WO2017160027A1 - Antireflection film - Google Patents

Abstract

The present invention relates to an antireflection film comprising: a low-refraction layer and a hard coating layer, wherein the low-refraction layer includes a binder resin and inorganic fine particles dispersed in the binder resin. The binder resin includes a photopolymerizable compound and a crosslinked polymer of a polysilsesquioxane and at least two kinds of fluorine-containing compounds which include photoreactive functional groups. In the polysilsesquioxane, at least one reactive functional group is substituted.

Description

 [Specifications

 [Name of invention]

 Antireflection film

 Technical Field

 Cross Citation with Related Application (s)

 This application claims the benefit of priority based on Korean Patent Application No. 10-2016-0030393 dated March 14, 2016 and Korean Patent Application No. 10-2017-0030173 dated March 9, 2017. All content disclosed in the literature is included as part of this specification.

 The present invention relates to an anti-reflection film, and more particularly, to an anti-reflection film that can simultaneously realize high scratch resistance and antifouling property while having a low reflectance and a high light transmittance, and can increase the sharpness of a screen of a display device.

 [Technique to become background of invention]

 In general, a flat panel display device such as a PDP or 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 of dispersing fillers such as inorganic fine particles in resin and coating on a base film and imparting irregularities (ant i ^¬ glare: AG coating); There are a method of forming a plurality of layers having different refractive indices on the base film to use interference of light (ant i-ref lect ion (AR coating)) or a method of using these all together.

 Among them, in the case of the AG coating, the absolute amount of reflected light is equivalent to that of 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 unevenness. However, since the AG coating has poor screen clarity due to surface irregularities, many studies on AR coatings have recently been made.

As the film using the AR coating, a multilayer structure in which a hard coating layer (high refractive index layer), a low reflection coating layer, and the like are laminated on a base film is commercially available. However, in the method of forming a plurality of layers as described above, the adhesion between layers (interface adhesion force) is reduced by separately performing the process of forming each layer. It is weak and has a disadvantage of poor scratch resistance.

 In addition, in order to improve scratch resistance of the low refractive layer included in the antireflection film, a method of adding various particles having a nanometer size (for example, particles of silica, alumina, zeolite, etc.) has been mainly attempted. However, in the case of using the nanometer size particles as described above, there was a limit that it is difficult to simultaneously increase the scratch resistance while lowering the reflectance of the low refractive index layer, and the antifouling property of the low refractive layer surface is large due to the nanometer size particles. Degraded.

 Accordingly, many studies have been made to reduce the absolute reflection of light incident from the outside and to improve the stain resistance along with the scratch resistance of the surface. However, the improvement of the physical properties is insufficient.

 [Content of invention]

 Problem to be solved

 The present invention is to provide an anti-reflection film having a low reflectance and a high light transmittance and at the same time can implement a high scratch resistance and antifouling resistance and can increase the sharpness of the screen of the display device. [Measures of problem]

 In the present specification, a binder resin and a binder resin comprising a cross-linked polymer between a photopolymerizable compound, two or more kinds of fluorine-containing compounds including a photoreactive functional group, and a polysilsesquioxane substituted with at least one semi-functional functional group There is provided an antireflection film comprising a low refractive index layer comprising an inorganic fine particle dispersed in the; and a hard coating layer.

 Hereinafter will be described in more detail with respect to the anti-reflection film in a specific embodiment of the invention. In the present specification, the photopolymerizable compound is collectively referred to as a compound that causes polymerization reaction when irradiated with light, for example, visible light or ultraviolet light. In addition, a fluorine-containing compound means the compound containing at least 1 or more fluorine elements among the compounds.

In addition, (meth) acryl [(Meth) acryl] is acryl (acryl) and Methacrylate (methacryl) is meant to include both.

 In addition, (co) polymer is meant to include both copolymers and homopolymers.

 Also, hollow silica particles (si li ca hol low part i cles) are silica particles derived from a silicon compound or an organosilicon compound, and particles having a form in which empty space exists on the surface and / or inside of the silica particles. Means

According to one embodiment of the invention, a binder resin comprising a cross-linked polymer between a photopolymerizable compound, two or more types of habso compound including a photo-reflective functional group and a polysilsesquioxane substituted with at least one semi-functional functional group And an anti-refractive layer comprising inorganic fine particles dispersed in the binder resin; and a hard coating layer. The present inventors have conducted research on the low refractive index layer and the antireflection film, and have a photopolymerizable compound, at least two kinds of fluorine-containing compounds including photoreactive functional groups, and polysilsesquioxanes having one or more semi-functional functional groups substituted therewith (polysi l sesquioxane). Anti-reflective film comprising a low refractive index layer formed from a photocurable coating composition, can achieve a lower reflectivity and a higher light transmittance, improve wear resistance or scratch resistance, and at the same time ensure excellent antifouling properties against external contaminants It was confirmed through the experiment to complete the invention.

 It is possible to increase the sharpness of the screen of the display device of the anti-reflection film while having excellent scratch resistance and high antifouling property can be easily applied to the display device or the polarizing plate manufacturing process without great limitation.

Previously, in order to improve scratch resistance of the low refractive layer included in the antireflection film, a method of adding various particles having a nanometer size (for example, particles of silica, alumina, zeolite, etc.) has been mainly attempted. However, in the case of using the nanometer sized particles as described above, there was a limit that it is difficult to increase the scratch resistance while lowering the reflectance of the low refractive index layer, and the antifouling property of the low refractive layer surface is greatly reduced due to the nanometer sized particles. It became. On the contrary, the anti-reflection film of the embodiment has two or more kinds of fluorine-containing compounds including photoreactive functional groups in a state of being cross-linked with other components in the low refractive layer included therein, thereby providing a lower reflectance and improved light transmittance. It can have and improve the mechanical properties such as scratch resistance can secure high antifouling to the outside.

 Specifically, due to the characteristics of the fluorine element included in the fluorine-containing compound including the photo-reflective functional group, the low refractive index layer and the antireflection film may have low interaction energy with respect to liquids or organic materials, and thus the low refractive index Not only can greatly reduce the amount of contaminants transferred to the layer and the anti-reflection film, but also can prevent the transferred contaminants from remaining on the surface, and can easily remove the contaminants themselves.

 In addition, in the process of forming the low refractive index layer and the anti-reflection film, the semi-aromatic functional group contained in the fluorine-containing compound including the photo-reflective functional group has a crosslinking effect, and thus the physical durability of the low refractive layer and the anti-reflection film, It can improve scratch resistance and thermal stability.

 In particular, by using two or more kinds of the fluorine-containing compound containing the photo-reflective functional group, it is possible to obtain a higher synergistic effect than when using a fluorine-containing compound containing one type of photo-reflective functional group, specifically higher physical Surface properties such as improved antifouling and slip resistance can be realized while securing durability and scratch resistance, and the large-area coating can be easily performed during the formation of the low refractive index layer and the anti-reflection film to increase productivity and efficiency of the final product manufacturing process. Can be.

In addition, the anti-reflection film of the embodiment exhibits a relatively low reflectance and an overall haze value to implement high light transmittance and excellent optical properties. Specifically, the total haze of the anti-reflection film may be 0.45% or less, or 0.05 to 0.45% or less, or 0.25% or less, or 0.1% to 0.25 or less. In addition, the antireflection film has an average reflectance of 2.0% or less, or 1.5% or less, or 1.0% or less, or 1.0% to 0.1%, or 0.40% to 0.80%, in the visible light wavelength range of 380 nm to 780 nm, or 0.54% to 0.69% It can have an average reflectance.

 On the other hand, two or more kinds of fluorine-containing compounds containing the photo-banung functional group may be classified according to the range of fluorine-containing, specifically, two or more kinds of fluorine-containing compounds containing the photo-banung functional group has a fluorine-containing range virtually depending on the type Do.

 Due to the properties resulting from the fluorine-containing compound having a higher fluorine content among two or more kinds of fluorine-containing compounds including the photo-banung functional groups, the low refractive index layer and the anti-reflection film may have improved antifouling properties while ensuring lower reflectance. .

 In addition, the fluorine-containing compound having a lower fluorine content among the two or more kinds of fluorine-containing compounds including the photo-reflective functional group may further improve compatibility with other components included in the low refractive layer, and further, the low refractive layer and The antireflective film may have higher physical durability and scratch resistance and have homogeneous surface properties and high surface slip properties with improved antifouling properties.

 More specifically, the two or more kinds of fluorine-containing compounds including the photo-banung functional group may be divided based on the content of 25% by weight of the fluorine included. The content of fluorine contained in each of the fluorine-containing compounds including the photo-banung functional group can be confirmed through a conventionally known analysis method, for example, an IC [Ion Chromatograph] analysis method.

 As a specific example, two or more kinds of the fluorine-containing compound including the photoreactive functional group may include a U-fluorine-containing compound including a photoreactive functional group and 25 to 60% by weight of fluorine.

 In addition, the two or more kinds of fluorine-containing compounds including the photo-banung functional group may include a second fluorine-containing compound containing the photo-banung functional group and containing fluorine in an amount of 1% by weight or more and less than 25% by weight.

The low refractive index layer comprises 1) a first fluorine-containing compound containing 25 to 60% by weight of fluorine and a photoreactive functional group, and 2) a fluorine in an amount of 1% by weight or more and less than 25% by weight. As the inclusion includes a moiety derived from a fluorine-containing compound, one kind of photoreactive functional group is included. Compared with the case of using a fluorine-containing compound, it is possible to achieve surface properties such as improved antifouling and slip resistance while ensuring higher physical durability and scratch resistance.

 Specifically, due to the first fluorine-containing compound having a higher fluorine content, the low refractive index and anti-reflective film may have improved antifouling properties while ensuring a lower reflectance, and a second fluorine-containing compound having a lower fluorine content Due to the low refractive index layer and the anti-reflection film may have a higher physical durability and scratch resistance and have a homogeneous surface properties and high surface slip properties with improved antifouling properties.

 The difference in fluorine content between the C1 fluorine-containing compound and the second fluorine-containing compound may be 5% by weight or more. As the difference in the fluorine content between the first fluorine-containing compound and the second fluorine-containing compound is 5% by weight or more, or 10% by weight or more, the effects of the above-described type 1 fluorine compound and crab fluorine-containing compound are higher. It can be maximized, and accordingly, a synergistic effect of using the first fluorine-containing compound and the bifluorine-containing compound together can also be enhanced.

 The first and second terms are used to specify the components to be referred to, and thus are not limited to the order or importance.

 Although the weight ratio between the first fluorine-containing compound and the second fluorine-containing compound is not particularly limited, in order that the low refractive index layer and the antireflection film may have homogeneous surface properties together with more improved scratch resistance and antifouling property, The weight ratio of the second fluorine-containing compound to the first fluorine-containing compound may be 0.01 to 0.5, preferably 0.01 to 0.4.

Each of the two or more kinds of fluorine-containing compounds including the photoreactive functional group may include or be substituted with one or more photoreactive functional groups, and the photoreactive functional group is polymerized by irradiation of light, for example, by irradiation of visible light or ultraviolet light. It means a functional group that can participate in reaction. The photoreactive functional group may include various functional groups known to be able to participate in a polymerization reaction by irradiation of light, and specific examples thereof include (meth) acrylate groups, epoxide groups, vinyl groups (Vinyl), or thiol groups ( Thiol) is mentioned. Each of the two or more kinds of fluorine-containing compounds including the photoreactive functional group is from 2, 000 to 200, 00, preferably from 5, 000 to 100,000 (weight average molecular weight in terms of polystyrene measured by GPC method). Can have

 If the weight average molecular weight of the fluorine-containing compound including the photo-reflective functional group is too small, the fluorine-containing compounds may not be uniformly and effectively arranged on the surface of the low refractive layer, and thus may be located therein. The antifouling property of the surface of the film is lowered and the crosslinking density inside the low refractive index layer and the antireflection film is lowered, so that mechanical properties such as overall strength and scratch resistance can be lowered.

 In addition, when the weight average molecular weight of the fluorine-containing compound including the photo-reflective functional group is too high, the haze of the low refractive index layer and the antireflection film may be increased or the light transmittance may be lowered, and the strength of the low refractive index layer and the antireflection film may also be Can be degraded.

 Specifically, the fluorine-containing compound including the photo-cyclic functional group is i) an aliphatic compound or aliphatic ring compound in which at least one photo-cyclic functional group is substituted, at least one fluorine is substituted in at least one carbon; i i) a heteroaliphatic compound or a heteroaliphatic ring compound substituted with one or more photocyclic functional groups, at least one hydrogen substituted with fluorine, and one or more carbons substituted with silicon; i i i) a polydialkylsiloxane polymer (eg, a polydimethylsiloxane polymer) in which at least one photoreactive functional group is substituted and at least one fluorine is substituted in at least one silicon; iv) a polyether compound substituted with at least one photoreactive functional group and at least one hydrogen is substituted with fluorine, or a mixture of two or more of the above i) to iv) or a copolymer thereof.

 The binder resin included in the low refractive layer may include a crosslinked polymer between two or more kinds of fluorine-containing compounds including a photopolymerizable compound and a photoreactive functional group.

The crosslinked polymer may contain two or more kinds of fluorine-containing fluorine-containing functional groups based on 100 parts by weight of a portion derived from the photopolymerizable compound. 20 to 300 parts by weight of a portion derived from the compound. The content of two or more kinds of fluorine-containing compounds including the photoreactive functional groups relative to the photopolymerizable compounds is based on the total content of two or more kinds of fluorine-containing compounds including the photoreactive functional groups.

 When the fluorine-containing compound including the photoreactive functional group is added in an excessive amount compared to the photopolymerizable compound, the low refractive index may not have sufficient durability or scratch resistance. In addition, when the amount of the fluorine-containing compound containing the photo-banung functional group compared to the photopolymerizable compound is too small, the low refractive index layer may not have a mechanical property such as layered antifouling or scratch resistance.

 The fluorine-containing compound including the photoreactive functional group may further include silicon or a silicon compound. In other words, the ambleo compound containing the photoreactive functional group may optionally contain a silicon or silicon compound therein, specifically, the content of silicon in the fluorine-containing compound containing the photoreactive functional group is from 0.01% by weight to 20% by weight May be ¾.

 The content of the silicon or silicon compound included in each of the fluorine-containing compounds including the photoreactive functional group may also be confirmed through a commonly known analysis method, for example, an ICP [Inductively Coupled Plasma] analysis method. Silicon contained in the fluorine-containing compound including the photo-banung functional group may increase compatibility with other components included in the photocurable coating composition of the embodiment, and thus haze is generated in the low refractive layer to be manufactured. It can prevent a role to increase the transparency, and also improve the scratch resistance of the surface of the low refractive index layer or the anti-reflection film to be manufactured to improve scratch resistance.

 On the other hand, when the content of silicon in the fluorine-containing compound including the photo-reflective functional group is too large, the low refractive index layer or the antireflection film does not have a sufficient light transmittance or antireflection performance and the antifouling property of the surface may also be reduced.

On the other hand, as described above, the binder resin included in the low refractive index layer is a photopolymerizable compound, two or more kinds of fluorine-containing compounds including a photoreactive functional group and polysilsesquioxane substituted with at least one semi-functional functional group (polysi sesquioxane ) Cross-linked polymers of the liver. More specifically, the photocurable coating composition for forming the low refractive layer includes a polysilsesquioxane substituted with at least one semi-functional functional group together with at least two fluorine-containing compounds including the photopolymerizable compound and the photo-functional functional group described above. can do.

 The polysilsesquioxane substituted with at least one semi-functional functional group has a semi-functional functional group on the surface thereof to increase mechanical properties of the low refractive layer, for example, scratch resistance, and is known as silica, alumina, zeolite, and the like. Unlike the case of using fine particles, the alkali resistance of the low refractive index layer can be improved, and the appearance characteristics such as average reflectance and color can be improved.

 The polysilsesquioxane may be represented by (! ^; ^ (Where n is 4 to 30 or 8 to 20), and may have various structures such as random, ladder, cage, and partial cage. Preferably, in order to increase the physical properties and quality of the low refractive index layer and the anti-reflection film, a polysilsesquioxane in which at least one semi-functional functional group is substituted with at least one reactive functional group and a polyhedron having a cage structure Oligomeric silsesquioxane (Polyhedral Ol igomeric Si l sesquioxane) can be used.

 Also, more preferably, the polyhedral oligomeric silsesquioxane having one or more functional groups and a cage structure may include 8 to 20 silicon in the molecule.

 In addition, at least one or more of the silicones of the polyhedral oligomeric silsesquioxane having a cage structure may be substituted with semi-functional functional groups, and the above-mentioned non-reactive functional groups may be substituted with silicones not substituted with the semi-functional functional groups. Can be substituted.

As at least one of the silicones of the polyhedral oligomeric silsesquioxane having the cage structure is substituted with a semi-ung functional group, the mechanical properties of the low refractive index layer and the binder resin may be improved, and the remaining silicones As the non-banung functional group is substituted, the molecular structural steric hinderance appears, thereby significantly reducing the frequency or probability of exposing the siloxane bond (-Si-0-) to the outside, thereby reducing the low refractive index layer and the binder. The alkali resistance of resin can be improved.

 The reactive functional groups substituted in the polysilsesquioxane are alcohols, amines, carboxylic acids, epoxides, imides, (meth) acrylates, nitriles, norbornenes, olepins [al ly, cycloalkenyl ( cycloalkenyl) or vinyldimethylsilyl, etc.], polyethyleneglycol, thiol and vinyl groups, and may include one or more functional groups, preferably epoxide or (meth) acrylate.

More specific examples of the semi-functional group include (meth) acrylate, alkyl (meth) acrylate having 1 to 20 carbon atoms, cycloalkyl epoxide having 3 to 20 carbon atoms, and alkyl cycloalkane having 1 to 10 carbon atoms ( cyc loalkane) epoxide. The alkyl (meth) acrylate means that the other part of ¹ alkyl 'which is not bonded with (meth) acrylate is a bonding position, and the cycloalkyl epoxide is the other part of cycloalkyl ¹ which is not bonded with epoxide This means that the bonding position, ^' alkyl cycloalkane epoxide means that the other portion of the' alkyl 'that does not bond with the cycloalkane epoxide is the binding position.

 On the other hand, the polysilsesquioxane substituted with at least one reactive functional group is a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclonuclear group having 6 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms, in addition to the aforementioned reactive functional group. One or more unbanung functional groups selected from the group consisting of may further comprise one or more. As such, the reactive functional group and the non-banung functional group are substituted on the surface of the polysilsesquioxane, and thus, a siloxane bond (-Si-0-) is formed in the molecule in the polysilsesquioxane in which the semi-maleic functional group is substituted at least one. While being positioned so as not to be exposed to the outside, the alkali resistance and scratch resistance of the low refractive index layer and the antireflection film may be further improved.

Examples of the polyhedral oligomeric silsesquioxane (POSS) having one or more such semi-functional functional groups and having a cage structure include TMP Diol lsobutyl POSS, Cyclohexanediol Isobutyl POSS, 1, 2- Propanediol Isobutyl POSS, 0cta (3-hydroxy-3 methylbutyldimethylsioxy) POSS substituted with at least one alcohol such as POSS; Aminopropyl Isobutyl POSS, Aminopropyl Isooctyl POSS,

POSS substituted with at least one amine such as Aminoethylaminopropyl Isobutyl POSS, NS Phenyl aminopropyl POSS, N_ Methylaminopropyl Isobutyl POSS, OctaAmmonium POSS, AminophenylCyclohexyl POSS, Aminophenyl Isobutyl POSS; POSS in which at least one carboxylic acid is substituted, such as Maleamic Acid-Cyclohexyl POSS, Maleamic Acid-Isobutyl POSS, Octa Maleamic Acid POSS; POSS substituted with at least one epoxide such as EpoxyCyc 1 ohexy 11 sobuty 1 POSS, Epoxycyclohexyl POSS, Glycidyl POSS, GlycidylEthyl POSS, Glycidyl Isobutyl POSS, Glycidyllsooctyl POSS; POSS maleimide Cyc 1 ohexy 1, POSS Maleimide Isobutyl, and the like; Acrylolsobutyl POSS, (Meth) acryl Isobutyl POSS, (Meth) acrylate Cyc 1 ohexy 1 POSS, (Meth) acrylate Isobutyl POSS, (Meth) acrylate Ethyl POSS, (Meth) acrylEthyl POSS, (Meth) acrylate Isooctyl POSS, (Meth) POSS substituted with one or more (meth) acrylates such as acryl Isooctyl POSS, (Meth) acrylPhenyl POSS, (Meth) acryl POSS, and Acrylo POSS; POSS in which at least one nitrile group such as Cyanopropyl Isobutyl POSS is substituted; POSS in which at least one norbornene group such as Norbornenyl ethyl Ethyl POSS, Norbornenyl ethyl Isobutyl POSS, Norbornenyl ethyl Di Si lan is substituted with sobuty 1 POSS and Tr isnorbornenyl Isobutyl POSS; POSS substituted with at least one vinyl group such as Allyllsobutyl POSS, MonoVinyllsobutyl POSS, OctaCyclohexenyldimethylsilyl POSS, OctaVinyldimethylsilyl POSS, OctaVinyl POSS; POSS substituted with at least one olefin such as Allyllsobutyl POSS, MonoVinyllsobutyl POSS, OctaCyclohexenyldimethylsilyl POSS, OctaVinyldimethylsilyl POSS, OctaVinyl POSS; POSS substituted with PEG of 5 to 30 carbon atoms; Or P0SS substituted with at least one thiol group such as Mercaptopropyl Isobutyl POSS or Mercaptopropyl Isooctyl POSS; Etc. can be mentioned.

The crosslinked polymer between the photopolymerizable compound, two or more kinds of fluorine-containing compounds including a photoreactive functional group, and a polysilsesquioxane in which at least one semi-functional functional group is substituted is the photopolymerizable polymer. It may comprise 0.5 to 60 parts by weight, or 1.5 to 45 parts by weight of polysilsesquioxane substituted with at least one semi-functional functional group relative to 100 parts by weight of the compound.

When the content of the portion derived from the binder resin of the photo-polymerization-derived Clarity over which the anti-male functionalities 1 substituted polysilsesquioxane (pol _ys il _sesqu i _oxane) from the compound is too small, the low refractive index layer It may be difficult to secure enough scratch resistance. In addition, even when the content of the portion derived from the polysilsesquioxane (polysi l sesquioxane) in which the semi-ungseong functional group is substituted at least one of the portion derived from the photopolymerizable compound of the binder resin, Transparency of the antireflection film may be lowered, and scratchability may be rather lowered.

 On the other hand, the photopolymerizable compound forming the binder resin may include a monomer or oligomer containing a (meth) acrylate or a vinyl group. Specifically, the photopolymerizable compound may include a monomer or oligomer containing (meth) acrylate or vinyl group of one or more, two or more, or three or more.

Specific examples of the monomer or oligomer containing the (meth) acrylate include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dapentaerythritol penta (meth) acrylate, Dipentaerythrione nucleated (meth) acrylate, Tripentaerythrione hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, nucleamethylene diisocyanate, trimethylolpropane tri (meth) acrylate, trimethyl Allpropane polyethoxy tri (meth) acrylate, trimethyl to propane trimethacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, nuxaethyl methacrylate, butyl methacrylate or two or more combinations thereof Or urethane modified acrylate oligomer, epoxy Id acrylate oligomers, ether acrylate hitting the bots, hitting the dendritic acrylate may be mentioned hairpins, or combinations of two or more common compound. Where the oligomer The molecular weight is preferably 1,000 to 10,000.

 Specific examples of the monomer or oligomer containing the vinyl group include divinylbenzene, styrene or paramethylstyrene.

 Although the content of the portion derived from the photopolymerizable compound in the binder resin is not particularly limited, the content of the photopolymerizable compound is 10% by weight to 80 in consideration of mechanical properties of the low refractive index layer or the antireflection film to be manufactured. Weight percent.

 On the other hand, the inorganic fine particles refers to inorganic particles having a diameter of nanometer or micrometer unit.

 Specifically, the inorganic fine particles may include solid inorganic nanoparticles and / or hollow inorganic nanoparticles.

 The solid inorganic nanoparticle refers to a particle having a maximum diameter of 100 nm or less and having no empty space therein.

 In addition, the hollow inorganic nanoparticles mean a particle having a maximum diameter of 200 nm or less and having a void space on the surface and / or inside thereof.

 The solid inorganic nanoparticles may have a diameter of 0.5 to 100 nm, or 1 to 50 nm.

 The hollow inorganic nanoparticles may have a diameter of 1 to 2 (X) nm, or 10 to 100 nm.

 On the other hand, each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles are at least one half selected from the group consisting of (meth) acrylate group, epoxide group, vinyl group (Vinyl) and thiol group (Thiol) on the surface It may contain male functional groups. As the solid inorganic nanoparticles and the hollow inorganic nanoparticles each contain the above-mentioned semi-functional functional groups on the surface, the low refractive index layer may have a higher degree of crosslinking. Therefore, it is possible to secure more scratch resistance and stain resistance.

As the hollow inorganic nanoparticles, those whose surfaces are coated with a fluorine compound may be used alone, or may be used in combination with the hollow inorganic nanoparticles whose surfaces are not coated with a fluorine compound. Of the hollow inorganic nanoparticles Coating the surface with a fluorine-based compound can lower the surface energy, thereby increasing the durability and scratch resistance of the low refractive layer. A particle coating method or a polymerization method commonly known as a method of coating a fluorine compound on the surface of the hollow inorganic nanoparticles can be used without great limitation. For example, the hollow inorganic nanoparticles and the fluorine compound may be used as a catalyst for water and By sol-gel reaction in the presence of the fluorine-based compound can be bonded to the surface of the hollow inorganic nanoparticles through hydrolysis and condensation reaction.

 Specific examples of the hollow inorganic nanoparticles include hollow silica particles. The hollow silica may include predetermined functional groups that are most ringed on the surface in order to be more easily dispersed in an organic solvent. Examples of the organic functional group that can be substituted on the surface of the hollow silica particles are not particularly limited, and for example, (meth) acrylate group, vinyl group, hydroxy group, amine group, allyl group (al lyl), epoxy group, hydroxy group, isocyanate group, An amine group or fluorine may be substituted on the hollow silica surface.

 The binder resin of the low refractive layer may include 10 to 600 parts by weight of the inorganic fine particles based on 100 parts by weight of the photopolymerizable compound. When the inorganic fine particles are added in an excessive amount, scratch resistance or abrasion resistance of the coating film may decrease due to a decrease in the content of the binder.

 On the other hand, the low refractive index layer may be obtained by applying a photocurable coating composition comprising at least two kinds of the habso compound and a photopolymerizable compound containing a semi-ungseong functional group on a predetermined substrate and photocuring the applied result. The specific kind or thickness of the substrate is not particularly limited, and a substrate known to be used in the manufacture of a low refractive index layer or an antireflection film can be used without any significant limitation.

As mentioned above; The low refractive index layer obtained from the photocurable coating composition containing two or more kinds of fluorine-containing compounds containing photoreactive functional groups can realize low reflectivity and high light transmittance, improve wear resistance or scratch resistance, and at the same time have excellent antifouling properties against external contaminants. It can be secured. Two or more kinds of fluorine-containing compounds containing the photo-banung functional group The low refractive index layer prepared from the photocurable coating composition may have low interaction energy with respect to the organic material, thereby greatly reducing the amount of contaminants transferred to the low refractive index layer and the antireflective film, as well as transferred contamination. The phenomenon that the material remains on the surface can be prevented, and the contaminant itself can be easily removed.

 As the photocurable coating composition forming the low refractive index layer contains two or more kinds of fluorine-containing compounds containing photoreactive functional groups, a higher synergistic effect is obtained than in the case of using one type of photosol-modified functional group-containing fluorine-containing compounds. In detail, the low refractive index layer of the embodiment can realize surface characteristics such as improved antifouling property and slip resistance while securing higher physical durability and scratch resistance.

 The photocurable coating composition may include 20 to 300 parts by weight of two or more kinds of fluorine-containing compounds including the photobanung functional group based on 100 parts by weight of the photopolymerizable compound. The content of the at least two types of fluorine-containing compounds including the photoreactive functional groups relative to the photopolymerizable compounds is based on the total content of at least two kinds of the fluorine-containing compounds including the photoreactive functional groups.

 When an excess amount of the fluorine-containing compound including the photoreactive functional group is added to the photopolymerizable compound, the coating property of the photocurable coating composition may be deteriorated or the low refractive layer may not have sufficient durability or scratch resistance. In addition, when the amount of the fluorine-containing compound including the photoreactive functional group relative to the photopolymerizable compound is too small, the low refractive index layer obtained from the photocurable coating composition may not have mechanical properties such as layered antifouling or scratch resistance. have.

 The ambleo compound including the photobanung functional group may further include silicon or a silicon compound. That is, the fluorine-containing compound including the photo-ungung functional group may optionally contain a silicon or silicon compound, specifically, the content of silicon in the fluorine-containing compound containing the photo-banung functional group is 0.01% by weight to 20% by weight May be%.

Silicon contained in each of the fluorine-containing compounds including the photo-banung functional group Or the content of silicon compounds is also commonly known analytical methods, for example

It can be confirmed by ICP [Inductively Coupled Pl asma] analysis method. Silicon contained in the fluorine-containing compound including the photoreactive functional group can increase the compatibility with other components included in the photocurable coating composition of the embodiment, and accordingly, haze is generated in the final refractive layer It can prevent the role of increasing the transparency, and also improve the slip resistance of the surface of the low refractive index layer or the anti-reflection film to be manufactured to improve the scratch resistance.

 On the other hand, when the content of silicon in the fluorine-containing compound containing the photo-banung functional group is too large, the compatibility between the other component and the fluorine-containing compound included in the photocurable coating composition of the embodiment may be rather reduced, and thus the final manufacturing The low refractive index layer or the antireflection film does not have a sufficient light transmittance or antireflection performance, and the antifouling property of the surface may also be degraded.

 The photopolymerizable compound included in the photocurable coating composition may form a binder resin of a low refractive index layer prepared. Specifically, the photopolymerizable compound may include a monomer or oligomer including a (meth) acrylate or a vinyl group. Specifically, the photopolymerizable compound may include a monomer or oligomer containing (meth) acrylate or vinyl group of one or more, two or more, or three or more.

Specific examples of the monomer or oligomer containing the (meth) acrylate include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythrione nucleated (meth) acrylate, Tripentaerythrione hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, nucleated methylene diisocyanate, trimethylolpropane tri (meth) acrylate ᅳ trimethyl Allpropane polyhydroxy tri (meth) acrylate, trimethyl to propane trimethacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, nuxaethyl methacrylate, butyl methacrylate or two or more combinations thereof Or urethane modified acrylate oligomer Foxside acrylate Oligomers, etheracrylate oligomers, dendritic acrylate oligomers, or combinations of two or more thereof. At this time, the molecular weight of the oligomer is preferably 1,000 to 10,000.

 Specific examples of the monomer or oligomer containing the vinyl group include divinylbenzene, styrene or paramethylstyrene.

 Although the content of the photopolymerizable compound in the photocurable coating composition is not particularly limited, the content of the photopolymerizable compound in the solid content of the photocurable coating composition in consideration of the mechanical properties of the low refractive index layer or the anti-reflection film to be produced finally Silver may be from 10% by weight to> 80% by weight. Solid content of the photocurable coating composition means only the components of the solid except the components of the liquid, for example, an organic solvent that may be optionally included as described below in the photocurable coating composition.

 In addition, the photocurable coating composition may include a polysilsesquioxane (polysisessesoxane) in which at least one semi-functional group is substituted. It includes all of the above-described information on the polysilsesquioxane in which the semi-ungsung functional group is substituted with at least one.

^{'' In} the case of using fine particles such as silica, alumina, zeolite, and the like previously known, the film or coating film is simply increased in strength, whereas the polysilsesquioxane in which the semi-functional functional group is substituted with one or more low In addition to increasing the strength of the refractive layer or the antireflection film, crosslinking can be formed over the entire region of the film, thereby improving the surface strength and the scratch resistance.

 More specific examples of the semi-functional group include (meth) acrylate, alkyl (meth) acrylate having 1 to 20 carbon atoms, cycloalkyl epoxide having 3 to 20 carbon atoms, and alkyl cycloalkane having 1 to 10 carbon atoms ( cycloalkane) epoxides.

The alkyl (meth) acrylate means that the other part of ¹ alkyl 'which is not bonded with (meth) acrylate is a bonding position, and the cycloalkyl epoxide is the other part of' cycloalkyl 'which is not bonded with epoxide Is the position of the bond, and the alkyl cycloalkane epoxide The other moiety of ¹ alkyl 'that does not bind to cycloalkane epoxide is the binding position.

 The photocurable coating composition may include 0.5 to 60 parts by weight of polysilsesquioxane, or 1.5 to 45 parts by weight, in which at least one semi-functional functional group is substituted with respect to 100 parts by weight of the photopolymerizable compound.

 On the other hand, the photocurable coating composition may further include inorganic fine particles. The inorganic fine particles may mean inorganic particles having a diameter of nanometers or micrometers, and specifically, the inorganic fine particles may include solid inorganic nanoparticles and / or hollow inorganic nanoparticles.

 In addition, the photocurable coating composition is the photopolymerizable compound

10 to 600 parts by weight of the inorganic fine particles may be included based on 100 parts by weight.

 More specific matters about the inorganic fine particles include all of the above-described contents with respect to the low refractive layer.

 In addition, the photocurable coating composition may further include a photoinitiator. Accordingly, the photopolymerization initiator may remain in the low refractive layer manufactured from the photocurable coating composition.

 The photopolymerization initiator may be used without any limitation as long as it is a compound known to be used in the photocurable resin composition, and specifically, a benzophenone compound, acetophenone compound, biimidazole compound, triazine compound, oxime compound, or the like. Two or more kinds thereof can be used. With respect to 100 parts by weight of the photopolymerizable compound, the photopolymerization initiator may be used in an amount of 1 to 100 parts by weight. If the amount of the photopolymerization initiator is too small, an uncured material remaining in the photocuring step of the photocurable coating composition may be issued. If the amount of the photopolymerization initiator is too large, the non-aqueous initiator may remain as an impurity or have a low crosslinking density, thereby lowering mechanical properties or reflectance of the film.

In addition, the photocurable coating composition may further include an organic solvent. Non-limiting examples of the organic solvents include ketones, alcohols, acetates and ethers, or combinations of two or more thereof. Specific examples of such organic solvents include ketones such as methyl ethyl kenone, methyl isobutyl ketone, acetylacetone or isobutyl ketone; Alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, or t-butanol; Acetates such as ethyl acetate, i-propyl acetate, or polyethylene glycol monomethyl ether acetate; Ethers such as tetrahydrofuran or propylene glycol monomethyl ether; Or these and 2 or more types of mixtures are mentioned.

 The organic solvent may be included in the photocurable coating composition while being added at the time of mixing each component included in the photocurable coating composition or in the state in which each component is dispersed or mixed in the organic solvent. If the content of the organic solvent in the photocurable coating composition is too small, defects may occur, such as streaks in the resulting film due to the flowability of the photocurable coating composition is reduced. In addition, when the excessive amount of the organic solvent is added, the solid content is lowered, coating and film formation are not divided, the physical properties and surface properties of the film may be lowered, and defects may occur in the drying and curing process. Accordingly, the photocurable coating composition may include an organic solvent such that the concentration of the total solids of the components included is 1% by weight to 50% by weight, or 2 to 20% by weight.

 On the other hand, the method and apparatus conventionally used to apply the photocurable coating composition can be used without particular limitation, for example, bar coating method such as Meyer bar, gravure coating method, 2 rol l reverse coating method, vacuum Slot die coating and 2 roll coating can be used.

In the step of photocuring the photocurable coating composition may be irradiated with ultraviolet light or visible light having a wavelength of 200 ~ 400nm, the exposure amount is preferably 100 to 4,000 mJ / cin ² when irradiated. Exposure time is not specifically limited, either, According to the exposure apparatus used, wavelength of an irradiation light, or exposure amount, it can change suitably.

 In addition, in the step of photocuring the photocurable coating composition may be nitrogen purging to apply nitrogen atmospheric conditions.

On the other hand, the hard coating layer is a large limitation to the known hard coating bug Can be used without

 As an example of the said hard coat layer, the hard coat layer containing the binder resin containing photocurable resin, and the organic or inorganic fine particle disperse | distributed to the said binder resin;

 The photocurable resin included in the hard coat layer is a polymer of a photocurable compound that may cause polymerization reaction when irradiated with light such as ultraviolet rays, and may be conventional in the art. Specifically, the photocurable resin is a semi-cyclic acrylate oligomer group consisting of urethane acrylate oligomer, epoxide acrylate oligomer, polyester acrylate, and polyether acrylate; And dipentaerythritol, nuxaacrylate ᅳ dipentaerythroxy, hydroxy pentaacrylate, pentaerythri tetraacrylate, pentaerythri triacrylate, trimethylene propyl triacrylate, propoxylated glycerol. Multifunctional acryl consisting of triacrylate, trimethylpropane ethoxy triacrylate, 1,6-nucleic acid diol diacrylate, propoxylated glycerol triacrylate, tripropylene glycol diacrylate, and ethylene glycol diacrylate It may contain one or more selected from the group of the rate monomers.

 The organic or inorganic fine particles are not particularly limited in particle size, for example, the organic fine particles may have a particle size of 1 to 10 / m, the inorganic particles may have a particle size of 1 ran to 500 ran, or lnm to 300 ran Can be. The particle size of the organic or inorganic fine particles may be defined as a volume average particle diameter.

 In addition, specific examples of the organic or inorganic fine particles included in the hard coating film are not limited. For example, the organic or inorganic fine particles may be organic fine particles made of acrylic resin, styrene resin, epoxide resin and nylon resin or silicon oxide. It may be an inorganic fine particle consisting of titanium dioxide, indium oxide, tin oxide, zirconium oxide and zinc oxide. The binder resin of the hard coating layer may further include a high molecular weight (co) polymer having a weight average molecular weight of 10, 000 or more.

The high molecular weight (co) polymer may be a cellulose polymer, an acrylic polymer, It may be at least one member selected from the group consisting of styrene polymer, epoxide polymer, nylon polymer, urethane polymer, and polyolefin polymer. On the other hand, as another example of the hard coating film, a binder resin of a photocurable resin; And the hard coat film containing the antistatic agent disperse | distributed to the said binder resin is mentioned.

 The photocurable resin included in the hard coat layer is a polymer of a photopolymerizable compound that can cause polymerization reaction when irradiated with light such as ultraviolet rays, and may be conventional in the art. However, preferably, the photopolymerizable compound may be a polyfunctional (meth) acrylate monomer or oligomer, wherein the number of the (meth) acrylate functional groups is 2 to 10, preferably 2 to 8, more preferably. Preferably, 2 to 7 is advantageous in terms of securing physical properties of the hard coating layer. More preferably, the photopolymerizable compound is pentaerythroxy tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythride (Meth) acrylate dipentaerythritol hepta (meth;) acrylate, tripentaerythroxy hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, nusamethylene diisocyanate, trimethylolpropane tri ( Meth) acrylate and trimethyl may be one or more selected from the group consisting of propane polyethoxy tri (meth) acrylate. The antistatic agent may be a quaternary ammonium salt compound, a conductive polymer or a combination thereof. Here, the quaternary ammonium salt compound may be a compound having one or more quaternary ammonium salt groups in the molecule, it can be used without limitation low molecular type or polymer type. In addition, the conductive polymer may be used as a low molecular type or a polymer type without limitation, the kind may be conventional in the art to which the present invention belongs, and is not particularly limited.

Binder resin of the photocurable resin; And an antistatic agent dispersed in the binder resin may further include one or more compounds selected from the group consisting of alkoxy silane oligomers and metal alkoxide oligomers. The alkoxy silane compound may be conventional in the art, but preferably tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methacryloxypropyl It may be at least one compound selected from the group consisting of trimethoxysilane, glycidoxypropyl trimethoxysilane, and glycidoxypropyl triethoxysilane.

 In addition, the metal alkoxide-based oligomer may be prepared by suppressing the sol-gel reaction of a composition containing a metal alkoxide-based compound and water. The sol-gel reaction can be carried out by a method similar to the method for producing an alkoxy silane oligomer described above.

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

 Here, the metal alkoxide-based 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, the anti-reflection film may further include a substrate bonded to the other surface of the hard coating layer. The substrate may have a light transmittance of 90% or more and a haze of 1% or less. In addition, the material of the substrate may be triacetyl cellulose, cycloolefin polymer, polyacrylate, polycarbonate, polyethylene terephthalate and the like. In addition, the thickness of the base film may be 10 to 300 kPa in consideration of productivity. However, the present invention is not limited thereto.

The low refractive index has a thickness of Iran to 200nm, the hard coating layer may have a thickness of 0.1 ffli to 100, or 1/10. 【Effects of the Invention】 According to the present invention, it can be provided with an anti-reflection film having a low reflectance and a high light transmittance and at the same time can implement high scratch resistance and antifouling, and can increase the sharpness of the screen of the display device.

 [Specific contents to carry out invention]

 The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of 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 (50 wt% solids, product name: LJD-1000) was coated on a triacetyl cellulose film with # 10 mayer bar.

After drying at 90 ° C. for 1 minute, a hard coating film having a thickness of 5 μm was prepared by irradiation with 150 mJ / cuf of ultraviolet rays.

<Examples and Comparative Examples: Preparation of the antireflection film>

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

 The components of Table 1 were mixed and mixed, and the mixture was diluted with a mixed solvent (1: 1 weight ratio) of MIBK methyl i sobutyl ketone) and diacetone alcohol (DM) so that the solid content was 3% by weight.

 (2) Preparation of low refractive index layer and antireflection film

 On the prepared hard coating film, the photocurable coating composition for producing a low refractive index layer, respectively obtained in Table 1 to # 3 mayer bar. Coating,

Dry at 60 ° C. for 1 minute. In addition, an antireflection film was prepared by irradiating 180 mJ / cuf of ultraviolet rays to the dried material under nitrogen purge to form a low refractive layer having a thickness of llOran.

Table 1 (Unit: g) Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6

THRULYA 4320 235 210 235 235 235 210 210 210

X71-1203M 125 85 85 85 85

0PT0OL-AR110 166.7

 OPTOOL-DAC-HP 125

 RS90 250

 RS-537 5 15 5 5 5

 TU2243 60 80

 RS907 20

MA0701 3 5 0 0 0 0 0 0

MIB-ST 33.3 43.3 33.3 33.3 33.3 50 50 50 Dipentaeryri 10 13 13 13 13 16 14 16 Pentaacrylate

Irgacure-127 3 4 3 3 3 4 4 4

1) THRULYA 4320 (catalyzed product): hollow silica dispersion (solids 20 weight in MIBK solvent «

 2) X71-1203M (Shinetsu): Fluorine-containing compound containing photoreactive functional group (diluted with 20 weight ¾ of solid in MIBK solvent, about 45 weight% of fluorine in solid)

 3) 0PT00L-AR110 (made by Daikin): Fluorine-containing compound containing photoreactive functional groups (diluted with 15 weight ¾ of solid content in MIBK solvent, about 60 weight% of fluorine content in solid content)

 4) 0PT00L-DAC-HP (made by Daikin): (diluted with 20% by weight of solids in MIBK / MEK mixed solvent (1: 1 weight ratio), about 39.5% by weight of fluorine in solids)

 5) RS90 (manufactured by DIC Corporation): Fluorine-containing compound containing photoreactive functional groups (diluted with 10 wt% of solids in Bi s (tri f luoromethyl) benzene solvent, 36.6% increase in fluorine content in solids)

RS537 (manufactured by DIC) Compound (diluted with 40 wt% solids in MIBK solvent, about 15 wt% fluorine content in solids)

 7) TU2243 (JSR): Fluorine-containing compound containing photoreactive functional groups (patterned with 10% by weight of solids in MIBK solvent, about 13% by weight fluorine in solids)

 8) RS907 (manufactured by DIC Corporation): Fluorine-containing compound containing photoreactive functional groups (diluted with 30 wt% solids in MIBK solvent, about 17 wt% fluorine content in solids)

 9) MA0701 ： Polysilsesquioxane (manufactured by Hybr id Plast ics)

 10) MIBK-ST (Ni ssan Chemi cal company): nano silica dispersion

Dilute to 30% solids in MIBK solvent

Experimental Example: Measurement of Physical Properties of Antireflection Film

 The antireflection films obtained in the Examples and Comparative Examples were subjected to the experiments as follows.

1. Average reflectance measurement

 After darkening the surface of the prepared antireflection film, Sol idspec 3700 (SHIMADZU) was applied to measure mode, and the average reflectance in the wavelength range of 380nm to 780nm was measured.

2. Scratch resistance measurement

 The steel wool (# 0000) was loaded and reciprocated 10 times at a speed of 27 rpm to rub the surface of the antireflective film obtained in the examples and the comparative examples. The maximum load at which one scratch or less of 1 cm or less observed with the naked eye was observed was measured.

3. Antifouling evaluation

The antifouling properties were evaluated by the number of times that a straight line was drawn with a black oil pen on the surface of each antireflection film obtained in Examples and Comparative Examples and then wiped off with a dust-free cloth. ©: cleared at less than 5 wipes

 0 ： Erase from 5 to 10 wipes

 Δ: erased in 11 to 20 wiping cycles

X ： Erase or do not erase in 21 or more wipes

4. Haze measurement

 For the antireflection film obtained in each of the above Examples and Comparative Examples, the average value was obtained by measuring the total haze of three places according to JIS K7105 standard using the HAZEMETER リ -150 equipment of Murakami color Research Laboratory.

Table 2

As shown in Table 2, the anti-reflection film of the embodiment exhibits a low reflectance of 0.7% or less and an overall haze value of 0.25% or less, thus showing relatively high light transmittance and excellent optical properties, and at the same time having high scratch resistance It was confirmed that it has excellent antifouling property.

 On the contrary, the antireflection film of the comparative example was found to have an average reflectance equivalent to that of the example, but to exhibit relatively high scratch resistance and antifouling resistance with a relatively high overall haze value.

Claims

[Claim]

 [Claim 1]

 A photopolymerizable compound, a binder resin comprising a crosslinked polymer between two or more kinds of fluorine-containing compounds including a photoreactive functional group and a polysilsesquioxane substituted with one or more reactive functional groups, and inorganic fine particles dispersed in the binder resin It comprises a low refractive index layer containing particles; and a hard coating layer;

 Anti-reflection film.

[Claim 2]

 In U,

 The total anti haze of the said antireflection film is 0.45% or less, The antireflection film.

[Claim 3]

 The method of claim 1,

 Two or more types of fluorine-containing compounds containing the said photo-banung functional group differ in the fluorine-containing range according to the kind, The antireflection film.

[Claim 4]

 According to claim 1,

 Two or more kinds of the fluorine-containing compound including the photo-reflective functional group comprises a first fluorine-containing compound comprising a photo-reflective functional group and containing 25 to 60% by weight of fluorine.

[Claim 5]

 The method of claim 4,

Two or more kinds of the fluorine-containing compound including the photo-reflective functional group comprises a second fluorine-containing compound comprising a photo-reflective functional group and containing fluorine in an amount of at least 1% by weight and less than 25% by weight.

[Claim 6]

 The method of claim 5,

 The antireflection film whose difference in fluorine content between the first fluorine-containing compound and the second fluorine-containing compound is 5% by weight or more.

[Claim 7]

 According to claim 15,

 The anti-reflection film of claim 1, wherein the weight ratio of the difluorine-containing compound to the first fluorine-containing compound is 0.01 to 0.5.

[Claim 8]

 The method of claim 1,

 Said crosslinked polymer contains 20-300 weight part of 2 or more types of fluorine-containing compounds containing the said photoreactive functional group with respect to 100 weight part of said photopolymerizable compounds.

[Claim 9]

 According to claim 1,

 The fluorine-containing compound including the photo-reflective functional group includes: i) an aliphatic compound or an aliphatic ring compound in which one or more photo-reflective functional groups are substituted, and at least one fluorine is substituted for at least one carbon; Π) hetero aliphatic compounds or heteroaliphatic ring compounds substituted with one or more photocyclic functional groups, at least one hydrogen substituted with fluorine, and one or more carbons substituted with silicon; i i i) a polydialkylsiloxane polymer substituted with at least one photoreactive functional group and substituted with at least one fluorine in 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; and at least one selected from the group consisting of: an antireflection film.

[Claim 10] The method of claim 1,

 The binder resin includes a photopolymerizable compound, a photoreactive functional group

An antireflection film further comprising a crosslinked polymer between two or more kinds of fluorine-containing compounds and a polysilsesquioxane in which one or more semi-functional groups are substituted.

[Claim 111]

 The method of claim 1,

 The cross-linked polymer between the photopolymerizable compound, two or more kinds of fluorine-containing compounds including photoreactive functional groups, and polysilsessesoxoxane in which one or more semi-aromatic functional groups are substituted is 100 parts by weight of the photopolymerizable compound. Is an antireflection film comprising 0.5 to 60 parts by weight of polysilsesquioxane substituted with at least one.

[Claim 12]

 In U,

 The semi-functional group substituted in the polysilsesquioxane is composed of alcohol, amine, carboxylic acid, epoxide, imide, (meth) acrylate, nitrile, norbornene, urepin, polyethylene glycol, thiol and vinyl group. An antireflection film comprising at least one functional group selected from the group.

[Claim 13]

 The method of claim 11,

 The polysilsesquioxane substituted with at least one semi-functional group is one or more selected from the group consisting of a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclonuclear group having 6 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. An antireflection film, wherein the unbanung functional group is substituted one or more more.

[Claim 14]

According to claim 1 The anti-reflective polysilsesquioxane substituted with at least one semi-functional functional group includes a polyhedral oligomeric silsesquioxane having at least one reactive functional group and having a cage structure. film.

[Claim 15]

 The method of claim 14,

 At least one or more of the silicones of the polyhedral oligomeric silsesquioxane having a cage structure is substituted with a semi-functional functional group and the other silicones in which the semi-functional functional group is not substituted are non-reflective functional groups. film.

[Claim 16]

 The method of claim 1,

 The inorganic fine particles include at least one selected from the group consisting of solid inorganic nanoparticles having a diameter of 0.5 to 100nm and hollow inorganic nanoparticles having a diameter of 1 to 200, anti-reflection film.