WO2017078428A1

WO2017078428A1 - Anti-reflective film and manufacturing method therefor

Info

Publication number: WO2017078428A1
Application number: PCT/KR2016/012591
Authority: WO
Inventors: 변진석; 김헌; 김부경; 장석훈; 장영래
Original assignee: 주식회사 엘지화학
Priority date: 2015-11-04
Filing date: 2016-11-03
Publication date: 2017-05-11

Abstract

The present invention relates to an anti-reflective film and a method for manufacturing an anti-reflective film. The anti-reflective film comprises: a hard coating layer; and a low refractive layer comprising a binder resin, hollow inorganic nanoparticles dispersed in the binder resin, and solid inorganic nanoparticles, wherein the solid inorganic nanoparticles are more heavily distributed near the interface between the hard coating layer and the low refractive layer than the hollow inorganic nanoparticles. The method for manufacturing an anti-reflective film comprises the steps of: applying, on a hard coating layer, a resin composition for forming a low refractive layer, wherein the resin composition comprises a photocurable compound or (co)polymer thereof, a fluorine compound comprising a photoreactive functional group, a photoinitiator, hollow inorganic nanoparticles, and solid inorganic nanoparticles; and drying and photocuring the resin composition at a temperature of 35°C to 100°C.

Description

【Specification】

Title of the Invention

Antireflection film and process for its production.

TECHNICAL FIELD

Cross-reference with related application (s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2015- 0154591 of November 04, 2015 and Korean Patent Application No. 1 2016-0142886 of October 31, 2016, The entire contents of which are incorporated herein by reference.

The present invention relates to an antireflection film and a method of manufacturing the same, and more particularly, to an antireflection film and an antireflection film capable of simultaneously realizing high scratch resistance and antifouling property with low reflectance and high light transmittance, And a process for producing the antireflection film.

TECHNICAL BACKGROUND OF THE INVENTION

Generally, a flat panel display device such as a PDP or an LCD is equipped with an antireflection film for minimizing reflection of light incident from the outside.

As a method for minimizing the reflection of light, a method in which a filler such as an inorganic fine particle is dispersed in a resin and coated on a base film and an irregularity is imparted (ant i glare: AG coating); A method of forming a plurality of layers having different refractive indexes on a base film to utilize light interference (AR coating) or a method of using them.

In the case of the AG coating, the absolute amount of the reflected light is equivalent to a general hard coating, but a low reflection effect can be obtained by reducing the amount of light entering the eye by using light scattering through the irregularities. However, since the AG coating deteriorates the sharpness of the screen due to the surface irregularities, much research on AR coating has been conducted recently.

As the film using the AR coating, a multi-layer structure in which a hard coating layer (high refractive index layer), a low reflection coating layer, and the like are laminated on a substrate film has been commercialized. However, as described above, (Interfacial adhesion) is weakened due to the separate steps of forming the layer, and the scratch resistance is deteriorated.

In order to improve the scratch resistance of the low refraction layer previously contained in the antireflection film, a method of adding various particles of nanometer size (for example, particles of silica, alumina, zeolite, etc.) has been mainly tried. However, in the case of using nanometer-sized particles as described above, there is a limit in increasing the scratch resistance while lowering the reflectance of the low refractive layer, and the antifouling property of the surface of the low refractive layer due to the nanometer- .

Accordingly, much research has been conducted to reduce the absolute reflection amount of light incident from the outside and to improve scratch resistance of the surface as well as to improve the antifouling property. However, the degree of improvement of the physical properties is insufficient.

DISCLOSURE OF THE INVENTION

[Problem to be solved]

An object of the present invention is to provide an antireflection film capable of simultaneously realizing high scratch resistance and antifouling property while having a low reflectance and a high light transmittance and capable of enhancing the clarity of a screen of a display device. Further, the present invention relates to a production method for providing an antireflection film having the above-mentioned characteristics.

MEANS FOR SOLVING THE PROBLEMS

In this specification, the term " hard coat layer " And a low refraction layer formed on one side of the hard coating layer and including a binder resin and hollow inorganic nanoparticles dispersed in the binder resin and solid inorganic nanoparticles, An antireflection film in which 70% by volume or more of the entire solid inorganic nanoparticles exists within 50% of the total thickness of the low refraction layer from the interface.

Also, in the present specification, a resin composition for forming a low refractive index layer containing a photosetting compound or its (co) polymer, a fluorine compound containing a photo-reactive functional group, a photoinitiator, hollow inorganic nanoparticles and solid inorganic nanoparticles Applied on the hard coating layer and drying at a temperature of 35 ° C to 100 ⁰ C; And a step of photocuring the dried product of the resin composition.

Hereinafter, a method for producing an antireflection film and an antireflection film according to a specific embodiment of the present invention will be described in detail. In the present specification, a photopolymerizable compound is collectively referred to as a compound which, when irradiated with light, generates a polymerization reaction, for example, when visible light or ultraviolet light is irradiated. Further, the fluorinated compound means a compound containing at least one fluorine element in the compound.

Also, (meth) acryl [(Meth) acryl]

(Meth) acrylate (Methacryl).

In addition, (co) polymers are meant to include both co-polymers and homo-polymers.

In addition, La hollow silica particles (sili ca hol low part i cles) also is a particle in the form of a surface and / or the empty space on the inside of the silica particles present in the form of silica particles derived from the silicon compound or an ^organic, a silicon compound it means. According to one embodiment of the invention, a hard coat layer is provided; And a low refraction layer formed on one side of the hard coating layer and including a binder resin and hollow inorganic nanoparticles dispersed in the binder resin and solid inorganic nanoparticles, An antireflection film in which 70% by volume or more of the entire solid inorganic nanoparticles are present within the total thickness of the low refractive index layer within 50% from the interface can be provided.

Previously, in order to increase the scratch resistance of the antireflection film, an excessive amount of inorganic particles was added. However, the antireflection film had a limitation in enhancing the scratch resistance, and the reflectance and antifouling properties were lowered.

Thus, the inventors of the present invention proceeded with research on an antireflection film, When the expandable inorganic nanoparticles and the solid inorganic nanoparticles are distributed so as to be distinguishable from each other in the low refraction layer included in the anti-fouling film, high scratch resistance and antifouling property can be realized simultaneously with low reflectance and high light transmittance Was confirmed through experiments and the invention was completed.

Specifically, solid-form inorganic nanoparticles are mainly distributed near the interface between the hard coat layer and the low refractive layer in the low refractive index layer of the antireflection film through a specific manufacturing method described later, Type inorganic nanoparticles are mainly distributed, it is possible to achieve a lower reflectance than the actual reflectance that could be obtained by using the inorganic particles in advance, and the low refractive index layer can realize a remarkably improved scratch resistance and antifouling property together .

As described above, the low refraction layer includes a binder resin, hollow inorganic nanoparticles dispersed in the binder resin, and solid inorganic nanoparticles, and may be formed on one side of the hard coating layer, 70% by volume or more of the whole particles may exist within 50% of the total thickness of the low refraction layer from the interface between the hard coating layer and the low refraction layer.

'More than 70% by volume of the solid type inorganic nanoparticles are present in a specific region. ¹ is defined as meaning that the solid inorganic nanoparticles are mostly present in the specific region in the cross section of the low refractive layer. Specifically, More than 70% by volume of the solid type inorganic nanoparticles can be identified by measuring the volume of the entire solid type inorganic nanoparticles.

The hollow inorganic nanoparticles and the solid type inorganic. Whether or not the nanoparticles are present in the specified region determines whether or not each of the hollow inorganic nanoparticles or the solid inorganic nanoparticles exists in the specified region, and the particles existing over the boundary of the specific region are excluded .

As described above, the hollow inorganic nanoparticles may be mainly distributed on the opposite side of the interface between the hard coating layer and the low refractive layer in the low refractive layer. Specifically, 30 Wherein at least a volume percentage of the hard-inorganic nanoparticles is greater than the entirety of the solid- And at a greater distance from the interface between the low refractive layers in the thickness direction of the low refractive layers.

More specifically, from the interface between the hard coating layer and the low refraction layer, 70% by volume or more of the entire solid inorganic nanoparticles may exist within 30% of the total thickness of the low refraction layer. In addition, from the interface between the hard coating layer and the low refractive layer, at least 70% by volume of the entire hollow inorganic nanoparticles may exist in a region having a total thickness of the low refraction layer of more than 30%.

The solid inorganic nanoparticles are mainly distributed near the interface between the hard coating layer and the low refractive index layer of the antireflection film and the hollow inorganic nanoparticles are mainly distributed on the opposite side of the interface, Two or more portions or two or more layers having different refractive indexes may be formed in the refraction layer, so that the reflectance of the antireflection film may be lowered.

The specific distribution of the solid inorganic nanoparticles and the hollow inorganic nanoparticles in the low refractive index layer can be controlled by controlling the density difference between the solid inorganic nanoparticles and the enhancement inorganic nanoparticles in a specific manufacturing method described below, A photocurable resin composition for forming a low refractive index layer containing nanoparticles of the species can be obtained by controlling the drying temperature.

Specifically, the difference between the density of the solid-type inorganic nano-particles and the hollow inorganic nanoparticles 0.30 g / cuf to about 3.00 g / cu, or 0.40 g / cin ³ to 1.50 g / cirf, or 0.50 g / ciu ³ to 0.90 g / cirf. According to the manufacturing method described below, the flow between the solid inorganic nanoparticles and the hollow inorganic nanoparticles becomes more smooth in the low refraction layer formed, and the distribution may be ubiquitous. Accordingly, in the antireflection film of one embodiment of the present invention, the solid inorganic nanoparticles in the low refractive layer formed on the hard coating layer may be located closer to the hard coating layer side. The solid inorganic nanoparticles may have a density of 2.00 g / cirf to 5.00 g / cuf. Further, the hollow inorganic nano-particles may have a density of 1.50 g / cin ³ to 3.50 g / cm ^3.

The hard coat layer and the hard coat layer in the low refractive index layer of the anti- When solid inorganic nanoparticles are mainly distributed near the interface between the low refraction layers and hollow inorganic nanoparticles are mainly distributed on the opposite side of the interface, the reflectance lower than that previously obtained using inorganic particles Can be implemented. Specifically, the reflection ring film may exhibit an average reflectance of 0/7% or less in the visible light wavelength band region of 380 nm to 780 nm.

On the other hand, in the anti-reflection film of the embodiment, the low refraction layer is composed of one layer containing not less than 70% by volume of the total solid inorganic nanoparticles and not more than 70% by volume of the whole hollow inorganic nanoparticles And the first layer may be located closer to the interface between the hard coat layer and the low refractive layer than the second layer. As described above, in the low refraction layer of the antireflection film, the solid inorganic nanoparticles are mainly distributed near the interface between the hard coating layer and the low refractive layer, and the hollow inorganic nanoparticles are mainly distributed toward the opposite surface of the interface. The regions in which the solid inorganic nanoparticles and the hollow inorganic nanoparticles are mainly distributed can form an independent layer that is visually confirmed in the low refractive layer.

The solid type inorganic nanoparticle means a particle having a maximum diameter of less than 100 ran and having no void space therein.

The hollow inorganic nanoparticles mean particles having a maximum diameter of less than 200 ran and having voids on the surface and / or inside thereof.

The solid inorganic nanoparticles may have a diameter of 0.5 to 100 nm, or 1 to 30 nm.

The hollow inorganic nanoparticles may have a diameter of 1 to 200 nm, or 10 to 100 nm.

On the other hand, each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles may have one or more half (s) selected from the group consisting of a (meth) acrylate group, an epoxide group, a vinyl group and a thiol group May contain maleic functional groups. As each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles contains the above-described semi-functional functional group on the surface, The low refraction layer can have a higher degree of crosslinking, and therefore, it is possible to secure more improved scratch resistance and antifouling property.

On the other hand, the above-mentioned low refraction layer can be produced from a photocurable coating composition including a photopolymerizable compound, a fluorinated compound containing a photoactive group, a hollow inorganic nanoparticle, a solid inorganic nanoparticle, and a photoinitiator.

Accordingly, the binder resin included in the low refraction layer may include a crosslinked (co) polymer of a fluoropolymer compound including a (co) polymer of a photopolymerizable compound and a photo-reactive functional group.

The photopolymerizable compound included in the photocurable coating composition of this embodiment can form the base of the binder resin of the low refractive index layer to be graded. Specifically, the photopolymerizable compound may include a monomer containing a (meth) acrylate or a vinyl group, or a lignan. More specifically, the photosensitizing compound may include monomers or oligomers containing one or more, or two or more, or three or more (meth) acrylates or vinyl groups.

Specific examples of the monomer or oligomer containing (meth) acrylate include tri (meth) acrylate, pentaerythritol, tetra (meth) acrylate, dipentaerythritol, (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, trilene diisocyanate, xylene diisocyanate, hexamethylene methylene diisocyanate, trimethyl, (Meth) acrylate, butane di (meth) acrylate, hexaethyl (meth) acrylate, butyl (meth) acrylate, Methacrylate, or a mixture of two or more thereof, or a urethane-modified acrylate An epoxy acrylate oligomer, an ether acrylate oligomer, a dendritic acrylate oligomer, or a mixture of two or more thereof. The molecular weight of the glycerol is preferably from 1,000 to 10,000.

Specific examples of the monomer or oligomer containing the vinyl group include divinylbenzene, styrene or paramethylstyrene. The content of the photo-curable coating composition is not particularly limited, but the content of the photo-polymerizable compound in the solid content of the photo-curable coating composition, considering the mechanical properties of the low refractive index layer and the anti- May range from 5% to 80% by weight). The solids content of the photocurable coating composition refers only to components of the solids in the photocurable coating composition, excluding components of the liquid phase, such as, for example, organic solvents that may optionally be included as described below.

The photopolymerizable compound may further include a fluorine-based (meth) acrylate-based monomer or oligomer other than the monomers or oligomers described above. When the fluorine-based (meth) acrylate monomer or oligomer is further contained, the weight ratio of the fluorine-based (meth) acrylate monomer or oligomer to the monomer or oligomer containing the (meth) acrylate or vinyl group is 0.1% 10%. &Lt; / RTI >

Specific examples of the fluorine-based (meth) acrylate-based monomer or oligomer include at least one compound selected from the group consisting of the following formulas (11) to (15).

(11)

In the general formula (11), R ¹ represents a hydrogen atom or a

Alkyl group, _a is an integer of 0 to 7, and b is an integer of 1 to 3.

[Chemical Formula 12]

In the above formula (12), c is an integer of 1 to 10. [Chemical Formula 13]

In the above formula (13), d is an integer of 1 to 11.

[Chemical Formula 14]

In Formula 14, e is an integer of 1 to 5.

15]

In the above formula (15), f is an integer of 4 to 10.

On the other hand, the low refraction layer may include a portion derived from a fluorinated compound containing the photoreactive functional group.

The fluorinated compound containing the photoreactive functional group may include or be substituted with at least one photoreceptive functional group which can participate in the polymerization reaction by irradiation of light, for example by irradiation of visible light or ultraviolet light &Lt; / RTI > The < RTI ID = 0.0 > (Meth) acrylate group, an epoxide group, a vinyl group or a thiol group, which are known to be capable of participating in the polymerization reaction by irradiation. Specific examples thereof include .

Each of the fluorine-containing compounds containing the photo-reactive functional groups may have a weight average molecular weight (weight average molecular weight in terms of polystyrene measured by the GPC method) of 2, 000 to 200, 000, preferably 5, 000 to 100, 000 have.

If the weight average molecular weight of the fluorine-containing compound containing the photoreactive functional group is too small, the fluorine-containing compounds in the photocurable coating composition can not be uniformly and effectively arranged on the surface, The antifouling property of the surface of the low refraction layer is lowered and the cross-linking density of the low refraction layer is lowered, and the mechanical properties such as overall strength and scratch resistance may be deteriorated.

In addition, if the weight average molecular weight of the fluorine-containing compound containing the photo-polymerizable functional group is too high, compatibility with other components in the photocurable coating composition may be lowered, and thus the haze of the low- Or the light transmittance may be lowered, and the strength of the low refractive layer may also be lowered.

Specifically, the fluorinated compound containing the optically active compound may be selected from i) an aliphatic compound or an aliphatic cyclic compound in which at least one optically active compound is substituted, and at least one fluorine is substituted for at least one carbon; i i) a heteroaliphatic compound or heteroaliphatic ring compound substituted with at least one photo-labile functional group, at least one hydrogen substituted with a bicyclic and at least one carbon substituted with silicon; i i) a polydialkylsiloxane-based polymer (for example, a polydimethylsiloxane-based polymer) in which at least one optically male functional group is substituted and at least one fluorine is substituted for at least one silicon; iv) a polyether compound which is substituted by at least one photo-labile functional group and at least one of which is substituted by fluorine, or a mixture of i) to iv) a mixture of two or more of them or a notarized mixture thereof.

Wherein the photocurable coating composition comprises 20 to 300 parts by weight of the fluoro compound containing the photo-functional group per 100 parts by weight of the photopolymerizable compound .

When the fluorinated compound containing the photo-polymerizable functional group is added in excess to the photopolymerizable compound, the coating properties of the photocurable coating composition of the embodiment may be deteriorated or the durability or scratch resistance of the low refractive layer obtained from the photocurable coating composition You may not have sex. If the amount of the fluorine-containing compound containing the photoreactive functional group is too small as compared with the photopolymerizable compound, the low refractive layer obtained from the photocurable coating composition may not have mechanical properties such as antifouling property and scratch resistance . The fluorinated compound containing the photoreactive functional group may further contain silicon or a silicon compound. In other words, the fluorinated compound containing the photo-reactive functional group may optionally contain silicon or a silicon compound. Specifically, the silicon content of the fluorinated compound containing the photo-reactive functional group may be 0.1 to 20 wt% %. &Lt; / RTI >

The silicon contained in the fluorine-containing compound containing the photoreactive functional group can increase the compatibility with other components contained in the photocurable coating composition of the embodiment, and thus haze is generated in the finally produced refractive layer Thereby enhancing transparency. On the other hand, if the content of silicon among the fluorinated compounds containing the photo-reactive functional group is too large, compatibility between the other components contained in the photocurable coating composition and the fluorinated compound may be lowered, The low refraction layer or the antireflection film does not have sufficient transparency and antireflection performance and the antifouling property of the surface may also be deteriorated.

The low refraction layer may include 10 to 400 parts by weight of the hollow inorganic nanoparticles and 10 to 400 parts by weight of the solid inorganic nanoparticles relative to 100 parts by weight of the (co) polymer of the photopolymerizable compound.

When the content of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the low refractive index layer is excessive, the phase separation between the hollow inorganic nanoparticles and the solid inorganic nanoparticles does not occur sufficiently during the production of the low refractive index layer, And the reflectance may be increased, and the surface irregularity may be excessively generated and the antifouling property may be lowered. Further, among the low refractive layers, When the content of the inorganic nanoparticles and the inorganic nanoparticles is too small, it is difficult to locate many of the solid inorganic nanoparticles in the region near the interface between the hard coating layer and the low refractive layer. The reflectance can be greatly increased.

The low refraction layer may have a thickness of from Iran to 300 nm, or from 50 nm to 200 ran.

On the other hand, the surface of each of the hollow inorganic nanoparticles and the solid inorganic nanoparticles contained in the low refractive layer may be substituted with a reactive functional group or a silane coupling agent.

More specifically, the semi-functional group is selected from the group consisting of alcohols, amines, carboxylic acids, epoxides, imides, (meth) acrylates, nitriles, norbornenes, urepins, polyethylene glycols, And may include one or more functional groups.

The silane coupling agent may be at least one selected from the group consisting of vinylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 3-glycidoxypropyl diethoxysilane, 3-glycidoxypropyltriethoxysilane, P-styryltrimethoxysilane, 3- (meth) acryloxypropyl tri (Meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldeperoxysilane, 3-acryloxypropyltri N-2- (aminoethyl) -3-aminopropyltrimethylcisilane, N-2- (aminoethyl) Aminopropylmethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl (1, 3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimecitylsilane, 3-mercaptopropyltrimethoxysilane, bis (triepoxysilylpropyl) tetrasulfide and 3-isocyanatepropyltriethoxysilane. Or more.

On the other hand, the low refraction layer may further include a silane-based compound containing at least one kind of semi-functional group selected from the group consisting of a vinyl group and a (meth) acrylate group.

The silane-based compound containing at least one kind of at least one semi-functional group selected from the group consisting of the vinyl group and the (meth) acrylate group may have mechanical properties such as scratch resistance of the low refractive layer due to its semi- . In addition, since the low refraction layer includes a silane-based compound containing at least one kind of at least one semi-functional group selected from the group consisting of the vinyl group and the (meth) acrylate group, it is possible to secure an improved scratch resistance have.

In addition, the silane functional group or the silicon atom contained in the silane compound containing at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group may improve internal characteristics of the low refractive index layer. More specifically, it is possible to realize a lower average reflectivity as the silane functional group or the silicon atom contained in the silane-functionalized water is uniformly distributed in the low refractive index layer, and the low refractive index layer The inorganic fine particles uniformly dispersed in the inorganic fine particles uniformly bind to the photopolymerizable compound and thus the scratch resistance of the finally produced antireflection film can be improved.

As described above, the silane-based compound containing at least one kind of the semi-functional group selected from the group consisting of the vinyl group and the (meth) acrylate group has a chemical structure including the reactive functional group and the silicon atom at the same time Therefore, the characteristics of the low refractive index layer can be optimized for lowering the refractive index. Accordingly, the low refractive index layer can realize a low reflectance and a high light transmittance, and a uniform crosslink density can be secured to provide a superior abrasion resistance or scratch resistance .

Specifically, the silane-based compound containing at least one kind of the at least one semipermeable functional group selected from the group consisting of the vinyl group and the (meth) acrylate group may contain the anti-maleic functional group at 100 to 1000 g / mol equivalent have.

When the content of the reactive functional group in the silane compound containing at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group is too small, the scratch resistance and mechanical properties of the low refractive layer It may be difficult to raise the floor.

On the other hand, if the content of the semi-functional group in the silane-based compound containing at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group becomes too high, The dispersibility of the fine particles may be lowered, and the transmittance of the low refractive index layer may be lowered.

The silane compound containing at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group has a weight average molecular weight (determined by GPC method) of 100 to 5,000, or 200 to 3,000 Weight-average molecular weight in terms of polystyrene).

Specifically, the silane-based compound having at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group may be at least one kind of a semi-functional group selected from the group consisting of a vinyl group and a (meth) acrylate group At least one trialkoxysilane group having at least one alkylene group having 1 to 10 carbon atoms, and an organic functional group containing a urethane functional group. The trialkoxysilane group may be a functional group in which three alkoxy groups having 1 to 3 carbon atoms are substituted with a silicon compound.

The specific chemical structure of the silane-based compound containing at least one of the above-mentioned at least one semi-functional group selected from the group consisting of a vinyl group and a (meth) acrylate group is not limited, but vinylchlorosilane, vinyltrimethoxysilane, (3-glycidoxypropyltrimethoxysilane), 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, (Meth) acryloxypropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, P-styryltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- Silane, 3- (meth) acryloxypropylmethyldimetecysilane, 3- (Meth) acryloxypropylmethyl diethoxysilane,

(Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propyl Amine, N-phenyl-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis Propyl) tetrasulfide, 3-isocyanatepropyltriethoxysilane, or a mixture of two or more thereof.

On the other hand, as the hard coat layer, a commonly known hard coat layer can be used without any limitation.

As an example of the hard coating film, a binder resin of a photocurable resin; And a hard coating film comprising an antistatic agent dispersed in the binder resin.

The photocurable resin included in the hard coat layer is a polymer of a photocurable compound which can cause a polymerization reaction upon irradiation with light such as ultraviolet rays, and may be conventional in the art. Preferably, however, the photocurable compound may be a polyfunctional (meth) acrylate monomer or an oligomer, wherein the number of (meth) acrylate functional groups is 2 to 10, preferably 2 to 8, more preferably Is preferably from 2 to 7 in terms of ensuring the physical properties of the hard coat layer. More preferably, the photocurable compound is at least one compound selected from the group consisting of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol, (Meth) acrylate, dipentaerythritol, hepta (meth) acrylate, tripentaerythritol, hepta (meth) acrylate, trilene diisocyanate, xylene diisocyanate, hexamethylene methylene diisocyanate, trimethylolpropane tri ) Acrylate, and trimethylol propane polyethoxy tri (meth) acrylate. The antistatic agent is a quaternary ammonium salt compound; Pyridinium salts; A cationic compound having 1 to 3 amino groups; Anionic compounds such as sulfonic acid bases, sulfuric acid ester bases, phosphoric acid ester bases, and phosphonic acid bases; Amphoteric or aminosulfuric ester compounds; Non-imbalanced compounds such as imino alcohols, glycerin compounds, and polyethylene glycol compounds; Organometallic compounds of metal alkoxide compounds including tin or titanium; A metal chelate compound such as an acetylacetonate salt of the organometallic compound; Two or more compounds or polymers of such compounds; It may be a fused product of two or more of these compounds. Here, the quaternary ammonium salt compound may be a compound having at least one quaternary ammonium salt group in the molecule, and a low molecular weight or polymer type may be used without limitation. As the antistatic agent, a conductive polymer and metal oxide fine particles may also be used. Examples of the conductive polymer include an aromatic conjugated poly (paraphenylene), a heterocyclic conjugated polypyrrole, a polythiophene, an aliphatic conjugated polyacetylene, a conjugated polyaniline containing a heteroatom, a conjugated poly Phenylene vinylene), a double bond type conjugated compound which is a conjugated system having a plurality of conjugated chains in the molecule, and an electrically conductive complex in which a conjugated polymer chain is grafted or block copolymerized with a saturated polymer. Examples of the metal oxide fine particles include zinc oxide, antimony oxide, tin oxide, cerium oxide, indium tin oxide, indium oxide, aluminum oxide, antimony doped tin oxide, and aluminum doped zinc oxide.

A binder resin of the photocurable resin; And an antistatic agent dispersed in the binder resin may further include at least one compound selected from the group consisting of alkoxysilane oligomers and metal alkoxide based lignans.

The alkoxysilane-based compound may be one that is conventional in the art, but preferably includes tetrameroxysilane, tetraisonosilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ) Acryloxypropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, and glycidoxypropyltriethoxysilane, and one kind selected from the group consisting of Or more.

Further, the metal alkoxide system can be prepared by sol-gel reaction of a composition comprising a metal alkoxide compound and water. The sol-gel repellency can be performed by a method similar to the method for producing the alkoxysilane-based oligomer.

However, since the metal alkoxide compound can rapidly react with water, the sol-gel reaction can be performed by diluting the metal alkoxide compound in an organic solvent and slowly dropping water. At this time, it is preferable that the molar ratio (based on metal ion) of the metal alkoxide compound to water is adjusted within the range of 3 to 170, considering the reaction efficiency and the like.

Here, the metal alkoxide compound may be at least one compound selected from the group consisting of titanium tetra-isopropoxide, zirconium isopropoxide, and aluminum isopropoxide.

On the other hand, as another example of the hard coating film, an antiglare film having a concavo-convex shape on the surface or a film having an antiglare treatment (haze treatment or the like) on the surface can be mentioned.

For example, as an example of the hard coating film, there can be mentioned a hard coating film comprising a binder resin containing a photocurable resin and organic or inorganic fine particles dispersed in the binder resin.

The photocurable resin included in the hard coat layer may be a polymer of a photocurable compound which can cause polymerization reaction upon irradiation with light such as ultraviolet rays, and may be conventional in the art. Specifically, the photo-curing resin is a reactive acrylate comprising a urethane acrylate oligomer, an epoxide acrylate, a lygomer, a polyester acrylate, and a polyether acrylate; And dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylene propyl triacrylate, propoxylated glycine, Triacrylate, In a group of multifunctional acrylate monomers consisting of trimethyl propane ethoxy triacrylate, 1,6-nucleic acid diol diacrylate, propoxylated glycerol triacrylate, tripropylene glycol diacrylate, and ethylene glycol diacrylate, And may include at least one kind selected.

The organic or inorganic fine particles may have a particle diameter of 1 to 10.

The organic or inorganic fine particles may be organic fine particles made of acrylic resin, styrene resin, epoxide resin and nylon resin, or inorganic fine particles made of silicon oxide, titanium dioxide, indium oxide, tin oxide, zirconium oxide and zinc oxide.

The hard coating layer may have a thickness of 0.1 to 100 mm.

And a substrate bonded to the other surface of the hard coating layer. The specific type and thickness of the substrate are not limited to a great extent, and descriptions known to be used in the production of a low refractive layer or an antireflection film can be used without any limitations. On the other hand, according to another embodiment of the present invention, a resin for forming a low refractive layer including a photo-curable compound or a (co) polymer thereof, a fluorine compound containing a photo-labile functional group, a photoinitiator, hollow inorganic nanoparticles and solid inorganic nanoparticles the method comprising applying the composition to the hard coating layer and dried at a temperature of 35 ° C to 100 ⁰ C; And a step of photocuring the dried product of the resin composition.

An antireflection film of one embodiment described above can be provided through such a method for producing an antireflection film.

Specifically, the antireflection film provided by the method for producing an antireflection film is characterized in that the hollow inorganic nanoparticles and the solid inorganic nanoparticles are distributed so as to be distinguishable from each other in the low refractive layer, and accordingly, a low reflectance and a high transmittance High scratch resistance and antifouling property can be realized at the same time.

More specifically, the antireflection film comprises a hard coat layer and a hard coat layer A binder resin, and a binder resin. And a low refractive index layer including solid inorganic nanoparticles dispersed in a binder resin and solid low refractive index layers containing inorganic nanoparticles dispersed in the binder resin, More than 70% by volume of the total inorganic nanoparticles may be present.

At least 30% by volume of the hollow inorganic nanoparticles may be present at a greater distance from the interface between the hard coating layer and the low refractive layer than the entire solid inorganic nanoparticles in the thickness direction of the low refractive layer.

In addition, from the interface between the hard coating layer and the low refraction layer, 70% by volume or more of the entire solid inorganic nanoparticles may exist within 30% of the total thickness of the low refraction layer. In addition, from the interface between the hard coating layer and the low refraction layer, at least 70% by volume of the entire hollow inorganic nanoparticles may exist in a region of the total thickness of the low refraction layer of more than 3OT.

In addition, in the antireflection film provided by the method for producing an antireflection film, the low refraction layer may include a first layer containing not less than 70% by weight of the total solid inorganic nanoparticles, The first layer may be located closer to the interface between the hard coating layer and the low refractive layer than the second layer.

Wherein the low refraction layer is formed by coating a resin composition for forming an antireflection film including a photo-curable compound or a (co) polymer thereof, a fluorine compound containing a photo-reactive functional group, a photoinitiator, hollow inorganic nanoparticles and solid inorganic nanoparticles on a hard coat layer by applying and drying at a temperature of 35 ° C to 100 ° C, or 40 ° C to 80 ⁰ C it can be formed.

If the temperature for drying the resin composition for forming a low refractive index layer coated on the hard coat layer is less than 35 ° C, the antifouling property of the low refractive layer formed may be significantly lowered. If the temperature for drying the resin composition for forming a low refraction layer coated on the hard coating layer is more than 100 ° C, The phase separation between the hollow inorganic nanoparticles and the solid inorganic nanoparticles does not occur in a layered manner during the manufacturing process, so that scratch resistance and antifouling property of the low refractive layer are reduced, and the reflectance can be greatly increased.

In the course of drying the resin composition for forming a low refractive index layer coated on the hard coat layer, the difference in density between the solid inorganic nanoparticles and the hollow inorganic nanoparticles is adjusted together with the drying temperature to obtain a low refractive index layer having the above- Can be formed.

Specifically, the difference between the density of the solid-type inorganic nano-particles and the hollow inorganic nanoparticles 0.30 g / crf to 3.00 g / citf, or 0.40 g / cuf to 1.50 g / cui ^3, or 0.50 g / cin ¹ to 0.90 g / cuf. According to the manufacturing method of the embodiment, the flow between the solid inorganic nanoparticles and the hollow inorganic nanoparticles becomes more smooth in the low refractive layer, and the distribution may be ubiquitous. Accordingly, in the antireflection film provided by the manufacturing method of the embodiment, the solid inorganic nanoparticles may be located closer to the hard coating layer in the low refractive layer formed on the hard coating layer.

The solid-type inorganic nanoparticles 2.00 g / cirf to 5.00 g / cirf has a density of the hollow inorganic nano-particles may have a density, of 1.50 g / cin ³ to 3.50 g / cuf.

On the other hand, the step of drying the resin composition for forming a low refraction layer coated on the hard coat layer at a temperature of 35 ° C to 100 ° C may be performed for 10 seconds to 5 minutes, or 30 seconds to 4 minutes.

If the drying time is too short, the phase separation phenomenon between the solid inorganic nanoparticles and the hollow inorganic nanoparticles may not be caused to a large extent. On the other hand, if the drying time is too long, the formed low refraction layer may erode the hard coating layer.

On the other hand, the low refraction layer may be formed of a photo-curable compound or its (co) polymer, a blush compound containing a photo-opaque functional group, a hollow inorganic nanoparticle, &Lt; / RTI > solid type inorganic nanoparticles, and photoinitiators.

The low refraction layer can be obtained by applying the photocurable coating composition onto a predetermined substrate and photocuring the coated resultant. The specific type and thickness of the substrate are not limited to a great extent, and descriptions known to be used in the production of a low refractive layer or an antireflection film can be used without any limitations.

The methods and apparatuses commonly used in applying the photocurable coating composition can be used without limitation, including, for example, a bar coating method such as Meyer bar, a gravure coating method, a 2 roll l reverse coating method, a vacuum s lot a diep coating method, a two roll coating method and the like can be used.

The low refraction layer may have a thickness of 1 nm to 300 nm, or 50 nm to 200 nm. Accordingly, the thickness of the photocurable coating composition applied on the predetermined substrate may be from about Iran to 300 ran, or from 50 nm to 200 ran.

In the step of photo-curing the photocurable coating composition, ultraviolet rays or visible rays having a wavelength of 200 to 400 nm can be irradiated, and an exposure dose is preferably 100 to 4,000 mJ / ciii ² . The exposure time is not particularly limited, and can be appropriately changed according to the exposure apparatus used, the wavelength of the irradiation light, or the exposure dose.

In the step of photo-curing the photocurable coating composition, nitrogen purging or the like may be applied to apply nitrogen atmosphere conditions.

Specific details regarding the above-mentioned photosetting compound, hollow inorganic nanoparticles, solid inorganic nanoparticles and blended compound including a photo-reactive functional group include the above-mentioned contents of the antireflection film of the embodiment.

Each of the hollow inorganic nanoparticles and the solid inorganic nanoparticles may be contained in a composition in a colloidal state dispersed in a predetermined dispersion medium. Each of the colloidal phases including the hollow inorganic nanoparticles and the solid inorganic nanoparticles may include an organic solvent as a dispersion medium.

The hollow inorganic nano-particles and / or the inorganic nanoparticles of the photo- The content of the colloidal phase of each of the hollow inorganic nanoparticles and the solid inorganic nanoparticles can be determined in consideration of the content range of each of the solid inorganic nano-particles and the viscosity of the photo-curable coating composition. For example, The solid content of each of the hollow inorganic nanoparticles and the solid inorganic nanoparticles may be 5 wt% to 60 wt%.

Examples of the organic solvent in the dispersion medium include alcohols such as methanol, isopropyl alcohol, ethylene glycol and butanol; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; Aromatic hydrocarbons such as rubrene and xylene; Dimethylformamide. Amides such as dimethylacetamide and N-methylpyrrolidone; Esters such as ethyl acetate, butyl acetate and gamma-butylolactone; Ethers such as tetrahydrofuran and 1,4-dioxane; Or a mixture thereof.

The photopolymerization initiator may be any compound known to be usable in the photocurable resin composition. The photopolymerization initiator may be a benzophenone based compound, an acetophenone based compound, a nonimidazole based compound, a triazine based compound, a oxime based compound, Two or more kinds of these compounds may be used. The photopolymerization initiator may be used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the photopolymerizable compound. If the amount of the photopolymerization initiator is too small, the photocurable coating composition may be uncured in the photocuring step to produce a residual material. If the amount of the photopolymerization initiator is too large, the unreacted initiator may remain as an impurity or the crosslinking density may be lowered, so that the mechanical properties of the produced film may be deteriorated or the reflectance may be greatly increased.

On the other hand, the photocurable coating composition may further include an organic solvent. Non-limiting examples of the organic solvent include ketones, alcohols, acetates and ethers, and mixtures of two or more thereof. Specific examples of such an organic solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetylacetone or isobutyl ketone; Alcohols such as methanol, ethane, diacetone alcohol, n-propane, i-propanol, n-butanol, i-butanol or t-butane; Ethyl acetate, i-propyl acetate, or polyethylene glycol monomethyl ether acetate; Ethers such as tetrahydrofuran or propylene glycol monomethyl ether; Or a mixture of two or more of these.

The organic solvent may be added to the photo-curable coating composition at the time when each component contained in the photo-curable coating composition is added, or may be added to the photo-curable coating composition while the components are dispersed or mixed in an organic solvent. If the content of the organic solvent in the photocurable coating composition is too low, the flowability of the photocurable coating composition may be deteriorated, resulting in defects such as streaks on the finally produced film. In addition, when the organic solvent is added in an excess amount, the solid content is lowered, and the coating and film formation are not layered, so that the physical properties and surface characteristics of the film may be deteriorated and defects may occur during the drying and curing process. Accordingly, the photocurable coating composition may comprise an organic solvent such that the concentration of the total solids of the components involved is between 1 wt% and 50 wt%, or between 2 wt% and 20 wt%.

The hard coat layer can be used without any limitations as long as it is a material known to be usable for the antireflection film.

Specifically, the manufacturing method of the antireflection film may further include coating a substrate with a polymer resin composition for forming a hard coating layer containing a photocurable compound or a (co) polymer thereof, a photoinitiator, and an antistatic agent, and photo- , The hard coat layer can be formed through the above steps.

The components used for forming the hard coat layer are as described above with respect to the antireflection film of one embodiment.

The hard coating layer-forming polymer resin composition may further comprise at least one compound selected from the group consisting of an alkoxysilane-based oligomer and a metal alkoxide-based oligomer.

For example, a bar coating method such as Meyer bar, a gravure coating method, a 2-roll reverse coating method, a roll coating method, vacuum s lot die coating method, 2 roll l coating method and the like can be used.

In the step of photo-curing the hard coat layer-forming polymer resin composition, ultraviolet rays or visible rays having a wavelength of 200 to 400 nm can be irradiated, and an exposure dose of 100 to 4,000 mJ / crf is preferable. The exposure time is also specially And can be appropriately changed depending on the used exposure apparatus, irradiation light and wavelength or exposure dose. In the step of photo-curing the hard coat layer-forming polymer resin composition, nitrogen purging or the like may be performed to apply nitrogen atmosphere conditions.

【Effects of the Invention】

According to the present invention, there can be provided an antireflection film and a method of manufacturing the antireflection film which can simultaneously realize high scratch resistance and antifouling property while having a low reflectance and a high light transmittance, and can improve the sharpness of the screen of a display device .

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 is a cross-sectional TEM photograph of the antireflection film of Example 1. Fig.

Fig. 2 is a cross-sectional TEM photograph of the antireflection film of Example 2. Fig.

Fig. 3 is a cross-sectional TEM photograph of the antireflection film of Example 3. Fig.

4 is a cross-sectional TEM photograph of the antireflection film of Example 4. Fig.

Fig. 5 is a cross-sectional TEM photograph of the antireflection film of Example 5. Fig.

6 is a cross-sectional TEM photograph of the antireflection film of Example 6. Fig.

7 is a cross-sectional TEM photograph of the antireflection film of Comparative Example 1. Fig.

8 is a cross-sectional TEM photograph of the antireflection film of Comparative Example 2. Fig.

DETAILED DESCRIPTION OF THE INVENTION

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples. <Production Example>

Preparation Example: Preparation of Hard Coating Film

KY0EISHA salt type antistatic hard coating solution (solid content: 50% by weight, product name: LJD-1000) was coated on a triacetylcellulose film with a # 10 mayer bar

After drying at 90 ° C for 1 minute, ultraviolet light of 150 mJ /

A hard coating film having a thickness of 6 liters was prepared.

Examples 1 to 5: Preparation of antireflection film [

Examples 1 to 4

(1) Preparation of a photocurable coating composition for preparing a low refractive layer

281 parts by weight of hollow silica nanoparticles (diameter: about 50 to 60 nm, density: 1.96 g / cu, manufactured by JSC catalyst and chemicals) were added to 100 parts by weight of triacrylate (PETA) 63 parts by weight of silica nanoparticles (diameter: about 12 nm, density: 2.65 g / cif), 131 parts by weight of a first fluorine compound (X-71-1203M, ShinEtsu) 19 parts by weight of DIC) and 31 parts by weight of an initiator (Irgacure 127, manufactured by Ciba) were diluted with a solvent of methyl isobutyl ketone (MIBK) to a solid content concentration of 3% by weight.

(2) Production of low refraction layer and antireflection film

The photocurable coating composition obtained above was coated on the hard coating film of the above preparation example to a thickness of about 110 to 120 nm with a # 4 mayer bar and dried and cured at the temperature and time shown in Table 1 below. During the curing, the dried coating was irradiated with ultraviolet rays of 252 mJ / cuf under a nitrogen purge. Example 5

268 parts by weight of hollow silica nanoparticles (diameter: about 50 to 60 ran, density: 1.96 g / cirf, manufactured by JSC catalyst and chemicals) were added to 100 parts by weight of propylene triacrylate (TMPTA) Silica nano 55 parts by weight of particles (diameter: about 12 nm, density: 2.65 g / cm ¹ ), 144 parts by weight of crab-like fluorine compound (X-71-1203M, ShinEt su) DIC) and 31 parts by weight of an initiator (Irgacure 127, manufactured by Ciba) were diluted with a solvent of MIBKOiiethyl i sobutyl ketone) to a solid concentration of 3% by weight.

(2) Production of low refraction layer and antireflection film

The photocurable coating composition obtained above was coated on the hard coating film of the above preparation example to a thickness of about 110 to 120 nm with a # 4 mayer bar and dried and cured by the silver coating and time shown in Table 1 below. At the time of curing, ultraviolet rays of 252 mJ / ciif were irradiated to the dried coating under nitrogen purge. Example 6

268 parts by weight of hollow silica nanoparticles (diameter: about 50 to 60 ran, density: 1.96 g / cirf, manufactured by JSC catalyst and chemistry) were added to 100 parts by weight of propylene triacrylate (TMPTA) 70 parts by weight of solid titanium dioxide particles (diameter: about 15 nm, density: 4.3 g / cuf), 149 parts by weight of the first fluorine compound (X-71-1203M, ShinEtsu) 537, DIC) and 31 parts by weight of an initiator (Irgacure 127, manufactured by Ciba) were diluted with a solvent of MIBK (methyl i sobutyl ketone) to a solids concentration of 3% by weight.

(2) Production of low refraction layer and antireflection film

The photocurable coating composition obtained above was coated on the hard coating film of the above preparation example to a thickness of about 110 to 120 nm with a # 4 mayer bar and dried and cured by the silver coating and time shown in Table 1 below. At the time of curing, ultraviolet rays of 252 mJ / cu were irradiated to the dried coating under nitrogen purge.

[Table 1]

Example 3 80 ° C 1 min Example 4 60 ° C 2 min Example 5 60 ° C 3 min Example 6 60 ° C 1 min

&Lt; Comparative Example: Preparation of antireflection film >

Comparative Example 1

An antireflection film was prepared in the same manner as in Example 1, except that the photocurable coating composition for preparing the low refractive layer was applied and dried at room temperature (25 ° C). Comparative Example 2

63 parts by weight of the solid type silica nanoparticles used in Example 1 and 63 parts by weight of triacylate (PETA) were replaced by pentaerythritol, the photocurable coating composition for preparing a low refractive layer And an antireflection film was prepared in the same manner as in Example 1. [

The anti-reflection film obtained in the above Example and Comparative Example was subjected to the following tests.

1. Measurement of average reflectance of antireflection film

The average reflectance of the antireflection films obtained in Examples and Comparative Examples in a visible light region (380 to 780 nm) was measured using a Sol idspec 3700 (SHIMADZU) equipment.

2. Antifouling measurement

Antifouling property was measured by confirming the number of times that the antireflection film obtained in Examples and Comparative Examples was rubbed with a black name pen to a straight line having a length of 5 cm and rubbed with a nonwoven cloth. <Measurement Standard>

0: 10 times or less to be erased

?: 11 to 20 times of erasing

X: More than 20 times to erase

3. Measurement of scratch resistance

The surface of the antireflection film obtained in Examples and Comparative Examples was rubbed on the steel wool (length * length: 2.5 cm * 2.5 cm) loaded with 10 times reciprocating at a speed of 27 rpm. The maximum load at which one or less scratches of 1 cm or less observed with the naked eye was observed was measured.

4. Confirm phase separation

In the cross section of the antireflection film of FIGS. 1 to 7, it was determined that phase separation occurred when 70% by volume of the solid type inorganic nanoparticles (solid type nanosilica particles) were used within 30 nm from the hard coat layer.

[Table 2]

As shown in FIGS. 1 to 6, in the low refraction layer of the antireflection film of Examples 1 to 6, the expansion type inorganic nanoparticles and the solid type inorganic nanoparticles are phase-separated, and the solid type inorganic nanoparticles are the anti- It is found that most of the hollow inorganic nanoparticles are present on the interface between the hard coating layer and the low refractive layer of the film and that the hollow inorganic nanoparticles mostly exist on the far side from the hard coating layer.

As shown in Table 2, the antireflection films of Examples 1 to 6 exhibit a low reflectance of 0.70% or less in the visible light region, and can simultaneously achieve high scratch resistance and antifouling properties.

On the other hand, as shown in Figs. 7 and 8, it was confirmed that the hollow inorganic nanoparticles and the solid inorganic nanoparticles are not phase-separated in the low refraction layer of the antireflection film of Comparative Examples 1 and 2, and are in common.

Further, as shown in Table 2, it was confirmed that the low refraction layers of the antireflection films of Comparative Examples 1 and 2 exhibited relatively high reflectance as well as low scratch resistance and antifouling property.

Claims

Claims:

[Claim 1]

Hard coating layer; And

And a low refraction layer formed on one side of the hard coating layer and including a binder resin, hollow inorganic nanoparticles dispersed in the binder resin, and solid inorganic nanoparticles,

Wherein at least 70% by volume of the total of the solid inorganic nanoparticles is present within a total thickness of the low refraction layer of 50% from an interface between the hard coating layer and the low refraction layer.

[Claim 2]

In Item 1,

The difference between the densities of the solid-type inorganic nano-particles and the hollow inorganic nanoparticles 0.30 g / cirf to 3.00 g / cin ³ the reflection preventing film.

[Claim 3]

The method according to claim 1,

Wherein at least 30 volume of the whole of the expansion-type inorganic nano-particles is from the interface between the hard-coating layer and the low-refractive layer than the entire solid-type inorganic nanoparticles _. Refractive index layer being present at a greater distance in the thickness direction of the low refractive layer.

Claim 4

The method according to claim 1,

Wherein at least 70% by volume of the total of the solid inorganic nanoparticles is present within the total thickness of the low refraction layer of 30% from the interface between the hard coating layer and the low refractive layer.

[Claim 5]

In Item 4, Wherein at least 70% by volume of the whole hollow inorganic nanoparticles are present in an area exceeding 30% of the total thickness of the low refraction layer from the interface between the hard coating layer and the low refraction layer.

[Claim 6]

In the above,

Wherein the low refraction layer comprises a first layer containing not less than 70% by volume of the entire solid inorganic nanoparticles and a second layer containing not less than 70% by volume of the whole hollow inorganic nanoparticles,

Wherein the first layer is located closer to the interface between the hard coating layer and the low refractive layer than the second layer.

7.

In the above,

Wherein the reflection ring film exhibits an average reflectance of 0.7% or less in a visible light wavelength band region of 380 nm to 780 nm.

[8]

The method according to claim 1,

Wherein each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles has at least one kind of semi-functional group selected from the group consisting of a (meth) acrylate group, an epoxide group, a vinyl group, and a thiol group, And an antireflection film.

[Claim 9]

In Item 2,

The solid-type inorganic nano-particles have a density of 2.00 g / cm ^s to about 5.00 g / cirf,

Wherein the expandable inorganic nanoparticles have a density of 1.50 g / cui ³ to 3.50 g / cuf, Antireflection film.

[Claim 10]

The method according to claim 1,

Wherein the binder resin contained in the low refraction layer comprises a crosslinked (co) polymer of a fluoropolymer compound containing a (co) polymer of a photopolymerizable compound and a photo-reactive functional group.

[Claim 11]

11. The method of claim 10,

Wherein the low refraction layer comprises 10 to 400 parts by weight of the hollow inorganic nanoparticles and 10 to 400 parts by weight of the solid inorganic nanoparticles relative to 100 parts by weight of the (co) polymer of the photopolymerizable compound.

[12]

11. The method of claim 10,

Wherein said photopolymerizable compound comprises a monomer or oligomer comprising a (meth) acrylate or vinyl group.

[13]

11. The method of claim 10,

Wherein the fluorinated compound containing the photo-reactive functional group has a weight average molecular weight of 2, 000 to 200, 000, respectively.

14.

11. The method of claim 10,

Wherein the binder resin comprises 20 to 00 parts by weight of a fluorinated compound containing the photo-propagating functional group per 100 parts by weight of the (co) polymer of the photopolymerizable compound.

15.

11. The method of claim 10,

Wherein the photo-foaming functional group contained in the fluorinated compound is at least one member selected from the group consisting of a (meth) acrylate group, an epoxide group, a vinyl group and a thiol group.

16. The method of claim 16,

11. The method of claim 10,

The fluorinated compound containing the photoreactive functional group may be selected from the group consisting of i) an aliphatic compound or an aliphatic cyclic compound in which at least one photoreactive functional group is substituted and at least one fluorine is substituted for at least one carbon; i i) a heteroaliphatic compound or heteroaliphatic ring compound substituted with at least one photoreactive functional group, at least one hydrogen substituted with fluorine and at least one carbon substituted with silicon; i i) a polydialkylsiloxane-based polymer in which at least one photoreactive functional group is substituted and at least one fluorine is substituted for at least one silicon; And iv) a polyether compound substituted with at least one photoreactive functional group and at least one hydrogen substituted with fluorine.

17.

The method according to claim 1,

Wherein the surface of each of the hollow inorganic nanoparticles and the solid inorganic nanoparticles is substituted with a semi-functional group or a silane coupling agent.

Claim 18

The method according to claim 1,

Wherein the semi-functional group is at least one functional group selected from the group consisting of alcohols, amines, carboxylic acids, epoxides, imides, (meth) acrylates, nitriles, norbornenes, olefins, polyethylene glycols, thiols, / RTI > The silane coupling agent may be selected from the group consisting of vinylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 Glycidoxypropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, P-styryltrimethoxysilane, 3- (meth) acryloxypropyl tri Ethoxysilane, 3-

(Meth) acryloxypropyltrimethoxysilane, 3-

(Meth) acryloxypropylmethyldimethoxysilane, 3-

(Meth) acryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- Propyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- But are not limited to, N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, (Triisostearyl propyl) tetrasulfide, and 3-isocyanate propyltriethoxysilane. 2. The method according to claim 1,

Antireflection film.

[19]

The method according to claim 1,

Wherein the low refraction layer further comprises a silane compound containing at least one reactive functional group selected from the group consisting of a vinyl group and a (meth) acrylate group.

Claim 20

A resin composition for forming a low refraction layer including a photo-curable compound or its (co) polymer, a fluorine compound containing a photo-reactive functional group, a photoinitiator, hollow inorganic nanoparticles and solid inorganic nanoparticles is coated on the hard coat layer Drying at a temperature of 35 ° C to 100 ⁰ C; And photo-curing the dried product of the resin composition.

21.

21. The method of claim 20,

The hard resin composition for forming the low refractive index layer is applied on the coating layer A method of manufacturing a reflection preventing film is dried at a temperature of 40 ° C to 80 ⁰ C.

Claim 22

21. The method of claim 20,

The method of the low refractive index comprising: a resin layer-forming composition was dried at a temperature of 35 ° C to 100 ⁰ C is performed for 10 seconds to 5 minutes, and the anti-reflection film applied on the hard coating layer.

Claim 23

21. The method of claim 20,

Of the difference between the density of the solid-type inorganic nano-particles and the hollow inorganic nanoparticles 0.30 g / cin ³ to 3.00 g / citf, method for producing the anti-reflection film.

24.

24. The method of claim 23,

The solid inorganic nanoparticles have a density of 2.00 g / cirf to 5.00 g / cuf,

The hollow inorganic nanoparticles 1.50 g / cin ³ to 3.50 g / has a density of cuf, method for producing the anti-reflection film.

25. 21. The method of claim 20,

A process for producing an antireflection film, which comprises the step of coating a photopolymerizable resin composition for forming a hard coat layer containing a photocurable compound or its (co) polymeric photoinitiator and an antistatic agent on a substrate and photo-curing the same.

[26]

26. The method of claim 25,

Wherein the polymer resin composition for forming a hard coat layer further comprises at least one compound selected from the group consisting of alkoxysilane oligomers and metal alkoxide oligomers.