silica which is reacted with a lithium metal compound, the adhesion between the high refractive index coating layer and the conductive layer is enhanced and the antistatic property and the total light transmittance are improved.

In addition, when the above-described layers are stacked, anti-electrification property of 10 ¹³ Ω / or less and anti-blocking property are obtained.

Further, the present invention has the properties of high transmittance and low haze, which improves the adhesion to the electrode layer using silver paste, maintains a reflectance of about 10 1% in the visible light region, has a transmittance of 91% or more and a haze of 1% .

1 is a cross-sectional view of an index matching film of the present invention.
2 is a flowchart of a method for producing an index matching film of the present invention.
3 is a flowchart of a first hard coating layer of the index matching film of the present invention.
FIG. 4 is a flowchart showing the manufacturing process of the second hard coat layer of the index matching film of the present invention. FIG.
FIG. 5 is a flowchart showing the manufacturing process of the high-refractive index coating layer of the index matching film of the present invention.
FIG. 6 is a flow chart showing the manufacturing process of the hollow silica low refractive index coating layer in the index matching film of the present invention.
FIG. 7A is a SEM photograph of the index matching film produced according to the first embodiment of the method for producing the index matching film of the present invention, and FIG. 7B is a graph of measured reflectance.
8A is a SEM photograph of the index matching film produced according to the first comparative example of the method for producing the index matching film of the present invention, and FIG. 8B is a graph of the measured reflectance.
9A is a SEM photograph of the index matching film prepared according to the second comparative example of the method for producing the index matching film of the present invention, and FIG. 9B is a graph of measured reflectance.

The present invention will now be described in detail with reference to the accompanying drawings. Hereinafter, a repeated description, a known function that may obscure the gist of the present invention, and a detailed description of the configuration will be omitted. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art. Accordingly, the shapes and sizes of the elements in the drawings and the like can be exaggerated for clarity.

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

1 is a cross-sectional view of an index matching film of the present invention.

1, the index matching film of the present invention comprises a transparent base film 100, a first hard coating layer 200 formed on the lower surface of the base film 100, a second hard coating layer 300 formed on the upper surface of the base film 100 ), A high refractive index coating layer 400 formed on the upper surface of the second hard coating layer 300, a hollow silica low refraction coating layer 500 formed on the upper surface of the high refractive index coating layer 400 and a conductive low refractive index coating layer 500 formed on the upper surface of the hollow silica low refractive index coating layer 500 Layer 600 as shown in FIG.

Specifically, the base film 100 may be made of PET (polyethylene terephthalate), PC (polycarbonate), PMMA (polymethyl methacrylate), PP (polypropylene), PE (polyethylene, Polyethylene (PE) and PS (polystyrene).

The first hard coat layer 200 formed on the lower surface of the base film 100 is formed of a compound obtained by reacting an ionic antistatic agent represented by the following Chemical Formula 1 with a metal oxide of an organic-inorganic hybrid type and a photo- .

The first hard coat layer 200 has antistatic properties and anti-blocking properties, and improves transmittance, shrinkage, antistatic property and resistance to metastasis in the index matching film of the present invention.

[Chemical Formula 1]

Wherein R ₁ -N is a heterocyclic compound selected from the group consisting of imidazole, pyridine, pyrrole, benzopyrrole, pyrazole, isothiazole, thiazole, indole, indazole, isoindole, indolizine and carbazole , R ₂ is a straight-chain alkyl group having the carbon number of 1 ~ 18, X is _{CF 3 SO 3, CF 3 CO} 2, FPO 3, CF 2 = CFCO 2, PF 6, BF 4, N (CN) 2, and N ( SO ₂ CF ₃ ) ₂ .

The ionic antistatic agent can be obtained by using a commercially available product (CHTA-402, KOY-101: KOY-101) or by using a heterocyclic compound containing nitrogen. The method for synthesizing an ionic antistatic agent will be described in detail as follows.

After the pyrrole was dissolved in toluene, 1.3 equivalents of bromomododecane to the pyrrole was added thereto, followed by refluxing overnight. When the reaction is complete, cool the reaction mixture to 40-50 ^° C. To the reaction mixture, water was added twice as much as the weight of the reactant, and the unreacted bromomododecane was removed by washing with diisopropyl ether several times to prepare a quaternary ammonium salt aqueous solution. Diisopropyl ether was added to the reaction solution in an amount of 50% based on the weight of the reaction solution, and 1 equivalent of lithium hexafluorophosphate was added to the pyrrole, followed by reaction at room temperature for 8 hours. After stopping the reaction, the reaction mixture was allowed to stand for 1 hour to separate the layers. The diisopropyl ether layer was dried under reduced pressure to obtain an anion PF ₆ ^- form.

The hard coating solution having the antistatic property, the anti-blocking property, and the converging light for forming the first hard coat layer 200 can be obtained by a reaction between an organic-inorganic hybrid nano-metal oxide sol and an ionic antistatic agent represented by the following formula 3 to 70% by weight of the mixture; 5 to 80% by weight of a photocurable resin; Solvent 15 to 90%; And 1 to 10% by weight of a photoinitiator.

When the refractive index of the hard coating solution is 1.40 or less, the hardness and substrate adhesion are poor. When the hard coating solution has a refractive index higher than 1.55, the refractive index of the hard coating solution tends to be increased. Therefore, the hard coating solution is preferably in the range of 1.41 to 1.55 on a solid basis.

For the nano-metal oxide sol is less than the particle size of 20nm, the fire no king-preventive property, as is lowered and the total light transmittance becomes higher haze value and when 100nm, greater than, and preferably formed of 20 ~ 100nm, hollow silica, SiO _2, TiO ₂ , ZrO ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , Nb ₂ O ₃ , and Y ₂ O ₃ . Further, the nano-metal sol may be surface-modified with a silane coupling agent and mixed with an ultraviolet curable resin.

Since the silane coupling agent contains a reactive group at the terminal group, the silane coupling agent can further react and increase the crosslinking density. Specific examples include 3-methacryloxypropylmethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltri (Aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- -Aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, Mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, bis (triethoxysilylpropyl) , 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 2- (3,4-epoxy (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) -ethyltriethoxysilane, 3- 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, para-styryltrimethoxysilane, para- Acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) -2-aminoethyl- 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, and one or more of these may be used. They can be used directly or by hydrolysis.

Organic-inorganic composite method of a hybrid-type nano-metal oxide sol is then put into a silane coupling agent in the contrast 5-200% by weight of solid content in the metal oxide dispersed in an organic solvent, stirred, 0 ~ 50 ^o hydrolysis catalyst in the C region (Acid or base) with 1 to 4 equivalents of water relative to the equivalent of the coupling agent.

If the silane coupling agent is less than 5% by weight based on the solid content of the metal oxide, the storage stability and the coating film layer after the coating are inhomogeneous, and even if the haze value is less than 1%, the haze is totally caused.

Examples of the hydrolysis and condensation catalyst include inorganic acids such as sulfuric acid, nitric acid and hydrochloric acid, organic acids such as acrylic acid, methacrylic acid, oxalic acid, acetic acid and formic acid, inorganic bases such as NaOH, KOH and LiOH, Amine series) can be used.

The first hard coat layer 200 may be prepared by preparing a nano-metal oxide sol of an organic-inorganic hybrid type surface-modified by surface-reacting a nano-metal oxide, for example, 40 nm hollow silica with a silane coupling agent, 1] to improve the dispersibility by improving the aggregation phenomenon caused by the ionic antistatic agent and to improve the dispersibility by ionic bonding of the nano-metal oxide sol of the organic-inorganic hybrid type and the ionic antistatic agent The occurrence of stain caused by the adiabatic effect generated in the post-lamination process was prevented. Also, by using a surface treated nano-metal oxide having a size of 20 to 100 nm, an anti-blocking hard coat layer having low haze and high transmittance was provided. A multifunctional photo-curing resin was blended therein to increase the hardness of the coating layer.

As the photo-curing resin, a polyfunctional monomer or a monofunctional or bifunctional monomer may be used. The monofunctional or bifunctional monomer may be a hydroxyl group or an ethylene oxide moiety and acrylate in order to maintain the dispersibility of the organic-inorganic hybrid type nano-metal oxide sol, for example, an ethylene oxide addition (2-8 mol) Phenol (meth) acrylate, ethylene oxide addition (2 to 10 mol) 1,6-hexanediol diacrylate, neopentyl glycol di (meth) acrylate, propylene oxide addition (2 to 4 mol) neopentyl glycol diacryl Acrylate, polyethylene glycol di (meth) acrylate, ethylene oxide-added polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di Acrylate, bifunctional urethane acrylate, silicone urethane (meth) acrylate and silicone polyester acrylate, bis A play may be used (ethylene oxide adduct 3-30 mole) di (meth) acrylate and bisphenol A 1 or more selected from the group consisting of epoxy acrylates.

(Meth) acrylate, an ethylene oxide addition (3 to 15 mol), trimethylol (meth) acrylate, or the like, may be used in order to improve the adhesion to the transparent substrate and the hardness of the coating film. (Meth) acrylate, trimethylolpropane tri (meth) acrylate, trifunctional urethane acrylate, glycerin triacrylate, pentaerythritol tri (meth) acrylate, propylene oxide addition (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tri (meth) acrylate, Acrylate and dipentaerythritol hexa (meth) acrylate hexafunctional urethane acrylate, 1 And 0-functional aliphatic urethane acrylate can be used.

Preferably, the resin solution comprises at least one component selected from the group consisting of acrylic acrylate and urethane acrylate.

In order to cure the coating film after coating the resin composition for hard coating, the photoinitiator may be used within 1 to 10% of the total resin composition.

Usable photoinitiators can be classified into chemical groups within the molecular structure. Examples of usable chemical structures include ketal series, acetophenone series, sulfide series, benzoate series, benzophenone series, phosphine series, and benzoylformate series. Specific examples include products of Ciba; Darocur 1173, MBF, TPO, 4265, or Double Bond Chemical Company: Doublecure BDK, TPO, TPO-L, 73W, 107, 173, 184, 200, 284, 560, 998, 1130, 1172, 1176, 1190, 1256 and the like. There is no particular limitation on the type of photoinitiator that can be used.

Further, in order to improve the wettability and functionality of the coating film upon coating the substrate, additives may be added in an amount of 1% by weight or less based on the total composition.

Usable additives include antifoaming agents, wetting agents, dispersants, flow control agents, leveling agents, adhesion promoters, and the like.

A solvent may be used for the purpose of enhancing the compatibility and coating property of the resin composition for hard coating. Examples of usable solvents include, but are not limited to, alcohols (methanol, ethanol, isopropanol, (Methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, diisopropyl ketone, diethyl ketone, diethyl ketone, (Hexane, heptane, octane, etc.) alone or in admixture with a total composition ratio of 10 to 95% by weight Lt; / RTI >

The thickness of the base film 100 is preferably 20 to 600 占 퐉, more preferably 25 to 250 占 퐉

The thickness of the first hard coat layer 200 having antistatic properties, anti-blocking properties and focusing light applied to one surface of the base film 100 is difficult to ensure the appearance of the coated surface when the thickness of the coating is within 0.01 pm, It is preferable that the thickness of the coating film is 0.01 to 10 占 퐉 because it causes not only an increase in manufacturing cost but also cracking when the coating film is bent. In addition, the surface hardness of the first hard coat layer 200 having antiblocking property, antistatic property and focusing light is 10 ¹³ ? / Cm or less.

On the upper surface of the base film 100, a second hard coating layer 300 is formed to improve the interlaminar adhesive force and transmittance. The second hard coating layer 300 is an organic-inorganic hybrid type, which improves the pattern visibility and improves the adhesion to the high refractive index coating layer 400 and the base film 100, reduces the roughness of the coating surface, The transmittance is prevented from lowering and the reflectance of the high refractive index coating layer 400 is constant in the visible ray region. Further, the shrinkage and curl of the base film 100 are improved to improve the reliability in the photolithography process.

In general, the adhesion between dissimilar materials is classified into primary bonding (ionic bonding, covalent bonding and metal bonding) and secondary bonding (dispersion, organic, orientation, hydrogen bonding) depending on the chemical properties of the interface and the surface state of the adherend .

In terms of bonding strength, the primary bond is 140-250 kcal / mol, the covalent bond is 15-170 kcal / mol, the metal bond is 27-83 kcal / mol, the hydrogen bond is 3-10 kcal / ) Is less than 5 kall / mol, and the organic force (Van der Waal's force) is less than 0.5 kall / mol. From the above results, it can be seen that the primary bonding is very large as compared with the secondary bonding.

Therefore, in order to increase the bonding force between the different material layers, the present invention induces metal bonding between the high refractive index coating layer 400 and the second hard coating layer 300 through the oil-inorganic hybrid type hard coating in order to induce primary bonding with high bonding force. Respectively. In addition, durability is improved by blending a photo-curable resin to maintain the adhesive strength with the base film.

The organic-inorganic hybrid hard coating solution comprises 3 to 70% by weight of an organic-inorganic hybrid nano-metal oxide sol prepared by reacting a nano-metal oxide sol with a silane coupling agent; 5 to 80% by weight of a photocurable resin; Solvent 15 to 90%; And 1 to 10% by weight of a photoinitiator.

When the refractive index of the organic-inorganic hybrid hard coating solution is less than 1.46, the hardness and substrate adherence are poor. When the refractive index exceeds 1.55, the manufacturing cost is increased. Therefore, the refractive index is preferably in the range of 1.46 to 1.55 on a solid basis.

As a metal material used for the oil-and-inorganic hybrid hard coating, a nano-metal oxide sol, SiO ₂ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ and Nb ₂ O _{3 having a} particle diameter of 5 to 30 nm , And Y ₂ O ₃ , and it is preferable to add a small amount of a metal oxide used for the high refractive index layer in order to improve the adhesion to the high refractive index layer by using nano silica sol as a main component. have.

The nano-metal oxide sol is surface-modified with a silane coupling agent. When it is used in an amount of less than 1% based on the total solid content, the adhesive strength with the high refractive index layer is lowered. When 95% by weight or more is used, surface roughness and coating appearance are deteriorated, Is used by mixing with an ultraviolet curable resin using 1 to 95% by weight based on the total solid content.

In addition, the particles of the nano-metal oxide sol have a particle size of 5 to 30 nm because the solution stability is poor when the particle diameter of the nano-metal oxide sol is less than 5 nm and the surface transmittance is lowered when the particle size exceeds 30 nm.

The thickness of the second hard coating layer 300 of the organic-inorganic hybrid type coated on one surface of the base film 100 is difficult to ensure the appearance of the coating surface when the thickness of the coating is within 0.01 pm, But also cracks occur when the coating film is bent. Therefore, it is preferable that the thickness is 0.01 to 10 mu m.

The silane coupling agent, photocurable resin, solvent, and photoinitiator used in the organic-inorganic hybrid hard coating solution can be applied to the same components used in the production of the first hard coat layer 200.

The high hardness coating layer 400 is further formed on the upper surface of the second hard coat layer 300 of the organic-inorganic hybrid type. This is for improving the pattern visibility and improving the reflectance and transmittance, and the high-refraction coating layer 400 is composed of a UV-curable type organic-inorganic hybrid type.

Specifically, a high-refraction coating layer 400 is formed of a high-refraction metal oxide and a curable resin of the following formula 2 and an organic-inorganic hybrid type.

(2)

(X is selected from CH ₂ ═CHCO-, CH ₂ ═C (CH _{3 )} CO-, Y is an aromatic ring compound selected from fluorene and xanthene, W is H, CH ₃ , It is selected from _{OH, OCH 3, Cl, Br} .)

In the composition of the high refractive index coating liquid, 3 to 20% by weight of a fluorene compound having an acryl group synthesized on the basis of a solid content, 5 to 55% by weight of a nano-metal oxide sol of an organic-inorganic hybrid type, 25 to 60% 15 to 30% by weight of a photocurable solvent having a double bond or an amide group having a hydroxy group and 1 to 10% by weight of a photoinitiator were prepared.

The high refractive index coating liquid for forming a high refractive index coating layer 400 includes a U-into a metal oxide-inorganic hybrid type, the nano-metal sol particle diameter of 5 ~ 60nm of _{TiO2, ZrO 2, Al 2 O} 3, SnO 2, Sb 2 O 5, Nb ₂ O ₃ , and Y ₂ O ₃ , and is prepared by surface-modifying a nano-metal sol with a silane coupling agent and mixing with an ultraviolet curable resin.

Here, the high-refraction coating solution for forming the ultraviolet-curable type organic-inorganic hybrid type high refractive index coating layer 400 can be prepared according to a process for producing a high refractive index hard coating composition for roll printing and a printing film using the same, disclosed in Korean Patent Publication No. 2011-0133209 (Manufactured by JSR Corporation: KZ series (refractive index 1.65-1.74), Pelnox company: A-2100 series (refractive index 1.65-1.77) can be purchased and used.

In order to improve the all-optical characteristic, the refractive index difference between the polymer binder and the inorganic oxide particle should be minimized and the inorganic oxide particle size used should be minimized do. Therefore, in the present invention, a fluorene derivative having an organic binder having a refractive index of 1.60 or more and excellent optical characteristics was used.

[Equation 1]

^{_{P scat = 128π 5 N A r}} 6 / 3ω 4 [n p 2 -n m 2 / n p 2 + 2n m 2]

n _p = refractive index of the metal oxide particle

n _m = refractive index of the binder

r = radius of metal oxide particle

N _A = Number of Avogadro

ω = wavelength of light

The refractive index of the high refractive index coating solution is a solution having a refractive index within it is a problem which was the reflectance after production index sheet called a film in the case of less than 1.60, based on solids is lower, the lower the transmissivity and adhesive strength when 1.80 excess is present, based on solids 1.60 ~ 1.80 Range Is preferably used.

If the diameter of the high-refractive-index metal oxide is less than 5 nm, the stability of the coating solution and the hardness of the coating film become poor, and when the particle size exceeds 60 nm, the transmittance decreases due to particle scattering.

As the photocurable crosslinking agent, a polyfunctional monomer or a monofunctional monomer is used, and a photocurable resin used for the first hard coating layer 200 and the second hard coating layer 300 may be used.

The photocurable solvent is composed of an amide group having an unsaturated double bond and a hydroxy group. When the coating solution is applied to the second hard coat layer 300, the base wettability is improved. When a leveling agent or a dispersing agent is not used to increase the interlaminar adhesive strength, poor wettability of the base material results in poor appearance of the hole-like shape, and such problems can be solved. In addition, since the melting point is low, the solvent is volatilized finally in the drying process, so that the reduction of the refractive index of the coating film due to the low refractive index of these solvents can be prevented.

Examples of the photocurable solvent having such properties include an amide series and a hydroxy series. Specific examples of the amide series include acrylamide, N-methylacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide , And N-vinylpyrrolidine. Examples of the solvent having a hydroxy group include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate. Or a mixture of two or more of them.

The photoinitiator is used to form a coating film by photoreaction after a high-refractive-index coating liquid of an organic-inorganic hybrid type is coated and dried. Accordingly, the photoinitiator used in the preparation of the first hard coat layer 200 may be used as the photoinitiator.

In order to form a thin film coating layer, a high refractive index layer is formed by coating the coating solution solely with 0.1 to 10% solids or by diluting it with a mixed solvent to form a high refractive index layer. In addition, a solvent used in the production of the first hard coat layer 200 may be used as a solvent for the high refractive index coating liquid.

A hollow silica low refractive index coating layer 500 is further formed on the upper surface of the high refractive index coating layer 400. The hollow silica low refractive coating layer 500 is formed by reacting with the lithium metal compound to enhance adhesion with the conductive layer 600 and to increase the antistatic property and the total light transmittance.

The hollow silica low refractive coating layer 500 has low refractive index and has high printing property for improving adhesion to the wiring electrode layer using a silver paste. Further, in order to improve the adhesion to the conductive layer 600, the improvement of the whitening phenomenon upon pattern etching of the conductive layer 600, and the antistatic property, a lithium compound represented by the following formula 3 is used and the reflectance in the visible light region is 10 An index matching film having a transmittance of 91% or more and a haze of 1% or less while maintaining a value within ± 1% was completed.

(3)

Li-Z

(Z represents an anion and is a substituent selected from the group consisting of (C ₂ F ₅ SO ₂ ) N, C ₃ F ₇ CO ₂ , (CF ₃ SO ₂ ) (CF ₃ CO) N)

The lithium compound of formula (3) improves the adhesion to the conductive layer by using the metal property of lithium ion. The anion improves the charging performance with the fluoro compound.

In the ultraviolet curing type organic-inorganic hybrid type hollow silica low refractive coating solution, an air layer is formed in the SiO ₂ sol nano particle having a nanoparticle diameter of 10 to 60 nm, so that not only the refractive index is low but also the electrooptic characteristic is improved by the air layer. This hollow silica sol was surface-modified with a coupling agent, and then ion-bonded with a lithium compound represented by Formula 3 to improve dispersion stability. An ultraviolet curing type resin was mixed with this to prepare an ultraviolet curing type organic-inorganic hybrid type hollow silica low refractive coating liquid.

The hollow silica sol may be JX1004SIV, JX1008SIV, JX1009SIV or JX1012SIV manufactured by Nikkiso Co., Ltd., Kasei Kogyo Co.,

When the hollow silica particle size is less than 10 nm, it is difficult to realize a low refractive index. When the hollow silica particle size exceeds 100 nm, the transmittance is lowered. Hollow silica having a particle size of 10 nm to 100 nm is preferably used.

Also, hollow silica particles having a porosity of 10 to 70% are preferably used because the refractive index of the hollow silica particles is less than 10% and the particles have a weak strength when the porosity exceeds 70%.

If the refractive index of the hollow silica particles is less than 1.2, the hollow silica is liable to be fragile, and when it exceeds 1.40, the refractive index is high and the desired electrooptic property can not be exhibited. Therefore, hollow silica having a refractive index of 1.2 to 1.40 is preferably used.

The colloidal sol state in which the hollow silica particles are dispersed in a solvent is preferably used. As the usable solvent, any of an alcohol-based or a ketone-based solvent may be used alone or in combination.

Inorganic hybrid type hollow silica coating liquid composition having a low refractive index has 5 to 60% by weight of an organic-inorganic hybrid hollow silica combined with a lithium compound on a solid basis, 10 to 90% by weight of a photo-curing resin, 1 to 10% by weight. In order to thinly coat the reaction mixture to a thickness of 200 nm or less, the hollow silica coating layer 500 is formed by diluting the mixed solution with a solids content of 0.1-10%.

When the refractive index of the low refraction coating solution is less than 1.30, the adhesion of the substrate to the conductive layer is weak. When the refractive index exceeds 1.40, there arises a problem that the reflectance in the visible light region is lowered when the refractive index exceeds 1.40. It is preferable to use a solution.

The silane coupling agent, the photocurable resin, the photoinitiator and the solvent used in the low refractive coating solution may be used in the same manner as that used in the production of the first hard coat layer 200.

The refractive index of each layer of the index matching film according to the present invention is listed in descending order. The index of refraction of each layer of the index matching film in the present invention is the refractive index of the hollow silica low refractive coating layer 500, the first hard coating layer 200, the second hard coating layer 300, The refractive index of the second hard coating layer 300 may be greater than or equal to the refractive index of the first hard coating layer 200. In this case,

2 is a flowchart of a method for producing an index matching film of the present invention.

Referring to FIG. 2, the index matching film of the present invention forms a first hard coating layer 200 on a lower surface of a transparent base film 100 (S100). At this time, the first hard coat layer 200 has properties of antistatic property and anti-blocking property and has a light-condensing property.

A specific manufacturing method of forming the first hard coat layer 200 (S100) includes a step of forming a first hard coat layer 200 on a surface of a nano-metal oxide, for example, 40 nm hollow silica by surface-reaction with a silane coupling agent, And then reacted with an ionic antistatic agent represented by the following formula (1) to improve the dispersibility of the ionic antistatic agent and to improve the dispersibility. In the case of the organic-inorganic hybrid type nano-metal oxide sol and Ionic bonding of the ionic antistatic agent prevents the generation of stains due to the adiabatic effect generated during the post-coating lamination process. Also, by using a surface treated nano-metal oxide having a size of 20 to 100 nm, an anti-blocking hard coat layer having low haze and high transmittance was provided. A multifunctional photo-curing resin was blended therein to increase the hardness of the coating layer.

[Chemical Formula 1]

Wherein R ₁ -N is a heterocyclic compound selected from the group consisting of imidazole, pyridine, pyrrole, benzopyrrole, pyrazole, isothiazole, thiazole, indole, indazole, isoindole, indolizine and carbazole, R ₂ is a straight chain alkyl group having 1 to 18 carbon atoms and X is CF ₃ SO ₃ , CF ₃ CO ₂ , FPO ₃ , CF ₂ ═CFCO ₂ , PF ₆ , BF ₄ , N (CN) ₂ , ₂ CF ₃ ) ₂ .

After the first hard coating layer 200 is formed (S100), the second hard coating layer 300 is formed on the opposite surface of the base film 100 on which the first hard coating layer 200 is not formed (S200) . At this time, the second hard coat layer 300 is formed of a metal oxide and a photo-curable resin of the organic-inorganic hybrid type so as to enhance the interlayer adhesion and improve the transmittance.

The second hard coating layer 300 induces a primary bond having a strong bonding force with the high refractive index coating layer 400 through a hard coating of the organic-inorganic hybrid type and a photocurable resin is added to enhance adhesion with the base film 100 .

The organic-inorganic hybrid hard coating solution forming the second hard coat layer 200 may be prepared by mixing 3 to 70% by weight of an oil-inorganic hybrid nano-metal oxide sol prepared by reacting a nano-metal oxide sol with a silane coupling agent; 5 to 80% by weight of a photocurable resin; Solvent 15 to 90%; And 1 to 10% by weight of a photoinitiator.

After forming the second hard coating layer 300 (S200), a high refractive index coating layer 400 is formed on the upper surface of the second hard coating layer 300 (S300). At this time, the high refractive index coating layer 400 is a layer improving the reflectance and transmittance to improve the pattern visibility.

Specifically, the high-refraction coating solution for forming the high-refractive index coating layer 400 is prepared by dissolving epichlorohydrin in the presence of biscuitcoolfluorene [9,9-bis (4,4'-dihydroxyphenyl) fluorene] (manufactured by Osaka Gas Co., Hydrin and t-butylammonium chloride catalyst to synthesize a fluorene derivative having an epoxy group. Using the synthesized epoxy fluorene derivative, a fluorene compound having an acryl group represented by the following formula (2) was synthesized using an acrylic acid and a quaternary ammonium salt phase transition catalyst.

The fluorene compound having an acryl group is a high-refraction organic compound having excellent transparency and heat resistance, so that the b ^* value can be kept low. Further, since the hydroxy group of the synthesized fluorene compound can be used to induce the bond with the metal oxide, the phase separation phenomenon between the dissimilar materials can be overcome.

(2)

(X is selected from CH ₂ ═CHCO-, CH ₂ ═C (CH _{3 )} CO-, Y is an aromatic ring compound selected from fluorene and xanthene, W is H, CH ₃ , It is selected from _{OH, OCH 3, Cl, Br} .)

After forming the high refractive index coating layer 400 in step S300, a hollow silica low refractive index coating layer 500 is formed on the high refractive index coating layer 400 in step S400. The hollow silica low refraction coating layer 500 is formed by reacting the high refractive index coating layer 400 and the conductive layer 600 with the lithium metal compound in order to increase the adhesion force, antistatic property and total light transmittance.

Specifically, the hollow silica low refractive index coating layer 500 has high printability in order to improve adhesion to the wiring electrode layer using a silver paste. The hollow silica particles have been surface-treated to improve the electrooptic characteristics. Further, in order to improve the adhesion to the conductive layer, the improvement of the whitening phenomenon upon etching of the conductive layer pattern, and the antistatic property, a lithium compound represented by the following formula 3 is used and the reflectance in the visible light region is about 10 1% And an index matching film having a transmittance of 91% or more and a haze of 1% or less was completed.

(3)

Li-Z

(Z represents an anion and is a substituent selected from the group consisting of (C ₂ F ₅ SO ₂ ) N, C ₃ F ₇ CO ₂ , (CF ₃ SO ₂ ) (CF ₃ CO) N)

The coating liquid forming the hollow silica low refraction coating layer 500 may be prepared in the following order. Inorganic hybrid hollow silica sol is prepared by reacting hollow silica with a silane coupling agent to prepare a surface-modified organic-inorganic hybrid hollow silica sol, which is then reacted with a lithium compound represented by Formula 3, which is an ionic antistatic agent. In this case, the silane coupling agent may be the same as the silane coupling agent used in the step (S100) in which the first hard coat layer 200 is formed. Thereafter, a photo-curing resin was blended to prepare a hollow silica-based liquid coating for oil-inorganic hybrid type for ultraviolet curing having low refractive index.

After the hollow silica low refractive coating layer 500 is formed, a transparent electrode is formed through ITO deposition (S500).

Inorganic hybrid hollow-silica low refractive index layer using indium-tin oxide by a sputtering deposition method at a deposition rate of 3 to 5 M / min, followed by heat treatment at 150 ^° C. for 1 hour, A transparent conductive film can be produced.

At this time, it is preferable that the conductive layer has a thickness of 10 to 500 nm in at least one metal or metal oxide form among Au, Ag, Zn, Ni, Al, Sn and In as the metal material of the transparent conductive film.

3 is a flowchart of a first hard coating layer of the index matching film of the present invention.

Referring to FIG. 3, a surface modified organic-inorganic hybrid type nano-metal oxide sol is prepared by surface-reacting a nano-metal oxide with a silane coupling agent (S110).

After the step S110, the synthesized nano-metal oxide sol and the ionic antistatic compound are reacted (S120)

At this time, the ionic antistatic compound may be a compound represented by the following formula (1).

[Chemical Formula 1]

Wherein R ₁ -N is a heterocyclic compound selected from the group consisting of imidazole, pyridine, pyrrole, benzopyrrole, pyrazole, isothiazole, thiazole, indole, indazole, isoindole, indolizine and carbazole, R ₂ is a straight chain alkyl group having 1 to 18 carbon atoms and X is CF ₃ SO ₃ , CF ₃ CO ₂ , FPO ₃ , CF ₂ ═CFCO ₂ , PF ₆ , BF ₄ , N (CN) ₂ , ₂ CF ₃ ) ₂ .

The ionic antistatic compound thus reacted is compounded in the photocurable resin to synthesize a first hard coating solution (S130).

The synthesized first hard coating solution is applied to the lower surface of the base film 100 to produce a first hard coating layer (S140).

If the thickness of the first hard coating layer is 0.01 μm or less, it is difficult to secure the appearance of the coating surface. If the thickness is 10 μm or more, the first hard coating layer may have a thickness of 0.01 to 10 μm desirable.

The first hard coating layer produced through the above process has antiblocking property, antistatic property and focusing light and may have a surface resistance of 10 ¹³ Ω / cm or less.

FIG. 4 is a flowchart showing the manufacturing process of the second hard coat layer of the index matching film of the present invention. FIG.

Referring to FIG. 4, a nano-metal oxide oxide is surface-reacted with a silane coupling agent to prepare a surface modified organic-inorganic hybrid type nano-metal oxide sol (S210).

After the step S210, the synthesized nano metal oxide sol is reacted with the ionic antistatic compound (S220).

At this time, the ionic antistatic compound may be a compound represented by the following formula (1).

[Chemical Formula 1]

Wherein R ₁ -N is a heterocyclic compound selected from the group consisting of imidazole, pyridine, pyrrole, benzopyrrole, pyrazole, isothiazole, thiazole, indole, indazole, isoindole, indolizine and carbazole, R ₂ is a straight chain alkyl group having 1 to 18 carbon atoms and X is CF ₃ SO ₃ , CF ₃ CO ₂ , FPO ₃ , CF ₂ ═CFCO ₂ , PF ₆ , BF ₄ , N (CN) ₂ , ₂ CF ₃ ) ₂ .

The reacted ionic antistatic compound is compounded in the photocurable resin to synthesize a second hard coating solution (S230).

The synthesized second hard coating liquid is applied to the upper surface of the base film 100 to produce a second hard coating layer 300 (S240).

When the thickness of the second hard coating layer 300 is 0.01 μm or less, it is difficult to ensure the appearance of the coating surface. If the thickness is 10 μm or more, the hard coat layer 300 is cracked when the coating layer is bent, To 10 m is preferable.

The second hard coating layer 300 formed by the above process has antiblocking property, antistatic property, and focusing light and may have a surface resistance of 10 ¹³ Ω / cm or less.

FIG. 5 is a flowchart showing the manufacturing process of the high-refractive index coating layer of the index matching film of the present invention.

Referring to FIG. 5, a nano-metal oxide sol of a surface-modified organic-inorganic hybrid type is prepared by surface-reacting a nano-metal oxide with a silane coupling agent (S310).

After the step S310, the synthesized nano-metal oxide is reacted with the fluorene compound (S320).

In this case, the fluorene compound may be a compound represented by the following formula (2).

(2)

(X is selected from CH ₂ ═CHCO-, CH ₂ ═C (CH _{3 )} CO-, Y is an aromatic ring compound selected from fluorene and xanthene, W is H, CH ₃ , It is selected from _{OH, OCH 3, Cl, Br} .)

The fluorene compound is added to the photocurable resin to synthesize a high-refraction coating solution (S330).

The synthesized high refractive index coating liquid is coated on the upper surface of the second hard coat layer 300 to produce a high refractive index coating layer 400 (S340).

At this time, the high refractive index coating liquid can be thin-coated by diluting the high refractive index coating liquid alone or in a mixed solvent so that the solid content of the coating liquid becomes 0.1 to 10% and coating the high refractive index coating layer 400.

FIG. 6 is a flow chart showing the manufacturing process of the hollow silica low refractive index coating layer in the index matching film of the present invention.

Referring to FIG. 6, hollow silica sol is surface-modified with a silane coupling agent to prepare a surface-modified organic-inorganic hybrid type hollow silica sol (S410).

After the step S410, the synthesized hollow silica sol is reacted with the lithium compound (S420).

At this time, the lithium compound may be a compound represented by the following formula (3).

(3)

Li-Z

(Z represents an anion and is a substituent selected from the group consisting of (C ₂ F ₅ SO ₂ ) N, C ₃ F ₇ CO ₂ , (CF ₃ SO ₂ ) (CF ₃ CO) N)

The reacted lithium compound is compounded in the photo-curing resin to synthesize a hollow silica low refractive-index organic / inorganic hybrid coating liquid for UV curing (S330).

The synthesized hollow silica low refraction coating liquid is applied on the upper surface of the high refractive index coating layer 400 to produce a hollow silica low refraction coating layer 500 (S340).

At this time, the hollow silica low refractive coating layer can be thinly coated to a thickness of 200 nm or less by diluting the coating liquid alone or in a mixed solvent so that the solid content of the coating liquid becomes 0.1 to 10%, and coating.

FIG. 7A is a SEM photograph of the index matching film produced according to the first embodiment of the method for producing the index matching film of the present invention, and FIG. 7B is a graph of measured reflectance.

8A is a SEM photograph of the index matching film produced according to the first comparative example of the method for producing the index-matched film of the present invention, and FIG. 8B is a graph of measured reflectance.

9A is a SEM photograph of the index matching film produced according to the second comparative example of the method for producing the index matching film of the present invention, and FIG. 9B is a graph of measured reflectance.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples with reference to FIGS. 7 to 9. FIG.

≪ Embodiment 1 >

Step 1: Blocking Preventiveness , Antistatic properties and Concentrating  The first hard coat layer 200 having the first hard coat layer 200

(Trade name: JX1004SIV, solid content 20% by weight, particle size: 40 nm, solvent: isopropyl alcohol), 80 g of silica nanosol (manufactured by Nissan Chemical Industries, Ltd., product name: MEK-ST -L (SiO ₂ content of 30% by weight, particle size of 40 ~ 50nm, solvent: methyl ethyl ketone)), 3-acryloxypropyl trimethoxysilane 30g (Shin-Etsu Corporation, product name: KBM-5103), a round of acetic acid 1.2g After the completion of the reaction, the reaction mixture was diluted with methyl ethyl ketone to a solid content of 30% by weight. Then, 7 g of water was slowly added dropwise at room temperature and reacted for 4 hours to synthesize an organic-inorganic hybrid nanosilica composite sol.

The ionic antistatic agent KOY-101 (manufactured by Koizu) was dissolved in methyl ethyl ketone to a concentration of 20% by weight based on solid solids of the composite sol, and then the stirring speed Was slowly added dropwise with stirring at a high rate of 500 rpm or more to allow the ion-binding reaction between the organic-inorganic hybrid nano-metal oxide complex sol and the ionic antistatic agent to react at room temperature for 3 hours. This photocurable resin in MU9500 200g (Aliphatic multifunctional acrylate, Miwon firm product), M3190 100g (Trimetylolpropane (PO ) 9 triacrylate, Miwon firm product), PU664 300g (Aliphatic hexafunctional acrylate , Miwon firm product) and the photoinitiator Irgacure 184 40g (Manufactured by Ciba), diluted with methyl ethyl ketone so that the total solid content became 30% by weight, and then stirred for 1 hour to prepare a resin composition for hard coating having antiblocking property and antistatic property.

Using the prepared hard coating composition, a microgravure (mesh # 150) was coated at a density of 10 M per minute using a PET film (Mitsubishi, product name: T910E) having a thickness of 125 um and dried at a temperature of 80 to 120 ^° C After hardening, ultraviolet irradiation was conducted to produce a hard coating film having a blocking thickness of 1.5 μm and antistatic properties.

Step 2: Ultraviolet curing type oil-weapon hybrid  Type 2 Hard coating layer (300) manufacture

(Trade name: MEK-ST-40 (SiO ₂ content: 40% by weight, particle size: 10 to 15 nm, solvent: methyl ethyl ketone)) and 3 g of 3-acryloxypropyltrimethoxysilane KBM-5103) and acetic acid (1.2 g) were added to a round-bottomed flask. After completion of the reaction, the reaction mixture was diluted with methyl ethyl ketone to a solid content of 30% by weight, and then 7 g of water was slowly added dropwise at room temperature. Inorganic hybrid nanosilica composite sol was synthesized.

Inorganic hybrid nano-metal oxide composite sol having a solid content of 30% by weight was charged with 300 g (Aliphatic multifunctional acrylate, product of Miwon Company), 300 g of photo-curable resin MU9500 (Aliphatic hexafunctional acrylate, product of MIWON) 184 (manufactured by Ciba), diluted with methyl ethyl ketone so that the total solid content became 30% by weight, and then stirred for 1 hour to prepare a resin composition for oil-inorganic hybrid hard coating.

Using the prepared hard coating composition, the hard coating film having anti-blocking property and antistatic property prepared in the first step was coated with microgravure (mesh # 150) at a rate of 10 M per minute and dried at 80 to 120 ^° C Dried and then irradiated with ultraviolet rays to prepare an oil-inorganic hybrid type hard coating film having a coating thickness of 1.2 탆.

Step 3: UV-curable oil-based weapon hybrid  Type High Refraction  Manufacturing coating layer 400

Inorganic hybrid titanium dioxide complex sol (particle size: 15 袖 m, solid content 20%) surface-treated (5% based on solid content) with 3-methacryloxypropyltrimethoxysilane manufactured according to Korean Patent Publication No. 2011-0133209, (Corresponding to the formula 2), 10 g of N-vinylpyrrolidone (Aldrich), 12 g of dipentaerythritol hexaacrylate (Aldrich), 10 g of urethane acrylate : Miramer HR3700) and 3 g of Irgacure 184 (Ciba) were mixed with a mixed solution of methyl ethyl ketone and propylene glycol monomethyl ester in a weight ratio of 3: 7 to a total solids content of 5% by weight.

Coated with a microgravure (mesh # 200) at a speed of 10 M / min on the surface of the hard-coated film (without blocking) of the organic-inorganic hybrid type prepared in the second step and dried at a temperature of 80 to 120 ^° C After the coating was rough, a coating film having a high refractive index layer with a thickness of 300 nm or less was prepared by ultraviolet irradiation.

Step 4: UV curing type oil-weapon hybrid  Type Hollow silica Low refractive  Fabrication of coating layer 500

(Trade name: JX1004SIV, solid content 20% by weight, particle size: 40 nm, solvent: isopropyl alcohol), 5 g of vinyltrimethoxysilane (product name: KBM- 1003) and acetic acid (0.2 g) were added to a round bottom flask. After completion of the reaction, the reaction mixture was diluted with methyl ethyl ketone to a solid content of 20% by weight, 2 g of water was slowly added dropwise at 0 ^° C. and reacted for 5 hours. Sol was synthesized.

Inorganic hybrid (manufactured by 3M, product name: HQ-115A, corresponding to formula (III)) was added to the prepared organic-inorganic hybrid hollow silica sol having a solid content of 20 wt% Inorganic hybrid hollow silica sol and ionic antistatic agent were ion-bonded at a rate of 3 rpm at room temperature so as to be dissolved in methyl ethyl ketone at a ratio of 10 wt% based on the solids content of the hollow silica sol, Lt; / RTI > 20 g of a photopolymerizable resin MU9500 (manufactured by Miwon Company) and 3 g of a photoinitiator IGACURE 184 (manufactured by Ciba) were dissolved in a mixed solution of methyl ethyl ketone and propylene glycol monomethyl ester in a weight ratio of 3: 7 to a total solids content of 2 wt% % By weight for 1 hour to prepare an ultraviolet curable organic-inorganic hollow silica resin composition having printability and antistatic property.

Inorganic hybrid type high refractive index coating film prepared in the third step was coated with a slot die at a rate of 10 M per minute and dried at a temperature of 80 to 120 ^° C to form a low refractive index layer having a coating thickness of 200 nm or less Lt; RTI ID = 0.0 > a < / RTI >

Step 5: Production of transparent conductive film

Indium-tin oxide was deposited on the low index layer of the index matching film prepared in the fourth step by sputtering at a rate of 3 M / min, and then heat-treated at 150 ^° C for 1 hour to prepare a transparent conductive film. The evaluation of the optical characteristics is shown in Tables 1 and 2.

≪ Embodiment 2 >

In the third step, the high-refraction coating liquid was changed to TiO ₂ -ZrO ₂ -SnO ₂ A transparent conductive film was prepared in the same manner as in Example 1, except that the surface treatment was performed using a nano-sol (particle size of 10 to 15 nm). The evaluation of the optical characteristics is shown in Tables 1 and 2.

≪ Comparative Example 1 >

The hard coating layer in the first and second steps was coated using LGB-04 (trade name: LGB-04, Oligomer type resin, refractive index: 1.50) and the high refractive layer in the third step was coated with SUP- 605 (refractive index: 1.61) was diluted to a solid content of 5% by weight. The low refraction layer of the fourth step was diluted with SUD-460 (refractive index 1.46) of Shin-T & C Co. to a solid content of 1 wt%, and a transparent electrode film was produced in the same manner as in Example 1. The evaluation of optical properties of the transparent electrode film thus manufactured is shown in Tables 1 and 2. [

≪ Comparative Example 2 >

Table 1 shows the evaluation of the optical properties of the index matching film MKZ-PN01 (Higashiyama, original thickness 125um), which is a commercially available product, as a comparative sample.

≪ Evaluation of physical properties &

① Haze and Transmittance

The haze and transmittance of the transparent substrate film surface were measured by using a spectrophotometer (Nakamura Co., Ltd., HM 150) to direct the surface of the transparent base film to a light source.

② Pencil Hardness

Pencil hardness was measured at 500 g load using a pencil hardness tester (PTH, Korea Science and Engineering). The pencil was made five times per pencil hardness using the product of Mitsubishi. If two or more pieces of gas were judged to be defective.

③ Adhesiveness

11 straight lines were drawn at intervals of 1 mm on the coated surface of the film to form 100 squares, and the peeling test was carried out using a tape. Three 100 squares were tested and the average value recorded.

Adhesion = n / 100

100: total number of rectangles

n: Indicates the number of squares that are not peeled off.

④ Anti-blocking property

Two coated backs are arranged facing each other, then pressed with a roller under a load of 2 kg, and after 10 minutes, whether or not the coated surface falls is observed.

If two floors fall: OK

When two layers are in close contact: NG

⑤ Rear surface resistance

The surface resistance value was measured five times using a surface resistance meter (SIMCO, ST-3) to give an average value.

⑥ Sheet resistance of transparent conductive layer

The average value was measured five times using Loresta-GP (Mitsubishi, Model: MCP-T610) as a 4-terminal measurement method.

⑦ My metastatic

The index-matching film is placed between two mirror-faced mirrors and pressed with a clip. The specimen is kept at 60 ^° C and 90% relative humidity for 12 hours, then left at room temperature for 30 minutes. The presence of staining was confirmed by visual inspection of the mirror surface with the naked eye.

If you can not see the mirror surface: OK

When the mirror surface is visible: NG

⑧ shrinkage rate

The transparent electrode film was precisely cut to 20 x 20 cm, and then kept in a thermostat at 150 ^° C for 1 hour and left at room temperature for 30 minutes. The film maintained at room temperature was measured by using a vernier caliper to measure the difference in shrinkage percentage in the TD direction before and after the reliability, and expressed as a percentage.

⑨ Measurement of refractive index

The coated coating solution was coated on a wafer, dried at 120 ^° C for 1 minute, cured using an ultraviolet lamp, and measured at a wavelength of 632.8 nm using a prism coupler analyzer.

⑩ Reflectance measurement

The b ^* value of the prepared index matching film was measured by reflectance and transmission method in a visible light region (400 to 700 nm) using a spectrophotometer (Konica Minolta Co., model name: CM3500d).

example Index matching film front Index matching film back The conductive film layer Transmittance
(%) Hayes
(%) surface
resistance
(Ω / cm) b ^* Adhesiveness blocking
Preventiveness surface
resistance
(Ω / cm) pencil
Hardness Metastatic Shrinkage rate
(TD%) Sheet resistance
(Ω / □) First Embodiment 91.2 0.79 10 ^12.5 -0.04 100 OK 10 ^11.4 H OK 0.52 126 Second Embodiment 91.0 0.82 10 ^12.8 0.054 100 OK 10 ^11.0 H OK 0.56 128 Comparative Example 1 89.7 1.13 10 ^13.5 0.152 92 NG 10 ^12.4 H NG 0.68 223 Comparative Example 2 89.0 0.71 10 ^14.6 0.024 100 OK 10 ^13.6 H OK 0.58 255

Film construction layer First Embodiment Second Embodiment Comparative Example 1 Hard coat layer refractive index 1.49 1.49 1.50 High refractive index layer refractive index 1.65 1.66 1.61 Refractive index layer refractive index 1.38 1.38 1.46 Anti-blocking layer (back layer) Refractive index 1.48 1.48 1.50

INDUSTRIAL APPLICABILITY As shown in the above results, the index matching film produced according to the present invention has excellent antistatic property, anti-blocking property, shrinkage ratio, adhesion property, and resistance to metastasis, and also has low resistance, high transmittance and low haze, Film. The index matching film is an index matching film capable of realizing a transmittance of 91% or more, a haze of 1% or less, a back electrification preventing property of 10 ¹² or less and a sheet resistance after ITO deposition of 150? /? Sensor electrodes, organic solar cells, smart windows, and transparent conductive films for shielding electromagnetic waves.

As described above, the index matching film and the manufacturing method thereof according to the present invention are not limited to the configuration and method of the embodiments described above, but the embodiments may be modified in various ways, All or a part of the above-described elements may be selectively combined.

100: base film 200: first hard coating layer
300: second hard coating layer 400: high refractive index coating layer
500: Hollow silica low refraction coating layer 600: Conductive layer

Claims (42)

A base film;
A first hard coating layer formed on the lower surface of the base film by reacting an ionic antistatic compound and an organic-inorganic hybrid nano-metal oxide;
A second hard coat layer formed on the upper surface of the base film by reacting an ionic antistatic compound and an organic-inorganic hybrid nano-metal oxide;
A high refractive index coating layer formed by reacting a fluorene compound having an acrylic group on the upper surface of the second hard coat layer with a nano-metal oxide of an organic-inorganic hybrid type; And
And a hollow silica low refraction coating layer formed by reacting a lithium compound with an ultraviolet curing type organic-inorganic hybrid type hollow silica on the high refractive index coating layer,
Wherein the ionic antistatic compound is a compound represented by Formula 1,
Wherein the first hard coating layer or the second hard coating layer comprises 3 to 70% by weight of a reaction mixture obtained by reacting the organic-inorganic hybrid nano-metal oxide and the ionic antistatic compound, 5 to 80% by weight of a photocurable resin, 15% To 90% and 1 to 10% by weight of a photoinitiator.
[Chemical Formula 1]

Wherein R ₁ -N is a heterocyclic compound selected from the group consisting of imidazole, pyridine, pyrrole, benzopyrrole, pyrazole, isothiazole, thiazole, indole, indazole, isoindole, indolizine and carbazole, R ₂ is a straight chain alkyl group having 1 to 18 carbon atoms and X is CF ₃ SO ₃ , CF ₃ CO ₂ , FPO ₃ , CF ₂ ═CFCO ₂ , PF ₆ , BF ₄ , N (CN) ₂ , ₂ CF ₃ ) ₂ . The method according to claim 1,
And a conductive layer formed on the upper surface of the hollow silica low refractive coating layer. delete The method according to claim 1,
Wherein the fluorene compound is a compound represented by the following formula (2).
(2)

(X is selected from CH ₂ ═CHCO-, CH ₂ ═C (CH _{3 )} CO-, Y is an aromatic ring compound selected from fluorene and xanthene, W is H, CH ₃ , It is selected from _{OH, OCH 3, Cl, Br} .) The method according to claim 1,
Wherein the lithium compound is a compound represented by the following formula (3).
(3)
Li-Z
(Z represents an anion and is a substituent selected from the group consisting of (C ₂ F ₅ SO ₂ ) N, C ₃ F ₇ CO ₂ , (CF ₃ SO ₂ ) (CF ₃ CO) N) delete The method according to claim 1,
First the oil contained in the hard coat layer-inorganic hybrid nano metal oxide particle diameter 20 ~ 100nm hollow _{silica, SiO 2, TiO 2, ZrO} 2, Al 2 O 3, SnO 2, Sb 2 O 5, Nb ₂ O ₃ , and Y ₂ O ₃ , and is surface-treated with a silane coupling agent. The method according to claim 1,
Wherein the oil contained in the second hard coating layer-inorganic hybrid nano metal oxide particle diameter of 5 ~ 30nm of the hollow _{silica, SiO 2, TiO 2, ZrO} 2, Al 2 O 3, SnO 2, Sb 2 O 5, Nb ₂ O ₃ , and Y ₂ O ₃ , and is surface-treated with a silane coupling agent. The method according to claim 1,
Wherein the high refractive index coating layer comprises 3 to 20% by weight of the fluorene compound, 5 to 55% by weight of a nano-metal oxide sol of an organic-inorganic hybrid type, 25 to 60% by weight of a photocurable resin, 15 to 30% by weight of a photo-curable solvent having a group and 1 to 10% by weight of a photoinitiator. The method of claim 9,
Wherein the composition is diluted to 0.1 to 10% of the total solids in the single or mixed solvent. The method of claim 9,
The organic-inorganic hybrid nano-metal oxide included in the high refractive index coating layer may be TiO ₂ , ZrO ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , Nb ₂ O ₃ , Y ₂ O ₃ Characterized in that it comprises at least one metal oxide selected from the group consisting of silane coupling agents and silane coupling agents. The method of claim 9,
The photocurable solvent may be selected from the group consisting of acrylamide, N-methylacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide and N-vinylpyrrolidine. Examples of the solvent having a hydroxy group include hydroxyethyl acrylate Wherein the index-matching film comprises at least one component selected from the group consisting of hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate. The method according to claim 1,
Wherein the hollow silica low refractive index coating layer comprises a reaction mixture composed of 5 to 60% by weight of the hollow silica, 10 to 90% by weight of a photocurable resin, and 1 to 10% by weight of a photoinitiator. 14. The method of claim 13,
Wherein the reaction mixture is diluted to 0.1 to 10% of the total solids in a single solvent or a mixed solvent. 14. The method of claim 13,
Wherein the hollow silica has a particle diameter of 10 to 60 nm, a particle porosity of 10 to 70%, a refractive index of 1.2 to 1.40, and a surface treatment with a silane coupling agent. The method according to claim 1,
The base film may be formed of at least one selected from the group consisting of polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), polypropylene (PP), polyethylene (PE) (PS: Polystyren). ≪ / RTI > The method according to claim 1,
Wherein the base film has a thickness of 20 to 400 mu m. The method according to any one of claims 7, 8, 11 and 15,
The silane coupling agent may be selected from the group consisting of 3-methacryloxypropylmethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- (Aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- Aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxy Silane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, bis (triethoxysilylpropyl) Tetrasulfide, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 2- (3,4-epoxide Cyclohexyl) -ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, para-styryltrimethoxysilane, para- Acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) -2-aminoethyl- 3-chloropropyltrimethoxysilane, and 3-chloropropyltriethoxysilane. Index matching film comprises. The method according to any one of claims 1, 9 and 13,
In order to maintain dispersibility of the photo-curable resin with the organic-inorganic hybrid nano-metal oxide complex sol, the photo-curable resin is added with a hydroxy or ethylene oxide monomer, and an ethylene oxide addition (2-8 mol) phenol (meth) acrylate, (2 to 10 moles) 1,6-hexanediol diacrylate, neopentyl glycol di (meth) acrylate, propylene oxide addition (2 to 4 moles) neopentyl glycol diacrylate, tripropylene glycol di (meth) Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, ethylene oxide addition polyethyleneglycol di (meth) acrylate, bifunctional urethane acrylate, Urethane (meth) acrylate and silicone polyester acrylate, bisphenol A (3 to 30 mol of ethylene oxide part) di (meth) acrylate Relate and bisphenol A epoxy acrylate index matching film comprising the one or more components selected from the group consisting of. Reacting an ionic antistatic compound and a metal oxide of an organic-inorganic hybrid type on the lower surface of the base film to form a first hard coat layer;
Reacting an ionic antistatic compound and a metal oxide of an organic-inorganic hybrid type on the upper surface of the base film to form a second hard coat layer;
Forming a high refractive index coating layer by reacting a fluorene compound with a high refractive index metal oxide sol of an organic-inorganic hybrid type on the upper surface of the second hard coat layer; And
Forming a hollow silica low refraction coating layer on the upper surface of the high refractive index coating layer by using a lithium compound and a UV-curable organic-inorganic hybrid type hollow silica;
Wherein the ionic antistatic compound is a compound represented by Formula 1,
Wherein the first hard coating layer or the second hard coating layer comprises 3 to 70% by weight of a reaction mixture obtained by reacting the organic-inorganic hybrid nano-metal oxide and the ionic antistatic compound, 5 to 80% by weight of a photocurable resin, 15% To 90% by weight of a photoinitiator and 1 to 10% by weight of a photoinitiator.
[Chemical Formula 1]

Wherein R ₁ -N is a heterocyclic compound selected from the group consisting of imidazole, pyridine, pyrrole, benzopyrrole, pyrazole, isothiazole, thiazole, indole, indazole, isoindole, indolizine and carbazole, R ₂ is a straight chain alkyl group having 1 to 18 carbon atoms and X is CF ₃ SO ₃ , CF ₃ CO ₂ , FPO ₃ , CF ₂ ═CFCO ₂ , PF ₆ , BF ₄ , N (CN) ₂ , ₂ CF ₃ ) ₂ . The method of claim 20,
Further comprising the step of forming a conductive layer on the upper surface of the hollow silica low refractive index coating layer by sputtering deposition using indium-tin oxide. delete The method of claim 20,
Wherein the fluorene compound contained in the high refractive index coating layer is a compound represented by the following formula (2).
(2)

(X is selected from CH ₂ ═CHCO-, CH ₂ ═C (CH _{3 )} CO-, Y is an aromatic ring compound selected from fluorene and xanthene, W is H, CH ₃ , It is selected from _{OH, OCH 3, Cl, Br} .) The method of claim 20,
Wherein the lithium compound contained in the hollow silica low refractive index coating layer is a compound represented by the following formula (3).
(3)
Li-Z
(Z represents an anion and is a substituent selected from the group consisting of (C ₂ F ₅ SO ₂ ) N, C ₃ F ₇ CO ₂ , (CF ₃ SO ₂ ) (CF ₃ CO) N) The method of claim 20,
Wherein forming the first hard coat layer comprises:
Preparing a surface modified organic-inorganic hybrid type nano-metal oxide sol by surface-reacting the nano-metal oxide with a silane coupling agent;
Reacting the nano metal oxide sol with an ionic antistatic compound;
Combining the ionic antistatic compound with the photocurable resin to synthesize a first hard coating solution; And
And applying the first hard coating liquid to a lower surface of the base film. delete 26. The method of claim 25,
The nano-metal oxide may be at least one of hollow silica having a particle diameter of 20 to 100 nm, SiO ₂ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , Nb ₂ O ₃ and Y ₂ O ₃ A method for producing an index-matched film, which comprises a metal oxide. The method of claim 20,
Wherein forming the second hard coat layer comprises:
Preparing a surface modified organic-inorganic hybrid type nano-metal oxide sol by surface-reacting the nano-metal oxide with a silane coupling agent;
Reacting the nano metal oxide sol with an ionic antistatic compound;
Synthesizing the ionic antistatic compound with the photocurable resin to synthesize a second hard coating solution; And
And coating the second hard coating liquid on the upper surface of the base film. delete 29. The method of claim 28,
The nano-metal oxide may include at least one metal oxide selected from the group consisting of SiO ₂ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , Nb ₂ O ₃ and Y ₂ O ₃ having a particle diameter of 5 to 30 nm The method for producing an index matching film according to claim 1, The method of claim 20,
The step of forming the high-
Preparing a surface modified organic-inorganic hybrid type nano-metal oxide sol by surface-reacting the nano-metal oxide with a silane coupling agent;
Reacting the nano metal oxide sol with the fluorene compound;
Adding a photo-curing resin to the fluorene compound to synthesize a high-refraction coating solution; And
And coating the high refractive index coating solution on the upper surface of the second hard coating layer to form the high refractive index coating layer. 32. The method of claim 31,
Wherein the high refractive index coating liquid contains 3 to 20% by weight of the fluorene compound, 5 to 55% by weight of the nano-metal oxide sol, 25 to 60% by weight of the photo-curable resin, light having an amide group or a hydroxy group having an unsaturated double bond, 15 to 30% by weight of a curable solvent and 1 to 10% by weight of a photoinitiator. 33. The method of claim 32,
Further comprising the step of diluting the composition alone or in a mixed solvent so that the total solid content of the composition becomes 0.1 to 10%, followed by coating treatment. 32. The method of claim 31,
The nano-metal oxide includes at least one metal oxide selected from TiO ₂ , ZrO ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , Nb ₂ O ₃ and Y ₂ O ₃ having a particle diameter of 5 to 60 nm ≪ / RTI > The method of claim 20,
Wherein the forming of the hollow silica low refractive index coating layer comprises:
Inorganic hybrid type hollow silica sol by surface-reacting the hollow silica with a silane coupling agent;
Reacting the hollow silica sol with the lithium compound;
Inorganic hybrid type hollow silica low refraction coating liquid for ultraviolet curing by adding a photo-curing resin to the reacted lithium compound; And
And coating the hollow silica low refraction coating solution on the high refractive index coating layer. 36. The method of claim 35,
Wherein the hollow silica low refractive coating solution comprises a reaction mixture composed of 5 to 60% by weight of an organic-inorganic hybrid hollow silica combined with the lithium compound, 10 to 90% by weight of the photocurable resin, and 1 to 10% by weight of a photoinitiator ≪ / RTI > 37. The method of claim 36,
Further comprising the step of thinning the reaction mixture by diluting the reaction mixture alone or in a mixed solvent so that the total solid content is 0.1 to 10%. 36. The method of claim 35,
Wherein the hollow silica has a particle diameter of 10 to 60 nm, a particle porosity of 10 to 70%, and a refractive index of 1.2 to 1.40. The method of any one of claims 25, 30 and 35,
The silane coupling agent may be selected from the group consisting of 3-methacryloxypropylmethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- (Aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- Aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxy Silane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, bis (triethoxysilylpropyl) Tetrasulfide, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 2- (3,4-epoxide Cyclohexyl) -ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, para-styryltrimethoxysilane, para- Acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) -2-aminoethyl- 3-chloropropyltrimethoxysilane, and 3-chloropropyltriethoxysilane. The method of index matching film comprising the component. The method of any one of claims 25, 28, 31 and 35,
The photocurable resin is a hydroxy or ethylene oxide moiety. The monomer is an ethylene oxide addition (2-8 mol) phenol (meth) acrylate, an ethylene oxide addition (2-10 mol) 1,6-hexanediol diacrylate, neopentyl Glycol di (meth) acrylate, propylene oxide addition (2 to 4 mol) neopentyl glycol diacrylate, tripropylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, ethylene glycol di (meth) acrylate, ethylene oxide addition polyethylene glycol di (meth) acrylate, difunctional urethane acrylate, silicone urethane (meth) acrylate and silicone polyester acrylate, bisphenol A Addition 3 to 30 moles) is selected from the group consisting of di (meth) acrylate and bisphenol A epoxy acrylate The method of manufacturing an index matching film characterized in that it comprises at least one component. The method of any one of claims 25, 28, 31 and 35,
The photocurable resin is preferably at least one selected from the group consisting of polyfunctional acrylates, trimethylolpropane (meth) acrylate, ethylene oxide addition (3 to 15 mol) trimethylolpropane (meth) acrylate, trifunctional urethane acrylate, glycerin triacrylate, Trimethylolpropane tri (meth) acrylate, tris 2-hydroxyethyl isocyanate triacrylate, ethylene oxide addition pentaerythritol tetraacrylate, di (meth) acrylate, propylene oxide adduct (Meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (metha) acrylate 6-functional urethane acrylate, trimethylolpropane tetra (meth) acrylate, pentaerythritol tetra , And 10-functional aliphatic urethane acrylate. By weight based on the total weight of the film. 33. The method of claim 32,
The photocurable solvent may be selected from the group consisting of acrylamide, N-methylacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide and N-vinylpyrrolidine. Examples of the solvent having a hydroxy group include hydroxyethyl acrylate Wherein at least one component selected from the group consisting of hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate is contained.

Images