KR101608962B1 - Index matching film and method of manufacturing the same - Google Patents

Index matching film and method of manufacturing the same Download PDF

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KR101608962B1
KR101608962B1 KR1020150085385A KR20150085385A KR101608962B1 KR 101608962 B1 KR101608962 B1 KR 101608962B1 KR 1020150085385 A KR1020150085385 A KR 1020150085385A KR 20150085385 A KR20150085385 A KR 20150085385A KR 101608962 B1 KR101608962 B1 KR 101608962B1
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coating layer
acrylate
metal oxide
nano
refractive index
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KR1020150085385A
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Korean (ko)
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최지선
서동규
변달석
김광배
김청
조재형
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(주)코이즈
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members

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Abstract

The present invention relates to an index matching film and a manufacturing method thereof and, more specifically, to an index matching film with improved visibility, having a hard coating layer, a high refraction coating layer, and low refraction coating layer of a porous structure laminated on a transparent base film, thereby having high adhesion between each layer, maintaining high transmittance, while having low haze, and to 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 of manufacturing the same. More specifically, a hard coating layer, a high refractive index coating layer, and a low refractive index coating layer of a porous structure are laminated on a transparent base film to maintain high transmittance, And a method for producing the same.

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 whitening, and the transmittance is reduced. When the wiring electrode is formed 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.

It is an object of the present invention 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 low refractive index coating layer of a porous structure on a transparent base film, And a manufacturing method thereof.

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- A high refractive index coating layer, and a low refractive index coating layer having a porous structure formed on the upper surface of the high refractive index coating layer by sol-gel reaction of the nanosilica and the silane coupling agent.

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

[Chemical Formula 1]

Figure 112015058217395-pat00001

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 .

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.

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

(2)

Figure 112015058217395-pat00002

(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 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 may contain 3 to 20% by weight of a fluorene compound, 5 to 55% by weight of a nano-metal oxide sol of a 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.

At this time, the composition 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 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.

In this case, the low refractive index coating layer of the porous structure is prepared by sol-gel reaction of 1 to 15 wt% of nano-silica sol, 10 to 30 wt% of silane coupling agent, 10 to 45 wt% of water and 10 to 45 wt% of ethanol, One reaction mixture.

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 nanosilica has a particle diameter of 1 to 40 mm and may have a porous structure by sol-gel reaction with the silane coupling agent at pH 4.

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.

According to another aspect of the present invention, there is provided a method of manufacturing an index matching film, comprising: forming a first hard coating layer on a bottom surface of a base film by reacting an ionic antistatic compound and a metal oxide of an organic- 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 low refractive index coating layer of a porous structure by sol-gel reaction of nanosilica and a silane coupling agent on the high refractive index coating layer.

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

[Chemical Formula 1]

Figure 112015058217395-pat00003

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 .

In this case, the first hard coating layer or the second hard coating layer comprises 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, To 90% and 1 to 10% by weight of a photoinitiator.

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

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

(2)

Figure 112015058217395-pat00004

(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 step of forming the first hard coating layer may include the steps of: preparing a nano-metal oxide sol of a surface-modified organic-inorganic hybrid type by surface-reacting a nano-metal oxide with a silane coupling agent; A step of reacting the antistatic compound with the ionic antistatic compound, the step of synthesizing the ionic antistatic compound with the photocurable resin to synthesize the first hard coating liquid, and the step of applying the first hard coating liquid to the lower surface of the base film can do.

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 includes the steps of: preparing a nano-metal oxide sol of a surface-modified organic-inorganic hybrid type by surface-reacting a nano-metal oxide with a silane coupling agent; Adding an ionic antistatic compound to the photocurable resin to synthesize a second hard coating liquid; and applying a second hard coating liquid to the upper surface of the base film .

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 >

The step of forming the high refractive index coating layer may include the steps of: preparing a nanometer metal oxide sol of a surface-modified organic-inorganic hybrid type by surface-reacting the nanometal oxide with a silane coupling agent; Forming a high refractive index coating solution by applying a photocurable resin to the reacted fluorene compound to form a high refractive index coating solution, and applying a high refractive index coating solution to an upper 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 resin having an amide group or a hydroxyl group having an unsaturated double bond 15 to 30% by weight of a solvent and 1 to 10% by weight of a photoinitiator.

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

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.

At this time, the step of forming the low refraction coating layer of the porous structure includes a step of reacting the nanosilica with the silane coupling agent, a step of diluting the sol-gel-reacted coating solution to prepare a low refractive coating liquid of a thermosetting porous structure , And applying a low refractive coating liquid having a porous structure to the upper surface of the high refractive index coating layer.

In this case, the low refractive index coating liquid having a porous structure may comprise 1 to 15% by weight of the nano silica sol having a size of 1 to 40 nm, 10 to 30% by weight of the silane coupling agent, 10 to 45% by weight of water and 10 to 45% Sol-gel reaction followed by dilution with a solvent.

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 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.

Also, by forming a low refractive coating layer by thermally curing a porous low refractive coating solution obtained by sol-gel reaction of nano silica and a silane coupling agent, the adhesion between the high refractive coating layer is enhanced, the physical properties are not changed during acid treatment, and the pattern visibility is 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 flowchart showing the manufacturing process of the low refraction coating layer of the porous structure in the index matching film of the present invention.
7 is a graph showing the reflectance of an index matching film produced according to the first embodiment of the method for producing an index matching film of the present invention.
8 is a graph of the reflectance of the index matching film prepared according to the second embodiment of the method for producing the index matching film of the present invention.
9 is a graph of the reflectance of the index matching film prepared according to the first comparative example for comparison with the method of producing the index matching film of the present invention.
10 is a graph of the reflectance of an index-matched film produced according to a second comparative example for comparison with the method of producing an index-matched film of the present invention.

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.

Referring to FIG. 1, the index matching film of the present invention includes 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 200 formed on the upper surface of the base film 100, A high refraction coating layer 400 formed on the upper surface of the second hard coating layer 300 and a low refractive coating layer 500 and a low refractive coating layer 500 formed on the upper surface of the high refractive index coating layer 400, And a conductive layer (600).

Specifically, the base film 100 may be formed of a material selected from the group consisting of polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), polypropylene (PP), polyethylene : Polyethylene) and polystyrene (PS: Polystyren).

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

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]

Figure 112015058217395-pat00005

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 compound is synthesized by using a commercially available product (CHTA-402, KOY-101: KOY-101) or using a heterocyclic compound containing nitrogen. The method for synthesizing an ionic antistatic compound 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 focusing light for forming the first hard coat layer 200 is obtained by a reaction between the organic-inorganic hybrid nano-metal oxide sol and the ionic antistatic compound represented by the formula (1) 3 to 70% by weight of the mixture; 5 to 80% by weight of a photocurable resin; 15 to 90% by weight of a solvent; And 1 to 10% by weight of a light-releasing agent.

When the refractive index of the hard coating liquid is 1.40 or less, the hardness and substrate adhesion are poor. When the hard coating liquid has a refractive index higher than 1.55, the refractive index of the hard coating liquid tends to be increased, which is preferable 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 may be used in an amount of 1 to 10% or less based on the total amount of the resin composition.

Available light-branching agents can be grouped 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 optical brightener 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 400 mu m, more preferably 25 to 250 mu m

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, improves the adhesion with the high refractive index coating layer 400 and the base film 100, lowers the roughness of the coating surface, 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.

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 photo-curable resin, 15 to 90% of a solvent, and light And 1 to 10% by weight of a release agent.

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, it is preferable to use the refractive index within 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 the amount is less than 1% by weight based on the total solid content, the adhesion to the high-refractive-index layer is inferior. When 95% by weight or more is used, surface roughness and coating appearance deteriorate, Is used in an amount of 1 to 95% by weight based on the total solid content and mixed with an ultraviolet curable resin.

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 photopolymerization agent 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, the high-refraction coating layer 400 is formed of a fluorene compound of the following formula (2), a high-refraction metal oxide of an organic-inorganic hybrid type, and a curable resin.

(2)

Figure 112015058217395-pat00006

Wherein 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 selected from H, CH 3 , it is selected from OH, OCH 3, Cl, Br.

In the composition of the high refractive index coating liquid, it is preferable that 3 to 20% by weight of a fluorene compound having an acrylic group synthesized on the basis of a solid content, 5 to 55% by weight of a nano- 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 light-releasing agent.

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 Avogadro's number =

ω = wavelength of light

When the refractive index of the high refractive index coating solution is less than 1.60 on the basis of the solid content, the reflectance after the index matching film is low, and when the refractive index exceeds 1.80, the transmittance and the adhesion are lowered. Therefore, a solution having a refractive index in the range of 1.60 to 1.80 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.

The photocurable resin may be a multifunctional monomer or a monofunctional monomer, 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 optical brightener used in the production of the first hard coat layer 200 may be used as the optical brightener.

In order to form a thin film coating layer, a high refractive index layer is formed by diluting the coating solution solely with 0.1 to 10 wt% of the total solids, or by diluting it with a mixed solvent. 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 low refraction coating layer 500 having a porous structure is further formed on the upper surface of the high refractive index coating layer 400. The low refraction coating layer 500 having such a porous structure is formed by sol-gel reaction of the nanosilica and the silane coupling agent in order to enhance adhesion with the high refractive index coating layer and increase the antistatic property and the total light transmittance.

The low refraction coating layer 500 having a porous structure has a low refractive index and has high printability in order to improve the adhesion to the wiring electrode layer using a silver paste. By using the nanosilica particles in a sol-gel reaction, And has a transmittance of 91% or more, a haze of 1% or less, a surface antistatic property of 10 12 Ω / cm or less, a surface resistance after ITO deposition of 15 Ω / □ or less Thereby completing the index matching film.

In the low refraction coating layer 500 of the porous structure, an air layer is formed in the nanosilica sol nanoparticles having a diameter of 1 to 40 nm, so that the refractive index is low and the electrophoresis property is improved by the air layer. The nanosilica sol was stirred with a silane coupling agent to perform a sol-gel reaction to prepare a low refraction coating composition having a porous structure.

Nano-silica sol can be used with NISSAN MEK-ST.

When the particle size of the nanosilica sol is less than 1 nm, it is difficult to realize a low refractive index. When the particle size exceeds 40 nm, the transmittance becomes low. It is preferable to use nanosilica having a particle size of 1 nm to 40 nm.

In addition, when the refractive index of the nanosilica particles is less than 1.2, the nanosilica tends to be fragile, and when the refractive index is higher than 1.40, the refractive index is high and the desired electrooptic property can not be exhibited. Therefore, nanosilica having a refractive index of 1.2 to 1.40 is preferably used.

The colloidal sol, in which the nanosilica 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.

The composition of the low refractive index coating composition of the porous structure is composed of 1 to 15% by weight of nano silica sol, 10 to 30% by weight of silane coupling agent, 10 to 45% by weight of water and 10 to 45% of ethanol, , A low refractive index coating layer of a porous structure is formed by diluting the coating liquid with a solids content of 0.1-10% solely or in a mixed solvent.

When the solids content of the porous low refractive index coating composition is less than 0.1%, the adhesive strength to the substrate is low. When the solubility exceeds 10%, the electrophotographic characteristics and the reflectance in the visible light range are lowered. % Of the total weight of the composition.

Nanosilica reacts with a silane coupling agent at a pH of 4 to obtain a low refractive coating composition having a porous structure having a stable viscosity.

The silane coupling agent used in the low refraction coating composition can 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 a descending order. The index of refraction of each layer of the low index coating layer 500, the first hard coating layer 200, the second hard coating layer 300, the base film 100, The refractive index of the second hard coating layer 300 may be equal to or greater than 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]

Figure 112015058217395-pat00007

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 liquid 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 light-releasing agent.

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)

Figure 112015058217395-pat00008

(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 low refraction coating layer 500 having a porous structure is formed on the high refractive index coating layer 400 in step S400. At this time, the low refractive index coating layer 500 having a porous structure is formed by sol-gel reaction of the nanosilica and the silane coupling agent to increase adhesion force, antistatic property and total light transmittance between the high refractive index coating layer 400 and the conductive layer 600 do.

Specifically, the low refraction coating layer 500 having a porous structure has high printability to improve the adhesion with the wiring electrode layer using silver paste, and improves the electrophotographic characteristics. After drying at a temperature of 80 to 120 占 폚, the film was aged at 60 占 폚 to obtain an index matching film having a low refraction coating layer having a coating thickness of 200 nm or less.

The coating liquid forming the low refraction coating layer 500 of the porous structure may be prepared in the following order. The nanoscale silica sol, silane coupling agent, distilled water, ethanol and formic acid are placed in a round bottom flask and sol-gel-reacted to prepare a low refraction coating composition having a porous structure.

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 low refraction coating composition is coated on the upper surface of the high refractive index coating layer 400 to form a low refraction coating layer 500 having a porous structure.

After forming the low refraction coating layer 500 having a porous structure, a conductive layer 600 which is a transparent electrode is formed through ITO deposition (S500).

The conductive layer 600 is formed by depositing indium-tin oxide on the upper surface of the low refraction coating layer 500 having a porous structure at a rate of 3 to 5 M per minute by a sputtering deposition method, and then subjected to a heat treatment process at 150 ° C. for 1 hour .

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 a metal material of the conductive film.

The index matching film can be produced by the above-described process.

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]

Figure 112015058217395-pat00009

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]

Figure 112015058217395-pat00010

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 secure the appearance of the coating surface. When the thickness is 10 μm or more, the hard coat layer 300 is cracked when 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)

Figure 112015058217395-pat00011

(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 flowchart showing the manufacturing process of the low refraction coating layer of the porous structure in the index matching film of the present invention.

Referring to FIG. 6, the low refraction coating layer of the porous structure is subjected to a sol-gel reaction with nanosilica having a particle size of 1 to 40 nm and a silane coupling agent (S410).

At this time, the nanosilica reacts solely with the silane coupling agent at pH 4 to obtain a coating liquid having a stable state of viscosity.

At this time, the silane coupling agent may be used in the same manner as that used in the production of the first hard coat layer 200.

After step S410, the sol-gel reacted coating solution is diluted with a solvent to produce a low refractive coating composition (S420).

In this case, distilled water, water, ethanol, methanol and the like may be used as the solvent.

After the step S420, the diluted coating liquid is applied on the upper surface of the high refractive index coating layer 400 (S430).

At this time, the low refraction coating composition may be thinned to a thickness of 200 nm or less by diluting the low refraction coating composition alone or in a mixed solvent so that the solid content thereof becomes 0.1 to 10%, and then performing a coating treatment.

The coating liquid applied on the upper surface of the high refractive index coating layer 500 is thermally cured to form a low refractive index coating layer having a porous structure.

In this case, the thermosetting can be aged at 60 ° C to obtain a high adhesive strength after drying at a temperature of 80 to 120 ° C for a uniform particle size distribution.

Hereinafter, the present invention will be described in more detail with reference to Figs.

7 is a graph showing the reflectance of an index matching film produced according to the first embodiment of the method for producing an index matching film of the present invention.

8 is a graph of the reflectance of an index matching film produced according to the second embodiment of the method for producing an index matching film of the present invention.

9 is a graph of reflectance of the index matching film prepared according to the first comparative example for comparison with the method of producing the index matching film of the present invention.

10 is a graph of the reflectance of the index matching film prepared according to the second comparative example for comparison with the method of producing the index matching film of the present invention.

≪ 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.

Stage 4: Porous structure through sol-gel reaction Low refractive  Fabrication of coating layer 500

(Manufactured by Shin-Etsu, product name: KBM-1003), distilled water 300 g, ethanol 300 g (manufactured by NISSAN Corporation, product name: MEK-ST, solid content 20 wt.%, Particle size 10 nm, solvent: MEK), vinyltrimethoxysilane 200 g And formic acid (0.2 g) were put into a round-bottomed flask and stirred for 24 hours to effect a sol-gel reaction. After completion of the reaction, MEK was added so that the solid content became 3 wt%, and the mixture was stirred at a stirring speed of 500 rpm or higher at a high speed to prepare a low refractive coating composition having a porous structure.

Coated on the high-refractive-index coating surface of the organic-inorganic hybrid type prepared in the third step with microgravure (mesh # 200) at a rate of 10 M / min, followed by drying at a temperature of 80 to 120 ° C, followed by aging at 60 ° C An index matching film having a low refractive index layer with a coating thickness of 200 nm or less was prepared.

Step 5: Transparent conductive film (Index matching  Film) manufacturing

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

≪ Embodiment 2 >

Except that a silane coupling agent was subjected to a sol-gel reaction with 3-glycidoxypropyltrimethoxysilane (Shin-Etsu, product name: KBM-403) in the fourth step, a transparent conductive A film was prepared. 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 coating layer of the fourth step was prepared by diluting SUD-460 (refractive index: 1.46) manufactured by Shin-Etsu Chemical Co., Ltd. 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 prepared coating solution was coated on a wafer, dried at 120 ° C for 1 minute, cured using a UV 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).

⑪ Stability against acid

The damage to the acid was confirmed to confirm the etching stability. The coating film was placed in a 10% H 2 SO 4 acid solution, and after 24 hours, the appearance was visually observed.

example Index matching film front Index matching film back The conductive film layer Transmittance
(%) Hayes
(%) b * Adhesiveness Damage to the mountain blocking
Preventiveness surface
resistance
(Ω / cm) pencil
Hardness Metastatic Shrinkage rate
(TD%) Sheet resistance
(Ω / □) 1st
Example 91.5 0.7 0.053 100 × OK 10 11.0 H OK 0.12 125 Second
Example 91.4 0.6 -0.021 100 × OK 10 11.2 H OK 0.09 127 1st
Comparative Example 89.7 1.2 0.152 92 ○ NG 10 12.5 H NG 0.68 223 Second
Comparative Example 89 0.7 0.024 100 △ OK 10 13.6 H OK 0.58 255

* Damage to acid: O: Damage severity,: Damage normal, X: No damage

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 1.65 1.61 Refractive index of low refraction coating layer 1.38 1.37 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 films of the first and second embodiments have an index matching of not less than 91% transmittance, haze of not more than 1%, antistatic of backside of not more than 10 12 , and sheet resistance after ITO deposition of 150? /? It can be used for touch sensor electrodes of display touch screen, organic solar cell, smart window, and transparent conductive film for shielding electromagnetic wave because there is no change in appearance when etching with film.

7 to 10, the index matching film of the first embodiment and the second embodiment has a difference in reflectance (b *) between the base film and the conductive layer, so that the circuit pattern printed on the conductive layer It is possible to solve the problem that is visible to the user.

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: low refraction coating layer of porous structure 600: conductive layer

Claims (33)

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 low refraction coating layer of porous structure formed on the upper surface of the high refractive index coating layer by sol-gel reaction of nanosilica and a silane coupling agent,
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 wt% and 1 to 10 wt% of a photoinitiator,
The low refraction coating layer of the porous structure is prepared by sol-gel reaction of 1 to 15% by weight of nano-silica sol, 10 to 30% by weight of silane coupling agent, 10 to 45% by weight of water and 10 to 45% by weight of ethanol, Lt; RTI ID = 0.0 > 1, < / RTI > and a reaction mixture.
[Chemical Formula 1]
Figure 112015116359702-pat00012

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,
Wherein the fluorene compound is a compound represented by the following formula (2).
(2)
Figure 112015058217395-pat00013

(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,
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 the organic-inorganic hybrid type, 25 to 60% by weight of a photocurable resin, 15 to 30% by weight of a photo-curable solvent having 1 to 10% by weight of a photoinitiator and 1 to 10% by weight of a photoinitiator. The method of claim 5,
Wherein the composition is diluted to 0.1 to 10% of the total solids in the single or mixed solvent. The method of claim 5,
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 5,
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. delete The method according to claim 1,
Wherein the reaction mixture is diluted to 0.1 to 10% of the total solids in a single solvent or a mixed solvent. The method according to claim 1,
Wherein the nanosilica has a particle diameter of 1 to 40 nm and has a porous structure by a sol-gel reaction with a silane coupling agent at a pH of 4, 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 1, 3, 4 and 7,
The silane coupling agent contained in any one of the first hard coating layer, the second hard coating layer, the high refractive index coating layer and the low refractive coating layer may be 3-methacryloxypropylmethoxysilane, 3-methacryloxypropyltriethoxysilane , Vinyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N Aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, Mercaptopropyltrimethoxysilane, mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, bis (triethoxysilylpropyl) 3-isocyanatopropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) -ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) -ethyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , Para-stearyltrimethoxysilane, para-stearyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane , 3-acryloxypropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, Aminopropyltriethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3- Furnace trimethoxysilane, index matching film characterized in that it comprises at least one member selected from the group consisting of 3-chloro-ethoxy propyl triethoxy silane. The method according to claim 1 or 5,
The photocurable resin contained in any one of the first hard coating layer, the second hard coating layer, and the high refractive index coating layer may contain a hydroxy or ethylene oxide moiety and / or a hydroxyl group to maintain dispersibility with the organic / inorganic hybrid nano- (2 to 10 moles) of 1,6-hexanediol diacrylate, neopentyl glycol di (meth) acrylate, propylene oxide addition (2 to 10 moles), ethylene oxide addition (Meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-ethylhexyl glycol di , Ethylene oxide-added polyethylene glycol di (meth) acrylate, difunctional urethane acrylate, silicone urethane (meth) acrylate, and silane Cone polyester acrylate, Bisphenol A (ethylene oxide adduct 3-30 mole) di (meth) acrylate 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
And a step of sol-gel-reacting nano silica and a silane coupling agent on the upper surface of the high refractive index coating layer to form a low refraction coating layer having a porous structure,
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,
Wherein the forming of the low refraction coating layer of the porous structure comprises:
Subjecting the nanosilica to a sol-gel reaction with a silane coupling agent;
Diluting the sol-gel-reacted coating liquid to prepare a low refractive coating liquid having a porous structure for thermal curing; And
And applying a low refractive coating liquid of the porous structure to the upper surface of the high refractive index coating layer,
The low refractive index coating solution of the porous structure is prepared by mixing 1 to 15% by weight of the nano silica sol having a size of 1 to 40 nm, 10 to 30% by weight of the silane coupling agent, 10 to 45% by weight of water and 10 to 45% Gel reaction, and then diluted with a solvent.
[Chemical Formula 1]
Figure 112015116359702-pat00014

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 . 18. The method of claim 16,
Further comprising the step of forming a conductive layer on the upper surface of the low refraction coating layer of the porous structure by a sputtering deposition method using indium-tin oxide. 18. The method of claim 16,
Wherein the fluorene compound contained in the high refractive index coating layer is a compound represented by the following formula (2).
(2)
Figure 112015058217395-pat00015

(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 .) 18. The method of claim 16,
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. The method of claim 19,
Wherein the nano-metal oxide contained in the first hard coating layer is a particle diameter 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, Y 2 > O < 3 & gt ;. 18. The method of claim 16,
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. 23. The method of claim 21,
The nano-metal oxide included in the second hard coat layer may be SiO 2 , TiO 2 , ZrO 2 , Al 2 O 3 , SnO 2 , Sb 2 O 5 , Nb 2 O 3 , Y 2 O 3 ≪ / RTI > wherein the metal oxide comprises at least one metal oxide. 18. The method of claim 16,
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. 24. The method of claim 23,
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. 27. The method of claim 24,
Further comprising the step of diluting the composition contained in the high refractive index coating solution with a solvent or a mixed solvent so that the total solid content is 0.1 to 10%, and coating the coated film. 24. The method of claim 23,
The nano-metal oxide included in the high refractive index coating layer may be at least one metal 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 Wherein the index-matching film comprises an oxide. delete delete 18. The method of claim 16,
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%. The method according to any one of claims 16, 19, 21 and 23,
The silane coupling agent contained in any one of the first hard coating layer, the second hard coating layer, the high refractive index coating layer and the low refractive coating layer may be 3-methacryloxypropylmethoxysilane, 3-methacryloxypropyltriethoxysilane , Vinyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N Aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, Mercaptopropyltrimethoxysilane, mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, bis (triethoxysilylpropyl) 3-isocyanatopropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) -ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) -ethyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , Para-stearyltrimethoxysilane, para-stearyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane , 3-acryloxypropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, Aminopropyltriethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3- Method of manufacturing a furnace trimethoxysilane, 3-chloro-index characterized in that the profile tree includes one or more components selected from the group consisting of silane matching film. The method of any one of claims 19, 21 and 23,
The photocurable resin contained in any one of the first hard coating layer, the second hard coating layer, and the high refractive index coating layer may include a hydroxy or ethylene oxide moiety and may be an ethylene oxide addition (2-8 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 moles of ethylene oxide) Di (meth) acrylate, and bisphenol A epoxy acrylate. The method for producing an index-matched film according to claim 1, The method of any one of claims 19, 21 and 23,
The photocurable resin contained in any one of the first hard coating layer, the second hard coating layer, and the high refractive index coating layer may be at least one selected from the group consisting of polyfunctional acrylate, trimethylolpropane (meth) acrylate, ethylene oxide addition (3 to 15 mol) (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 6-functional urethane acrylate A method for manufacturing a 10-functional aliphatic urethane index matching film characterized in that it comprises one or more components selected from the group consisting of acrylate. 27. The method of claim 24,
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.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110499083A (en) * 2019-09-05 2019-11-26 特普罗(深圳)应用科技有限公司 A kind of display screen and its display material and preparation process of use
CN111300936A (en) * 2020-02-26 2020-06-19 江苏斯迪克新材料科技股份有限公司 High-transmittance protective film for camera
CN111300942A (en) * 2020-02-26 2020-06-19 江苏斯迪克新材料科技股份有限公司 Anti-fingerprint oil-stain-proof high-transmittance protective film

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JP2009162989A (en) 2008-01-07 2009-07-23 Hoya Corp Antireflection film and optical component having the same, interchangeable lens and imaging device
KR101405076B1 (en) * 2013-09-09 2014-07-01 (주)코이즈 Index matching film and method of manufacturing the same

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JP2009162989A (en) 2008-01-07 2009-07-23 Hoya Corp Antireflection film and optical component having the same, interchangeable lens and imaging device
KR101405076B1 (en) * 2013-09-09 2014-07-01 (주)코이즈 Index matching film and method of manufacturing the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110499083A (en) * 2019-09-05 2019-11-26 特普罗(深圳)应用科技有限公司 A kind of display screen and its display material and preparation process of use
CN111300936A (en) * 2020-02-26 2020-06-19 江苏斯迪克新材料科技股份有限公司 High-transmittance protective film for camera
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