WO2017150938A1

WO2017150938A1 - Anti-reflective film

Info

Publication number: WO2017150938A1
Application number: PCT/KR2017/002332
Authority: WO
Inventors: 김부경; 변진석; 송인영; 장영래; 장석훈
Original assignee: 주식회사 엘지화학
Priority date: 2016-03-04
Filing date: 2017-03-03
Publication date: 2017-09-08

Abstract

The present invention relates to an anti-reflective film comprising a low-reflective layer and a hard coating layer, the low-reflective layer comprising: a binder resin comprising a crosslinked polymer between a photo-polymerizable compound and polysilsesquioxane having at least one reactive functional group substituted thereon; and inorganic microparticles dispersed in the binder resin, wherein the ratio of internal haze (Hi) to total haze (Ha) is 97% or less and the variation of a color coordinate value (b*) before and after alkaline treatment is 0.7 or less.

Description

【Specification】

[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. 10-2016-0026376 dated March 4, 2016 and Korean Patent Application No. 10-2017-0027321 dated March 2, 2017. All content disclosed in the literature is included as part of this specification. The present invention relates to an antireflective film, and more particularly, to an antireflective film having high reflectivity and scratch resistance at the same time with low reflectance and high light transmittance, and which can increase the sharpness of a screen of a display device. will be.

[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 a filler such as inorganic fine particles in a resin, coating on a base film and imparting irregularities (ant i-gl are: AG coating); The method of using the interference of light by forming a plurality of layers having different refractive indices on the base film (AR coating), or a common method thereof.

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, much research has recently been conducted on AR coatings.

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, as described above, a method of forming a plurality of worms is As the process of forming the layer is performed separately, the adhesion between the layers (interface adhesion) is weak, and thus scratch resistance is inferior.

Accordingly, many studies have been made to reduce the absolute reflection amount of light incident from the outside and to improve the scratch resistance of the surface. However, the improvement of the physical properties is insufficient. In addition, a method of adding a component such as an inorganic filler to the polymer film applied to the anti-reflection film to increase scratch resistance is known. According to this, the alkali resistance of the polymer film is greatly reduced and thus the manufacturing process of the polarizing plate and the like. There was a limit to being inadequate to apply to.

[Content of invention]

Problem to be solved

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

In the present specification, a binder resin comprising a crosslinked polymer between a photopolymerizable compound and a polysilsesquioxane (po lys l sesqui oxane) in which at least one semi-functional group is substituted; And an inorganic fine particle dispersed in the binder resin; and a low refractive index layer and a hard coating layer, wherein the ratio of the internal haze (Hi) to the total haze (Ha) is 97% or less and before and after the alkali treatment. b *) is provided with an antireflection film having a variation of 0.7 or less.

Hereinafter, 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 that causes polymerization reaction when light is irradiated, for example, visible light or ultraviolet light. In addition, (meth) acryl [(Meth) acryl] is meant to include both acryl and Methacryl.

In addition, a (co) polymer is meant to include both a copolymer and a homopolymer. Also, hollow silica particles (si li ca hol low part icl es) are silica particles derived from a silicon compound or an organosilicon compound, and particles having a form having an empty space on the surface and / or inside of the silica particles. it means. According to one embodiment of the invention, a binder resin comprising a cross-linked polymer between a photopolymerizable compound and a polysilsesquioxane (polysyl sesquioxane) substituted with at least one semi-active functional group; And an inorganic fine particle dispersed in the binder resin; and a low refractive index layer and a hard coating layer, wherein the ratio of the internal haze (Hi) to the total haze (Ha) is 97% or less, and before and after the alkali treatment. An antireflection film having a variation of (b *) of 0.7 or less can be provided.

As a result of the researches of the present inventors, the ratio of the internal haze (Hi) to the total haze (Ha) described above including the low refractive index layer and the hard coating layer described above and the reflection satisfying the variation of the color coordinate value (b *) before and after the alkali treatment The anti-reflective film can realize lower reflectance and high light transmittance, improve alkali resistance and secure excellent abrasion resistance or scratch resistance, and the anti-reflective film can increase the sharpness of the screen of the display device while providing excellent mechanical properties. It was confirmed through the experiment that can represent and completed the invention.

Specifically, the antireflection film may have a ratio of internal haze (Hi) to total haze (Ha) of 97% or less, or 95% or less, or 30% to 90%, or 52% to 89%.

The total haze (Ha) is defined as the sum of the surface haze (Hs) and the internal haze (Hi), the total haze can be obtained by measuring the haze on the anti-reflection film itself, the internal haze is subjected to alkali treatment A planarization layer may be coated and measured on the surface of one antireflective film, and the surface haze value may be defined as the overall haze and internal haze values are defined.

In general, the higher the surface haze, the greater the reflectance reduction effect due to scattering, and the lower the refractive index reduction due to the low refractive index layer within the same refractive index range. The effect is further increased, and the surface haze must be secured to some extent so as to ensure a smooth visibility in the display device.

In contrast, when the ratio of the internal haze (Hi) to the total haze (Ha) of the anti-reflection film exceeds 97¾, the ratio of the surface haze (Hs) of the total haze (Ha) is substantially reduced, Not only is the antireflection film not easy to ensure a low reflectance, but also the interference fringes of the antireflection film are easily exposed, so that the sharpness or visibility may be degraded in the final applied display device.

Although not limited to the total haze (Ha) of the anti-reflection film — for example 5) aha, or 0.05 — to 4%, or iii). It may be 100 to 3.2%. In addition, the internal haze of the anti-reflection film is also not limited, but may be, for example, 4% or less, or 0.1 to 3%, or 0.300 to 2.800.

In addition, the anti-reflection film may realize a low reflectance and a high light transmittance, and in particular, surface properties and optical properties may not change significantly before and after exposure to alkali. Specifically, the reflective anti-magnetic film may have a variation in color coordinate values (b *) before and after a predetermined alkali treatment of 0.7 or less, or 0.05 to 0.7, or 0.5 or less, or 0.1 to 0.5, or 0.28 to 0.4.

The measurement of the variation of the color coordinate value (b *) of the anti-reflection film before and after the predetermined alkali treatment was performed before and after the alkaline pretreatment by soaking for 1 second to 100 seconds in an alkaline aqueous solution (sodium hydroxide, etc.) which was distilled with 5 to 50% with distilled water. Can be measured using an optical device.

The antireflection film is characterized by the properties of the low refractive layer including the polysilsesquioxane substituted with at least one semi-functional functional group. Specifically, the polysilsesquioxane substituted with at least one reactive functional group has a reactive functional group present on the surface thereof to increase mechanical properties of the low refractive index layer, for example, scratch resistance, and may include silica, alumina, and the like. Unlike the case where fine particles such as light are used, 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. On the other hand, when the ellipticity of the polarization measured by the ellipsometry for the low refractive layer is optimized by the Cauchy model of the following formula (1), the following A is 1.20 to 1.65, B Is 0 to 0.05 and the following C can satisfy the conditions of 0 to 0.05, and also the following A is 1.35 to 1.40, the following B is 0.00200 to 0.00800 and the following C can satisfy the conditions of 0 to 0.005.

[

In Formula 1, ^η (λ) is the refractive index at the wavelength λ (λ), λ is in the range of 300 ran to 1800 nm, A, B and C are Kosh parameters.

In addition, when the ellipticity of the polarization measured by ellipsometry of the hard coating layer is optimized by the Cauchy model of Formula 1, A is 1.30 to 1.75, and B is 0 to 0.05 and the following C may satisfy the conditions of 0 to 0.005, the A is 1.500 to 1.520, the following B is 0.00100 to 0.00600 and the following C may satisfy the conditions of 0.00001 to 0.0.

The ellipticity of the polarization and related data (Ellipsometry (1 ^ 3 (Ψ, Δ)) measured by the ellipsometry can be measured using a commonly known method and apparatus. With respect to the low refractive index layer and the hard coating layer of the film, by using the apparatus of JA Woo 11 am Co. M-2000, an angle of incidence of 70 ° may be applied and linearly polarized light may be measured in the wavelength range of 380 nm to 1000 ran. The linear light measurement data (Ellipsometry (1 ^ 3 (Ψ, Δ)) can be optimized so that the MSE is 3 or less with the Cauchy model of the above formula 1 using the Complete EASE software.

The above-described Coke parameters A, B and C in the low refractive index layer and the hard coating layer are respectively related to the change of the refractive index and the extinction coefficient according to the wavelength, and each of the low refractive index layer and the hard coating layer described above Model (Cauchy In case of satisfying Kosh parameter A, B and C range by the result of optimizing with model), internally optimized electron density and refractive index distribution can be maintained, which results in lower reflectance and scratch. Alternatively, it may have a relatively stable structure against external pollutants.

Specifically, the Kosh parameter A is related to the lowest refractive index for each wavelength, and B and C are related to the degree of decrease of the refractive index with increasing wavelength. The low refractive index layer may have a thickness of about Iran to 200 nm, and the hard coating layer may have a thickness of about 100 1, or about 1 / im to about 10 nm. The thickness of each of the low refractive index layer and the hard coating layer may be confirmed by optimizing the ellipticity of the polarization measured by ellipsometry (Cauchy model) of Formula 1 below (f i tt ing). On the other hand, the low refractive index layer includes a binder resin containing a cross-linked polymer between the photopolymerizable compound and a polysilsesquioxane (polys i I sesquioxane) substituted with at least one semi-functional group and inorganic fine particles dispersed in the binder resin can do.

On the other hand, the polysilsesquioxane is (^;? ^ Can be expressed as and (wherein, n will have a variety of structures, such as 4 to 30 or 8 to 20), a random, ladder-type, cage and partial _cage. Can be.

However, in order to increase the physical properties and quality of the low refractive index layer and the anti-reflection film prepared from the photopolymerizable coating composition of the embodiment, the semi-functional functional group is at least one of polysilsesquioxane substituted with at least one semi-functional functional group. Substituted polyhedral oligomeric silsesquioxanes having a cage structure can be used.

Also, more preferably, the polyhedral oligomeric silsesquioxane having one or more functional groups and having 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 a reactive functional group, and the above-mentioned non-reactive functional groups may be substituted with silicones not having a substituted functional group. Can be. As the reactive functional group is substituted in at least one of the polysilicon polysaccharide oligomeric silsesquioxane silicones having a cage structure, the mechanical properties of the coating film or the binder resin formed during photopolymerization of the photopolymerizable coating composition may be improved. As non-acyclic functional groups are substituted in the remaining silicones, molecular structural steric hinderances may occur, thereby greatly reducing the frequency or spread of siloxane bonds (-Si— 0-) exposed to the outside. The alkali resistance of the coating film and binder resin formed at the time of photopolymerization of a synthetic coating composition can be improved.

The semi-functional groups substituted in the polysilsesquioxanes are alcohols, amines, carboxylic acids, epoxides, imides, (meth) acrylates, nitriles, norbornenes, olefins [al ly, cycloalkenyl ( cycloalkenyl) or vinyldimethylsilyl and the like], polyethylene glycol, thiol and vinyl groups, and may include one or more functional groups selected from the group consisting of epoxides or

(Meth) acrylate.

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

On the other hand, the polysilsesquioxane substituted with at least one semi-active functional group is a linear or branched alkyl group of 1 to 20 carbon atoms, a cyclonuclear group of 6 to 20 carbon atoms and 6 to 20 carbon atoms in addition to the above-mentioned semi-functional functional group At least one non-banung functional group selected from the group consisting of aryl groups may further include at least one. As such, the semi-functional male group and the un-functional male group are substituted on the surface of the polysilsesquioxane, so that the reactive functional group is at least one. In the substituted polysilsesquioxane, the siloxane bond (-Si-0-) is located inside the molecule and is not exposed to the outside, thereby improving alkali resistance and scratch resistance of the low refractive index layer and the antireflection film.

Examples of the polyhedral oligomeric silsesquioxane (POSS) having one or more such reactive functional groups and having a cage structure include TMP Diol Isobutyl POSS, Cyclohexanediol Isobutyl POSS, 1,2-Propanediol Isobutyl POSS, POSS substituted with one or more alcohols such as 0c ta (3-hydroxy-3 methylbutyldimethylsiloxy) POSS; Aminopropyl Isobutyl POSS, Aminopropyl Isooctyl POSS, Am i noe t fiy 1 am i nopr opy 1 Isobutyl POSS, N-Pheny 1 am i nopr dpy 1 POSS, N ᅳ Met hy 1 am i nopr opy 1 Isobutyl POSS, OctaAmmonium POSS,

POSS substituted with at least one amine such as AminophenylCyclohexyl POSS and Am inophenyl Isobutyl POSS; POSS in which at least one carboxylic acid is substituted, such as Maleamic Acid-Cyclohexyl POSS, Maleamic Acid-Isobutyl POSS, Oct a Maleamic Acid POSS; POSS substituted with at least one epoxide such as EpoxyCyclohexyl Isobutyl POSS, Epoxycyclohexyl POSS, Glycidyl POSS, GlycidylEthyl POSS, Glycidyl Isobutyl POSS, Glycidyl Isooctyl POSS; POSS in which at least one imide is substituted, such as POSS Maleimide Cyclohexyl and POSS Maleimide Isobutyl; Acrylolsobutyl POSS, (Meth) acryl Isobutyl POSS, (Meth) acrylate Cyclohexyl POSS, (Meth) acrylate Isobutyl POSS, (Meth) acrylate Ethyl POSS, (Meth) acrylEthyl POSS, (Meth) acrylate Isooctyl POSS,

P0SS substituted with one or more (meth) acrylates such as (Meth) acryl Isooctyl POSS, (Meth) acrylPhenyl POSS, (Meth) acryl POSS, and Acrylo POSS; P0SS in which at least one nitrile group such as Cyanopropyl Isobutyl POSS is substituted; POSS in which at least one norbornene group is substituted, such as NorbornenylEthyl POSS, Norbornenyl ethyl Isobutyl POSS, Norbornenyl ethyl DiSi lanolsobutyl POSS, and Tr isnorbornenyl Isobutyl POSS; POSS substituted with at least one vinyl group such as Allyllsobutyl POSS, MonoVinyl Isobutyl POSS, OctaCyclohexenyldimethylsiyl POSS, OctaVinyldimethylsiyl POSS, OctaVinyl POSS; Allyllsobutyl POSS, MonoVinyl Isobutyl POSS, OctaCyclohexenyldimethylsi lyl POSS, POSS in which one or more olefins such as OctaVinyldimethyl silyl POSS and OctaVinyl POSS are substituted; POSS substituted with PEG of 5 to 30 carbon atoms; Or P0SS in which one or more thiol groups, such as Mercaptopropyl Isobutyl POSS or Mercaptopropyl Isooctyl POSS, are substituted; Etc. can be mentioned.

The weight ratio of the portion derived from polysilsesquioxane in which at least one semi-amen functional group is substituted with the portion derived from the photopolymerizable compound in the binder resin is 0.005 to 0.50, or 0.005 to 0.25, or 0.015. To 0. 19. The alkali resistance of the low refractive index layer is too small when the content of the portion derived from polysilsesquioxane in which the semi-ungsung group is one or more substituted with the portion derived from the photopolymerizable compound in the binder resin is too small. However, it may be difficult to sufficiently secure scratch resistance.

Further, when the content of the portion derived from polysilsesquioxane in which the reactive functional group is substituted at least one of the portion derived from the photopolymerizable compound of the binder resin in the photopolymerizable coating composition is too large, Transparency of the low refractive index layer or the antireflection film may be lowered, and scratchability may be lowered.

On the other hand, the photopolymerizable compound forming the binder resin may include a monomer or oligomer containing (meth) acrylate or 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.

As a specific example of the monomer or oligomer containing the said (meth) acrylate, a pentaerythri is tri (meth) acrylate, a pentaerythri (tetra) (meth) acrylate, dipentaerythritol (penta) acrylate ， Dipentaerythrione nucleated (meth) acrylate ， Tripentaerythrione hepta (meth) acrylate ， Tylene diisocyanate ， Xylene diisocyanate ， Hexamethylene diisocyanate ， Trimethylolpropane tri (meth) acrylate ， Trimethylolpropane polyethoxy Tri (meth) acrylate ᅳ trimethyl to propanetrimethacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, nuxaethyl methacrylate, butyl methacrylate or two or more kinds thereof, or urethane modified Acrylate oligomers, epoxide acrylate oligomers, ether acrylate 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.

In the binder resin, the content of the portion derived from -the—photopolymerizable compound is not particularly limited, but the content of the photopolymerizable compound is 20 wt% in consideration of mechanical properties of the low refractive index layer or the antireflection film to be manufactured. ¾> -80% by weight.

In addition, as described above, the low refractive layer may further include a portion derived from a fluorine-based compound including a photoreactive functional group. As the fluorine-based compound including the photo-reflective functional group is included, the low refractive index layer and the antireflection film may have a lower reflectance and an improved light transmittance, and may further improve alkali resistance and scratch resistance. Accordingly, the binder resin may further include a crosslinked polymer between a photopolymerizable compound, a fluorine-based compound including a photoreactive functional group, and a polysilsesquioxane in which at least one semi-reactive functional group is substituted.

The fluorine-based compound may include or replace one or more photo-reflective functional groups, and the photo-reflective functional group refers to a functional group capable of participating in the polymerization reaction by irradiation of light, for example, by irradiation of visible light or ultraviolet light. The photo-reflective functional group may include various functional groups known to be able to participate in the polymerization reaction by irradiation of light, and specific examples thereof include (meth) acrylate groups, epoxide groups, vinyl groups, or cyclo groups ( Thiol) is mentioned.

The fluorine-based compound including the photoreactive functional group may have a fluorine content of 1 to 60 weight ¾>. Fluorine-based including the photo-banung functional group If the content of fluorine in the compound is too small, it may be difficult to sufficiently secure the physical properties such as alkali resistance because the fluorine component is not arranged to the surface of the low refractive index layer. In addition, if the fluorine content in the fluorine-based compound including the photo-reflective functional group is too large, the surface properties of the low refractive index layer may be lowered or the incidence of defective products during the post-stage process to obtain the final result. On the other hand, when the low refractive layer is formed on one surface of the hard coating layer having an anti-reflection function, in order to minimize the problems caused by peeling electrification voltage that may occur in the manufacturing process or the actual application of the anti-reflection film, the low The refractive layer may include a fluorine-based compound including a photoreactive functional group having a fluorine content of 1 wt% to 25 wt%.

The fluorine-based compound including the photoreactive functional group may further include silicon or a silicon compound. That is, the bloso-based compound including the photoreactive functional group may optionally contain a silicon or silicon compound therein, and specifically, the content of silicon in the fluorine-based compound including the photoreactive functional group is 0.1 weight ¾> to 20 weight May be).

Silicon included in the fluorine-based compound including the photoreactive functional group may serve to increase transparency by preventing haze from occurring in the low refractive layer. On the other hand, when the content of silicon in the fluorine-based compound including the photo-reflective functional group is too large, the alkali resistance of the low refractive index layer may be lowered.

The fluorine-based compound including the photoreactive functional group is from 2,000 to

It may have a weight average molecular weight (weight average molecular weight of polystyrene conversion measured by GPC method) of 200, 000. If the weight average molecular weight of the fluorine-based compound including the photoreactive functional group is too small, the low refractive layer may not have a layered alkali resistance. In addition, if the weight average molecular weight of the fluorine-based compound including the photoreactive functional group is too large, the low refractive index layer may not have sufficient durability or scratch resistance, and also the compatibility between the fluorine-based compound and the other components including the photoreactive functional group Since the property is lowered, there is no uniform dispersion during the production of the low refractive index layer, thereby lowering the internal structure or surface properties of the final product. . Specifically, the fluorine-based 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; ii) heteroaliphatic compounds or heteroaliphatic ring compounds substituted with one or more photoreactive functional groups, at least one hydrogen substituted with fluorine, and one or more carbons substituted with silicon; iii) polydialkylsiloxane polymers (eg, polydimethylsiloxane polymers) in which at least one photoreactive functional group is substituted and at least one fluorine is substituted in at least one silicon; iv) substituted by one or more photoreactive functional groups there may be mentioned a polyether compound, or the Π to iv) at least two of the common ^u compound or a copolymer thereof is substituted by at least one of the hydrogen fluoride.

The low refractive layer may include 1 to 75 parts by weight of the fluorine-based compound including the photoreactive functional group based on 100 parts by weight of the photopolymerizable compound. When the fluorine-based compound including the photoreactive functional group is added in excess to the photopolymerizable compound, the low refractive layer may not have sufficient durability or scratch resistance. In addition, when the amount of the bloso-based compound including the photoreactive functional group relative to the photopolymerizable compound is too small, the low refractive index layer may not have a layered alkali resistance.

On the other hand, the binder resin may further include a portion derived from the fluorine-based (meth) acrylate compound in addition to the photopolymerizable compound described above. The fluorine-based (meth) acrylate compound may also be in a state crosslinked with any one or more of the other components included in the binder resin.

When further comprising the fluorine-based (meth) acrylate compound, the weight ratio of the fluorine-based (meth) acrylate compound to the monomer or oligomer containing the (meth) acrylate or vinyl group may be 0.1% to 10¾ » have.

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

[Formula 11]

In Formula 11, R ¹ is a hydrogen group or a C 1 alkyl group, a is an integer of 0 to 7, b is an integer of 1 to 3.

[Formula 12]

In Chemical Formula 12, c is an integer of 1 to 10.

[Formula 13]

In Formula 13, d is an integer of 1 to 11.

[Formula 14]

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

[Formula 15]

In Formula 15, f is an integer of 4 to 10. 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 nanoparticles refer to particles having a maximum diameter of 100 ran or less and no hollow 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 200 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. The solid inorganic nanoparticles and the hollow inorganic nanoparticles As the particles each contain the above-mentioned semi-functional functional groups on the surface, the low refractive index layer may have a higher degree of crosslinking, thereby ensuring improved scratch resistance and antifouling resistance.

As the hollow inorganic nanoparticles, the surface of the hollow inorganic nanoparticles may be used alone or in combination with the hollow inorganic nanoparticles whose surface is not coated with the fluorine-based compound. Coating the surface of the hollow inorganic nanoparticles with a fluorine-based compound may 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-based compound on the surface of the hollow inorganic nanoparticles may be used without any significant limitation. For example, the hollow inorganic nanoparticles and the bloso-based compound may be mixed with water. By sol-gel reaction in the presence of a catalyst, the fluorine-based compound may be bonded to the surface of the hollow inorganic nanoparticle 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. For example, (meth) acrylate group, vinyl group, hydroxy group, amine group, allyl group, allyl group, 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 index layer may include 10 to 350 parts by weight of the inorganic fine particles, or 50 to 280 parts by weight based on 100 parts by weight of the photopolymerizable compound. When the hollow 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 layer is applied to a predetermined substrate by applying a photopolymerizable coating composition comprising a polysilsesquioxane (polysi l sesquioxane) substituted with at least one photopolymerizable compound, inorganic fine particles and semi-aromatic functional groups It can be obtained by photopolymerizing the result. The specific kind or thickness of the substrate is not particularly limited, and is used in the manufacture of a low refractive index layer or an antireflection film. Known substrates can be used without great limitation.

In addition, the photopolymerizable coating composition may further include a fluorine-based compound including the photoreactive functional group.

In addition, the photopolymerizable coating composition may further include a photoinitiator. The photopolymerization initiator may be used without any limitation as long as it is a compound known to be used in the photopolymerizable resin composition. Specifically, a benzophenone compound, acetophenone compound, biimidazole compound, triazine compound, oxime compound or 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, a material that remains uncured in the photopolymerization step of the photopolymerizable coating composition may be issued. If the amount of the photopolymerization initiator is too large, the unreacted initiator may remain as an impurity or have a low crosslinking density, thereby lowering mechanical properties or significantly increasing reflectance of the film.

In addition, the photopolymerizable 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 two or more kinds thereof.

The organic solvent may be included in the photopolymerizable coating composition while being added at the time of mixing the respective components included in the photopolymerizable coating composition or in the state in which each component is dispersed or mixed in the organic solvent. When the content of the organic solvent in the photopolymerizable coating composition is too small, defects may occur such as streaks in the final manufactured film due to deterioration in flowability of the photopolymerizable coating composition. In addition, when the excess amount of the organic solvent As the solid content is lowered, coating and film formation are not delaminated, so that physical properties and surface properties of the film may be degraded, and defects may occur during drying and curing. Accordingly, the photopolymerizable coating composition may include an organic solvent such that the concentration of the total solids of the components included is 1 weight ¾) to 50 weight ¾>, or 2 to 20 weight%.

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

In the step of photopolymerizing the photopolymerizable coating composition

Ultraviolet light or visible light having a wavelength of 200 to 400 nm can be irradiated, and the exposure dose during irradiation is preferably 100 to 4, 000 mJ / cuf. 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 photopolymerizing the photopolymerizable coating composition, nitrogen purging may be performed to apply nitrogen atmospheric conditions.

The antireflection film may have an average reflectance of 2.2% or less, 1.5% or less, or 1.20% or less.

On the other hand, the hard coating layer can be used without a large limitation to the conventional known hard coating layer.

Examples of the hard coat film include a binder resin including a photopolymerizable resin and a high molecular weight (co) polymer having a weight average molecular weight of 10, 000 or more, and a hard coat film including organic or inorganic fine particles dispersed in the binder resin. Can be mentioned.

The high molecular weight (co) polymer may be one or more selected from the group consisting of cellulose-based polymers, acrylic polymers, styrene-based polymers, epoxide-based polymers, nylon-based polymers, urethane-based polymers, and polyolefin-based polymers. The photopolymerizable resin included in the hard coating layer is a polymer of a photopolymerizable compound which may cause a polymerization reaction when light such as ultraviolet rays is irradiated, and may be conventional in the art. Specifically, the photopolymerizable resin is A semi-active acrylate oligomer group consisting of urethane acrylate oligomers, epoxide acrylate oligomers, polyester acrylates, and polyether acrylates; And dipentaerythritol nucleoacrylate, dipentaerythroxy hydroxy pentaacrylate, pentaerythriri tetraacrylate, pentaerythriri triacrylate, trimethylene propyl triacrylate, propoxylated glycerol Multifunctional acrylic consisting of triacrylate, trimethylpropane ethoxy triacrylate, 1, 6-nucleic acid diol diacrylate, propoxylated glycerol triacrylate, tripropylene glycol diacrylate, and ethylene glycol diacrylate It may include one or more selected from the rate monomer group.

The organic or inorganic fine particles are not particularly limited in particle size, but for example, the organic fine particles may have a particle size of 1 to 10 mm 3, and the inorganic particles may have a particle size of 1 ran to 500 nm or lnm to 300 nm. have.

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 hard coat film may be formed from an anti-glare coating composition comprising organic or inorganic fine particles, a photopolymerizable resin, a photoinitiator, and a high molecular weight (co) polymer having a weight average molecular weight of 10, 000 or more.

On the other hand, as another example of the hard coating film, a binder resin of a photopolymerizable resin; And the hard coat film containing the antistatic agent disperse | distributed to the said binder resin is mentioned.

The photopolymerizable resin included in the hard coating layer is a polymer of a photopolymerizable compound that may 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 (meth) acrylate functional groups is 2 to 10, preferably 2 to 8, more preferably 2 to 7 is advantageous in terms of securing physical properties of the hard coat 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, tripentaerythritol hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, nusamethylene diisocyanate, trimethylolpropane tri ( It may be at least one selected from the group consisting of meth) acrylate, and trimethylolpropane polyethoxy tri (meth) acrylate. The "cheoncheon-cho" inhibitor may be a quaternary ammonium salt compound-,-a conducting 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 photopolymerizable 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, methacryl It may be at least one compound selected from the group consisting of oxypropyltrimethoxysilane, glycidoxypropyl trimethoxysilane, and glycidoxypropyl triethoxysilane.

In addition, the metal alkoxide-based oligomer may be prepared through the sol-gel reaction of the composition comprising 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 rapidly with water, 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 the reaction efficiency and the like, 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. ᅳ — ― ᅳ —

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 in consideration of productivity. However, the present invention is not limited thereto.

【Effects of the Invention】

According to the present invention, it is possible to provide an anti-reflection film which can simultaneously have high alkali resistance and scratch resistance with low reflectance and high light transmittance and can increase the sharpness of the screen of the display device. The anti-reflection film does not significantly reduce the appearance properties such as reflectance or light transmittance and the mechanical properties such as wear resistance or scratch resistance even when exposed to alkali, so that the application of an additional protective film for protecting the external surface can be omitted. To simplify and reduce production costs.

[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 1 Preparation of Hard Coating Film 1 (HD1)

A homogeneous mixture of 30 g of triacrylate, 2.5 g of high molecular weight copolymer (BEAMSET 371, Arakawa, Epoxy Acrylate, molecular weight 40,000), 20 g of methyl ethyl ketone and 0.5 g of leveling agent (Tego wet 270) Thereafter, 2 g of acryl-styrene copolymer resin fine particles having a refractive index of 1.525 (volume average particle size: 2 ^ m, manufacturer: Sekisui Plastic) were added to prepare a hard coating composition.

"A hard coating solution composition obtained as described above was added to a triacetyl cellulose film.

Coated with # 10 mayer bar and dried at 90 ° C. for 1 minute. The dried material was irradiated with ultraviolet light of 150 mJ / cirf to prepare a hard coat film having a thickness of 4. Preparation Example 2: Preparation of Hard Coating Film 2 (HD2)

After homogeneously mixing 30 g of pentaerythritol triacrylate, 2.5 g of high molecular weight copolymer (BEAMSET 371, Arakawa, Epoxy Acrylate, molecular weight 40,000), 20 g of methyl ethyl ketone and 0.5 g of leveling agent (Tego wet 270) 2 g of acrylic-styrene copolymer resin fine particles (volume average particle diameter: 2 im, manufacturer: Sekisui Plastic) having a refractive index of 1.515 were added thereto to prepare a hard coating composition.

The hard coating solution composition thus obtained was coated with a # 10 mayer bar on a triacetyl cellulose film and dried at 90 ° C. for 1 minute. The dried material was irradiated with ultraviolet light of 150 mJ / ciif to prepare a hard coat film having a thickness of 4 m. Preparation Example 3 Preparation of Hard Coating Film 3 (HD3)

Pentaerythriri triacrylate 30g, high molecular weight copolymer (BE 舰 SET

371, Arakawa, Epoxy Acrylate, molecular weight 40,000) 2.5 g, methyl ethyl ketone 20 g and 0.5 g of leveling agent (Tego wet 270) after uniform mixing A hard coating composition was prepared by adding 2 g of acrylic-styrene copolymer resin fine particles (volume average particle diameter: 2, manufacturer: Sekisui Plastic) having a refractive index of 1.544.

The hard coating solution composition thus obtained was coated with a # 10 mayer bar on a triacetyl cellulose film and dried at 90 ^° C. for 1 minute. The dried material was irradiated with ultraviolet light of 150 mJ / cin ² to prepare a hard coat film having a thickness of 4. Preparation Example 4 Preparation of Hard Coating Film 4 (HD4)

KY0EISHA salt type antistatic hard coating solution (50 wt% solids, product name: LJD—1000) coated with triacetyl cellulose film with # 10 mayer bar and dried at 90 ^° C for 1 minute, UV light of 150 mJ / cuf Was investigated to prepare a hard coat film (HD4) having a thickness of 4 mm 3. <Examples and Comparative Examples: Preparation of the antireflection film>

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

The components shown in Table 1 were mixed, and MIBKOnethyl isobutyl ketone) and diacetone alcohol (DM) were diluted in a weight ratio of 1: 1 so that the solid content was 3 weight ¾>.

Table 1

(Unit: g) LR1 LR2 LR3 LR4 LR5 Hollow Silica Dispersion 220 130 220 130 0

(THRULYA (THRULYA (THRULYA (THRULYA

4320) 4320) 4320) 4320)

Nano Silica Dispersion 0 0 0 0 16.7

(MIB-SD) trimethylolpropane 41 62 47 67

Triacrylate

1H, 1H, 6H, 6 H- 0 0 0 0 1 perfluoro— 1,6-nucleodiol diac

(MA0701) (MA0701) (AC-SQ-F) Fluorine containing photoreactive functional groups 13.33 6.667 13.333 6.667 0.1001 Compound RS907

Photoinitiator 5 5 5 5 0.25

(Irgacure-127,

Ciba company)

1) THRULYA 4320 (catalytic product): Hollow silica dispersion (20 wt ¾ solid in MIBK solvent)

2) RS907 (manufactured by DIC Corporation): Fluorine compound containing photoreactive functional group and containing trace amount of silicon, diluted to 30% by weight of solids in MIBK solvent

3) MA0701: Product of Hybrid Plast ics

4) AC-SQ-F: manufactured by Dong-A Synthetic Co., Ltd. (silsesquioxane resin functional group concentration 678 g / mol, inorganic fraction 15%, refractive index 1.39) (2) Preparation of low refractive index layer and antireflection film (Examples and Comparative Examples) On the hard coat film shown in Table 2 below, the photopolymerizable coating composition obtained in Table 1 was coated with # 3 mayer bar, and dried at 60 ^° C. for 1 minute. In addition, an antireflection film was prepared by irradiating ultraviolet light of 180 mJ / cuf to the dried material under nitrogen purge to form a low refractive layer having a thickness of llOnm.

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. Alkali pretreatment

The antireflection films obtained in Examples and Comparative Examples were soaked for 30 seconds in a 55 ^° C. NaOH aqueous solution diluted with 1OT with distilled water, washed with water, and then wiped dry.

2. Average reflectance and color coordinate (b *) measurements

About the antireflection film obtained by the said Example and the comparative example After darkening the back side of the film before and after the pretreatment, the average reflectance and color coordinate values (b *) in the wavelength range of 380 nm to 780 ran were measured using the SolTspec 3700 (SHIMADZU) 100T mode.

In the case of the color coordinate value (b *), the obtained average reflectance data was obtained by converting the UV-240 IPC program.

3. Scratch resistance measurement

At the time before and after the pretreatment, the steel wool (# 0000) was loaded and reciprocated 10 times at a speed of 24 rpm to rub the surface of the antireflective film obtained in Examples and Comparative Examples. The maximum load at which one scratch or less of 1 cm or less was observed with the naked eye was measured.

4. Haze measurement

For the antireflection film obtained in each of the above Examples and Comparative Examples, three hazes were measured according to the J IS 7105 standard by using the HAZEMETER 匪 -150 equipment of Murakami color Research Laboratory to obtain an average value.

(1) Total Haze (Ha): Surface Haze (Hs) + Internal Haze (Hi)

(2) Total haze measures haze with respect to the antireflection film itself

(3) The internal haze was coated with a flattening layer on the surface of the antireflection film subjected to the alkali treatment, and the haze of the entire film was measured.

(4) Alkali treatment: after the Examples and Comparative Examples, the anti-reflection film each obtained in the NaOH aqueous solution of 30 ^° C is diluted to 10% with distilled water two minutes damgwotdaga wiped dry and then washed by flowing water, 50 ^° at C oven It dried for 1 minute.

(5) Flattening layer coating: pentaerythriri triacrylate and Ebecryl

220 (Lyligomer of SK cytec) was mixed at a weight ratio of 6: 1, and diluted to a weight ratio of 60: 1 by weight in a solvent mixture of methyl ethyl ketone and toluene at a weight ratio of 1: 1, and dried using wi re bar. The surface irregularities were flattened after coating and drying and curing so that the film thickness was 8 // m. 5. Ellipsometry Measurements

The ellipticity of the polarization was measured by ellipsometry on the antireflection film obtained in each of Examples and Comparative Examples.

Specifically, for the antireflection film obtained in each of the above Examples and Comparative Examples, JA Woo 11 am Co. Using the apparatus of the M-2000, an incident angle of 70 ^ο was applied and linearly polarized light was measured in the wavelength range of 380 ran to 1000 ran. The measured linear light measurement data (Ellipsometry data (W, A)) was optimized to a MSE of 3 or less with a Cauchy model of the following general formula 1 using Complete EASE software.

[ ^"

In Formula 1, ^η (λ) is the refractive index at the λ wavelength, λ is in the range of 300 nm to 1800 nm, A, B and C is a Kosh parameter.

[Table 2]

Color coordinate value (b *)

Variation of

El l ipsometry measurement results

Low Refraction A 1.37 1.36 1.38 1.4 1.38 1.36 1.41 1.36

B 0.00426 0.00253 0.00282 0.00789 0.0059 0.00334 0.0069 0.00326

C 0 0.00019 6.93 * 10 2.5 * 10— ³ 0.0011 5.2 * 10— ⁴ 0 0

8

Hardco A 1.514 1.513 1.513 1.509 1.511 1.513 1.519 1.512

¾ ^ ^ ΰ B 0.00518 0.00354 0.00132 0.00343 0.00491 0.00506 0.00114 0.00423

C 1.63 4.04 0.00024 0.00025 1. 13 3.87 0.00048 1.28 * 10

* 10 ^"5 * 10— ⁵ 1 4 * 10 ^{" 5} * 10— ⁶ 5 As shown in Table 2 above, the antireflection film of the example exhibits a relatively low average reflectance and does not have a large variation in color coordinates even after alkali treatment. Moreover, it was confirmed that it has more excellent scratch resistance compared with the comparative example.

Specifically, the anti-radiation film of the embodiment has a ratio of the internal haze (Hi) to the total haze (Ha) of 97% or less, and the anti-reflective film of the anti-reflection film has a variation of the color coordinate value (b *) after alkali pretreatment of 0.28 It was confirmed that the range is from 0.40.

In addition, when the ellipticity of the polarization measured by the ellipsometry (el l ipsometry) with respect to the antireflection film of Example 1 was optimized by the Cauchy model of the general formula (1), the low refractive index layer is A 1.20 to 1.65, the following B is 0 to 0.05 and the following C satisfies the Kosh parameter condition of 0 to 0.05, the hard coating layer A is 1.30 to 1.75, the following B is 0 to 0.05 and the following C is 0 to 0.005 Satisfies the Kosh parameter.

On the contrary, it was confirmed that the antireflection films of Comparative Examples 1 to 3 had relatively high color coordinate values or low scratch resistance after alkali treatment. In addition, the antireflective film of the comparative example has an internal haze ratio to the total haze (Ha) of more than 97% or alkali. It is confirmed that the variation in color coordinate values is relatively large after the treatment, indicating a relatively low light transmittance and poor alkali resistance and optical properties.

Claims

【Claims】

[Claim 1]

A binder resin containing a cross-linking polymer between a photopolymerizable compound and polysilsesquioxane ( _polysil _sesqu i _oxane ) substituted with one or more semi-male functional groups; And a low refractive index layer and a hard coating layer including inorganic fine particles dispersed in the binder resin,

The ratio of internal haze (Hi) to total haze (Ha) is 97% or less, and the variation of color coordinate value (b*) before and after alkali treatment is 0.7 or less,

Anti-reflective film.

【Claim 2】

In clause 1,

The variation of the color coordinate value (b*) before and after the alkali treatment is determined by measuring the color coordinate values before and after the alkaline pretreatment by immersing the anti-reflection film in an aqueous alkaline solution diluted by 5 to 50% with distilled water for 1 to 100 seconds. ，Anti-reflective film.

【Claim 3】

In clause 1,

When the ellipticity of polarization measured by ellipsometry for the low refractive index layer was optimized by fitting the Cauchy model of the following general formula 1,

A is 1.20 to 1.65, B is 0 to 0.05, and C is 0 to 0.05. An anti-reflective film that satisfies the following conditions:

[General Formula 1]

- ^■ * ^■■ -■：： - . -β. -'≠. In General Formula 1, η(λ) is the refractive index at λ wavelength, λ is in the range of 300 ran to 1800 ran, and A, B, and C are Cauchy parameters.

[Claim 4]

In clause 1,

When the ellipticity of polarization measured by ellipsometry for the hard coating layer was optimized (fitting) with the Cauchy model of the following general formula 1,

An anti-reflective film that satisfies the following conditions: A is 1.30 to 1.75, B is 0 to 0.05, and C is 0 to 0.005:

[General Formula 1]

In General Formula 1, η(λ) is the refractive index at λ wavelength, λ is in the range of 300 ran to 1800 nm, and A, B, and C are Cauchy parameters.

【Claim 5】

In clause 1,

The low refractive index layer has a thickness of 1 nm to 200 nm, and the hard coating layer has a thickness of 0.1 nm to 100 nm.

【Claim 6】

According to clause 1,

Among the binder resins included in the low refractive index layer, the weight ratio of the portion derived from polysilsesquioxane substituted with one or more semi-male functional groups compared to the portion derived from the photopolymerizable compound is 0.005 to 0.50,

Anti-reflective film.

[Claim 7]

In clause U, The reactive functional group substituted for the polysilsesquioxane includes alcohol, amine, carboxylic acid, epoxide, imide, (meth)acrylate, nitrile, norbornene, olefin, polyethylene glycol, thiol, and vinyl group. selected

An anti-reflective film comprising one or more functional groups.

【Claim 8】

In clause 1,

The polysilsesquioxane substituted with one or more semi-male functional groups includes a polyhedral oligomeric silsesquioxane substituted with one or more semi-male functional groups and having a cage structure. anti-film.

【Claim 9】

In clause 8,

At least one of the silicones of the polyhedral oligomer silsesquioxane having the cage structure is substituted with a semi-male functional group, and the remaining silicones that are not substituted with the reactive functional group are substituted with a non-reactive functional group. anti-film.

【Claim 10】

In clause 1,

The photopolymerizable compound is an anti-reflective film containing a monomer or oligomer containing (meth)acrylate or a vinyl group.

【Claim 11】

According to clause 1,

The binder resin is an antireflection film further comprising a crosslinking polymer between a photopolymerizable compound, a fluorine-based compound containing a photoreactive functional group, and polysilsesquioxane substituted with one or more reactive functional groups.

[Claim 12]

In clause 11,

The photoreactive functional group included in the fluorine-based compound is at least one selected from the group consisting of a C (meth)acrylate group, an epoxide group, a vinyl group, and a thiol group.

[Claim 13]

In clause 11,

The fluorine-based compound containing the photoreactive functional group ranges from 1% by weight to

Anti-reflective film with a fluorine content of 60% by weight.

【Claim 14】

According to clause 11,

The fluorine-containing compound containing the photoreactive functional group is i) an aliphatic compound or an aliphatic ring compound in which one or more photoreactive functional groups are substituted and at least one carbon is substituted with one or more fluorines; ii i) A hetero aliphatic compound or hetero aliphatic ring compound substituted with one or more photoreactive functional groups, at least one hydrogen is substituted with fluorine, and one or more carbons are substituted with silicon; i i i) a polydialkylsiloxane-based polymer in which one or more photoreactive male functional groups are substituted and at least one silicon is substituted with one or more fluorines; and iv) a polyether compound substituted with one or more photoreactive functional groups and at least one hydrogen is substituted with fluorine; Containing at least one member selected from the group consisting of,

Anti-reflective film.

[Claim 15]

In clause 11,

The fluorine-based compound containing the photoreactive functional group has a weight average molecular weight of 2,000 to 200,000.

【Claim 16】

In clause 1,

The inorganic fine particles include at least one selected from the group consisting of solid inorganic nanoparticles with a diameter of 0.5 to 1OOran and hollow inorganic nanoparticles with a diameter of 1 to 200 nm.

【Claim 17】

In clause 1,

The hard coating film is an anti-reflection film comprising a binder resin containing a photopolymerizable resin and a high molecular weight (co)polymer with a weight average molecular weight of 10,000 or more, and organic or inorganic fine particles dispersed in the binder resin.