WO2017155336A1

WO2017155336A1 - Antireflective film

Info

Publication number: WO2017155336A1
Application number: PCT/KR2017/002581
Authority: WO
Inventors: 김부경; 장영래; 심재훈; 박진영; 구재필
Original assignee: 주식회사 엘지화학
Priority date: 2016-03-09
Filing date: 2017-03-09
Publication date: 2017-09-14

Abstract

The present invention relates to an antireflective film comprising a hard coating layer and a low-refractive-index layer, which comprises: a binder resin comprising a cross-linked polymer between a photopolymerizable compound and a polysilsesquioxane substituted with one or more reactive functional groups; and inorganic microparticles dispersed in the binder resin, wherein the ten-point mean roughness (Rz) of the shape of the irregularities on the surface of the low-refractive-index layer is 0.05-0.2 μm.

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. 10-2016-0028464 dated March 9, 2016 and Korean Patent Application No. 10-2017-0029955 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 anti-reflection 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); 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.

Incidentally, 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 using scattering of light 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 commercialized. However, in the method of forming a plurality of layers as described above, the interlayer adhesion force (interface adhesion force) is increased 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 (eg, 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 due to the nanometer size particles, the antifouling property of the low refractive layer surface is greatly increased. Degraded.

Accordingly, many studies have been made to reduce the absolute reflection of light incident from the outside and to improve the antifouling property together 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 comprising a crosslinked polymer between a photopolymerizable compound and a polysilsesquioxane substituted with at least one semi-functional 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 10-point average roughness (Rz) of the concave-convex shape of the surface of the low refractive layer is 0.0 an to 0.2. This is provided. Hereinafter, an antireflection film according to a specific embodiment of the present invention will be described in detail. 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, (meth) acryl [(Meth) acryl] is meant to include both acryl and Methacryl.

In addition, (co) polymers are co-polymers and homopolymers (homo— polymer) means to include both.

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. it means. According to one embodiment of the invention, a binder resin comprising a cross-linked polymer between the photopolymerizable compound and polysilsesquioxane (polysi 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 10-point average roughness (Rz) of the concave-convex shape of the surface of the low refractive layer is 0.05 ffli to 0.2 m. Prevention films may be provided.

The present inventors have conducted research on the low refractive index layer and the antireflection film, and include the aforementioned low refractive index layer and the hard coating layer, and the above-described numerical values relating to the 10-point average roughness Rz of the uneven shape of the surface of the low refractive index layer. A satisfactory anti-reflective film can realize lower reflectance and high light transmittance, improve alkali resistance, secure excellent wear resistance or scratch resistance, and increase the sharpness of the screen of the display device while showing excellent mechanical properties. Through experiments that can confirm and completed the invention.

Specifically, the 10-point average roughness Rz of the uneven shape of the surface of the low refractive index layer is 0.05 // m to 0.2, or 0.10 / -0.180 ^, or 0.127 / m-0.141 kPa Can be.

As the ten-point average roughness (Rz) of the concave-convex shape of the surface of the low refractive index layer is 0.05 / m to 0.2 rni, the anti-reflection film derives an optimal surface concave-convex structure that can realize antireflection effect and visibility simultaneously. Could.

The surface roughness of the antireflection film is represented by the ten-point average roughness Rz of the surface irregularities. The ten-point average roughness refers to the sum of the average values of the absolute values of the five highest height peaks and the five lowest valleys, based on the average line, within the measurement length in the surface unevenness curve.

In this case, Rz, which is the height of 10-point unevenness, is 0.05 to 0.2 / ΛΠ, or 0. 10 / ΛΠ To 0.180, or 0.127 / ΛΠ to 0.141, the antireflection effect and visibility may be simultaneously implemented. If the 10-point average roughness (Rz) of the concave-convex shape of the surface of the low refractive index layer is less than 0.0¾, the antireflection effect and the poor hiding power of the panel are reduced, and the 10-point average roughness (Rz) of the concave-convex shape of the surface of the low refractive layer is reduced. ) Is more than 0.9 Hz, the resolution degradation and sharpness, such as sparkling may be reduced.

The ten-point average roughness Rz of the uneven shape of the surface of the low refractive layer can be measured using a non-contact surface profiler (3D Optical Profiler).

10 point average roughness Rz of the uneven | corrugated shape of the surface of the low refractive layer contained in the said antireflection film is 0.05 / im-0.2 / im, and the total haze of the said antireflection film is 5% or less, or 1%-5 May be%. Such an antireflection film can improve hiding power of panel defects while maintaining visibility, and can realize low reflectance and high light transmittance. Specifically, when the total haze of the antireflection film exceeds 5%, it may cause a decrease in visibility, such as a decrease in contrast ratio.

In addition, the total haze and the internal haze of the anti-reflection film may be less than, respectively, specifically, the total haze of the anti-reflection film may be 3% or less, or 2% to 3%, or 2.5% to 2/75%. In addition, the internal haze of the antireflection film may be 2.7% or less, or 2% to 2.7%, or 2.30% to 2.65%.

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 addition, the anti-reflection film has a ratio of the internal haze (Hi) to the total haze (Ha) of 97% or less, or 96% or less, or 30% to 96%, or 90% to 96%, or 92.0% to 95.90 ¾).

In general, the higher the surface haze, the more the reflection reduction effect due to scattering In this case, the effect of reducing the reflectance due to the low refractive index layer is further increased within the same refractive index range, and a smooth viewing time may be secured in the display device only when the surface haze is secured to some extent.

On the contrary, when the ratio of the internal haze to the total haze (Ha) in the anti-reflection film exceeds 97%, the surface haze (Hs) ratio of the total haze (Ha) becomes less, substantially the Not only is the antireflective film not easy to ensure a sufficiently low reflectance, but also the interference fringes of the antireflective film are easily exposed, so that the sharpness or visibility may be degraded in the finally applied display device.

In addition, the anti-reflection film may implement a low reflectance and a high light transmittance, and specifically, surface properties and optical properties may not change significantly before and after exposure to alkali. Specifically, the antireflection 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, 0.2 to 0.45, or 0.3 to 0.42. have.

The anti-reflection film was measured before and after the predetermined alkali treatment, and the measurement of the variation of the color coordinate value (b *) was carried out for 1 second to 100 seconds in an alkaline aqueous solution (sodium hydroxide, etc.) diluted with 5 to 5 OT in distilled water after optical pretreatment. It can be measured using.

The antireflection film may have an average reflectance of 2.5% or less, or 2.0% or less, 1.6% or less, or 1.10% to 2.25% in the visible light wavelength range of 380 nm to 780 nm.

The low refractive layer has a thickness of Iran to 200nm, the hard coating layer may have a thickness of 0.1 to 1 or 10. 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 semi-ungular functional group on its surface to increase mechanical properties of the low refractive index layer, for example, scratch resistance, and may include silica, alumina, Unlike the case of using fine particles such as zeolite, the alkali resistance of the low refractive index layer While improving, external appearance characteristics such as average reflectance and color can be improved.

On the other hand, the low refractive index layer is a binder resin containing a cross-linked polymer between a photopolymerizable compound and a polysilsesquioxane (po lys i I sesqui oxane) substituted with at least one semi-functional group and inorganic fine particles dispersed in the binder resin It may include.

On the other hand, the polysilsesquioxane may be represented as (! ^ ^ ^ (Where n is 4 to 30 or 8 to 20), and may have a variety of structures, such as random, ladder, cage and partial cage have.

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 substituted with one or more polysilsesquioxanes having one or more reactive functional groups substituted therein. Polyhedral oligomeric silsesquioxane (Polyhedral Oligomeric Si I sesquioxane) 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-acyclic functional groups may be substituted with silicones not having a semi-active functional group substituted therein. Can be.

As at least one of the silicones of the polyhedral oligomer silsesquioxane having the cage structure is substituted, the mechanical properties of the coating film or the binder resin formed during photopolymerization of the photopolymerizable coating composition may be improved. In addition, as the non-acyclic functional group is substituted in the remaining silicon, the molecular structural steric hindrance appears, thereby greatly reducing the frequency or probability of exposing the siloxane bond (-Si-0-) to the outside and thus the photopolymerizable property. The alkali resistance of the coating film and binder resin formed at the time of photopolymerization of a coating composition can be improved.

The semi-functional group substituted in the polysilsesquioxane is alcohol, amine, Carboxylic acids, epoxides, imides, (meth) acrylates, nitriles, norbornenes, olefins [ally, cycloalkenyl or vinyldimethylsilyl], polyethylene glycol, thiol and vinyl groups It may include one or more functional groups selected from the group consisting of, 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 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 bond site, alkyl cycloalkane (epoxy) epoxide means that the other portion of the 'alkyl' that does not bond with the cycloalkane (cyc loalkane) epoxide is the binding site.

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. In this way, as the semi-functional and un- semi-functional groups are substituted on the surface of the polysilsesquioxane, a siloxane bond (-Si-0-) is formed in the molecule in the polysilsesquioxane in which the reactive functional group is substituted at least. 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 polyhedral oligomeric silsesquioxanes (P0SSs) in which one or more of these reactive functional groups are substituted and have a cage structure include TMP Diol lsobutyl P0SS, Cyclohexanediol Isobutyl P0SS, 1, 2 ᅳ Propanediol P0SS wherein Is is substituted with at least one alcohol such as Duty 1 P0SS, 0c ta (3-hydroxy-3 methylbutyldimethyl sioxy) P0SS; Aminopropyl Isobutyl P0SS, Aminopropyl Isooctyl P0SS, Aminoethylaminopropyl Isobutyl POSS, N-Pheny 1 am i nop r opy 1 POSS, N ᅳ Me t hy 1 am i no r opy 1 Isobutyl POSS, OctaAmmonium POSS,

POSS substituted with at least one amine such as Am i nopheny 1 Cy c 1 ohexy 1 POSS and Aminophenyl Isobutyl POSS; POSS in which at least one carboxylic acid is substituted, such as Maleamic Ac-Cycl ohexy 1 POSS, Maleamic Acid-Isobutyl POSS, Oct a Maleamic Acid POSS; POSS substituted with at least one epoxide such as EpoxyCyc 1 ohexy 1 Isobutyl POSS, Epoxycycl ohexy 1 POSS, Glycidyl POSS, GlycidylEthyl POSS, Glycidyl Isobutyl POSS, Glycidyl Isooctyl 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,

POSS in which one or more (meth) acrylates are substituted, such as (Meth) 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 is substituted, such as NorbornenylEthyl POSS, Norbornenyl ethyl Isobutyl POSS, Nor bornenyl ethyl DiSi lanolsobutyl 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 in which at least one olephine such as Allyllsobutyl POSS, MonoVinyl Isobutyl POSS, OctaCyclohexenyldimethylsilyl POSS, OctaVinyldimethylsilyl POSS, OctaVinyl POSS and the like are substituted; POSS substituted with PEG of 5 to 30 carbon atoms; Or POSS 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 a portion derived from the binder resin compared to a part derived from a photopolymerizable compound from the male half functional group is one or more substituted polysilsesquioxane (p ₀ ly _S il _sesqu _oxane i) the

0.005 to 0.50, or 0.005 to 0.25, or 0.015 to 0.19. Compared to the portion derived from the photopolymerizable compound in the binder resin When the content of the portion derived from polysilsesquioxane (polysyl sesquioxane) in which at least one semi-functional functional group is substituted is too small, it may be difficult to sufficiently secure alkali resistance or scratch resistance of the low refractive index layer.

In addition, when the content of the portion derived from the polysilsesquioxane (polysi l sesquioxane) in which at least one semi-amen functional group is substituted with the portion derived from the photopolymerizable compound in the binder resin of the photopolymerizable coating composition, 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

A monomer or oligomer containing a (meth) acrylate or a vinyl group may be included. 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 tri (meth) acrylate for pentaerythrite, tetra (meth) acrylate for pentaerythri, penta (meth) acrylate for dipentaerythr, Dipentaerythri nucleus (meth) acrylate, tripentaerythrib hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, nucleamethylene diisocyanate, trimethylolpropane tri (meth) acrylate, Trimethylolpropane polyespecial tri (meth) acrylate, trimethyl propane trimethacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, nuxaethyl methacrylate, butyl methacrylate or two or more thereof Compounds, or urethane modified acrylate oligomers, epox Hitting the de acrylate Murray, ether hitting the acrylic byte can be given Murray, dendritic acrylate oligomer, or traces of these two types of compounds or more. 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 portion derived from the photopolymerizable compound in the binder resin is not limited to a large amount, the content of the photopolymerizable compound is 20% by weight to 80 in consideration of mechanical properties of the low refractive index layer or the antireflection film to be manufactured. Weight%.

In addition, as described above, the low refractive index 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 further increase 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 one or more semi-active functional groups are 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 photoreactive 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 thiol groups ( Thiol) is mentioned.

—Based—fluorine-based compounds, including photoreactive functional groups, may have a fluorine content of 1 to 60 weight ¾>. If the content of fluorine is too small in the fluorine-based compound including the photoreactive functional group, it may be difficult to sufficiently secure physical properties such as alkali resistance because the fluorine component may not be sufficiently arranged on the surface of the low refractive index layer. In addition, if the content of the fluorine 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 index layer is formed on one surface of the hard coating layer having an anti-reflection function, the anti-reflection film is subjected to a peeling voltage during a post-process to produce a product (for example, a TV or a monitor) to which the antireflection film is finally applied. In order to minimize the problems that may occur, the fluorine content of the 1% to 25% by weight A fluorine-based compound including a photobanung functional group having can be used.

The fluorine-based compound including the photoreactive functional group may further include silicon or a silicon compound. That is, the fluorine-based compound including the photoreactive functional group may optionally contain a silicon or silicon compound therein, specifically, the content of silicon in the fluorine-based compound including the photoreactive functional group is from 0.01% to 20% by weight> day. Can 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 bloso-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 may have a weight average molecular weight (weight average molecular weight in terms of polystyrene measured by the GPC method) of 2,000 to 200, 000. If the weight average molecular weight of the fluorine-based compound including the photoreactive functional group is too small, the low refractive index layer may not have sufficient alkali resistance. In addition, when the weight average molecular weight of the fluorine-based compound including the photo-reflective 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 photo-reflective 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 at least one photo-reflective functional group is substituted, and at least one fluorine is substituted for at least one carbon; ii) a heteroaliphatic compound or a heteroaliphatic ring compound 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 with at least one photoreactive functional group and at least one hydrogen is substituted with fluorine Polyether compounds, or a mixture of two or more of the above i) to iv) or a copolymer thereof.

The low refractive layer may include 1 to 75 parts by weight of the fluorine 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 fluorine-based compound including the photoreactive functional group relative to the photopolymerizable compound is too small, the low refractive index layer may not have sufficient alkali resistance.

On the other hand, the binder resin is fluorine-based in addition to the photopolymerizable compound described above

It may further include a part derived from a (meth) acrylate type compound. 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.

In the case of 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 is from 0.01% to 0.1%. May be 10%.

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 carbon number 1

It is an alkyl group, a is an integer of 0-7, b is an integer of 1-3.

[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.

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 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 ran or less and a hollow space present on the surface and / or inside thereof.

The solid inorganic nanoparticles may have a diameter of 0.5 to ΙΟΟ ^η ι ^η , or from 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. 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, thereby improving scratch and antifouling properties. It can be secured.

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 bloso-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 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 can be used as a catalyst for water and a catalyst. Hydrolysis and condensation by sol-gel reaction in the presence of Through the reaction, the fluorine-based compound may be bonded to the surface of the hollow inorganic nanoparticle.

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 organic functional groups that can be substituted on the surface of the hollow silica particles are not particularly limited, and examples thereof include (meth) acrylate groups, vinyl groups, hydroxy groups, amine groups, and allyl groups; ^An epoxy group, a hydroxyl group, an 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 300 parts by weight based on the loo 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 layer is a photopolymerizable coating composition comprising a photopolymerizable compound, inorganic fine particles and polysilyl sesquioxane substituted with one or more semi-functional functional groups on a predetermined substrate and applied It can be obtained by photopolymerizing the 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 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 is greatly limited as long as it is a compound known to be used in the photopolymerizable resin composition. It may be used without, and specifically, a benzophenone compound, acetophenone compound, biimidazole compound, triazine compound, oxime compound, or a combination of two or more thereof may 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-butane, 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. If the content of the organic solvent in the photopolymerizable coating composition is too small, defects may occur such that the flowability of the photopolymerizable coating composition is lowered, resulting in streaks in the final film. 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 photopolymerizable 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 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 may be irradiated with ultraviolet rays 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 also special It is not limited, It can change suitably according to the exposure apparatus used, the wavelength of irradiation light, or an exposure amount.

In addition, in the step of photopolymerizing the photopolymerizable coating composition, nitrogen purging may be performed to apply nitrogen atmospheric conditions. On the other hand, the hard coating layer can be used without a large limitation to the conventional known hard coating layer. As an example of the said hard coat film, the hard coat film containing the binder resin containing a photopolymerizable resin, and organic or inorganic fine particles disperse | distributed to the said binder resin;

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. Specifically, the photopolymerizable resin is a semi-ungsung acrylate oligomer group consisting of urethane acrylate oligomer, epoxide acrylate oligomer, polyester acrylate, and polyether acrylate; And dipentaerythritol nucleoacrylate, dipentaerythritol hydroxy pentaacrylate, pentaerythroli tetraacrylate, pentaerythroli triacrylate, trimethylene propyl triacrylate, propoxylated glycerol Triacrylate Trimethylpropane polyfunctional acrylate consisting of 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 monomer group.

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, and the inorganic particles may have a particle size of 1 ran to 500 nm, or 1 nm to 300 nm. .

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 acrylic resin, styrene resin, epoxide resin, and nylon. It may be organic fine particles made of a resin or inorganic fine particles made of silicon oxide, titanium dioxide, indium oxide, tin oxide, zirconium oxide and zinc oxide. The binder resin of the hard coating film 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 at least one selected from the group consisting of a cellulose polymer, an acrylic polymer, a styrene polymer, an epoxide polymer, a nylon polymer, a urethane polymer, and a polyolefin polymer. 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 the (meth) acrylate functional groups is 2 to 10, preferably 2 to 8, more preferably Preferably it is 2 to 7, it 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, tripentaerythritol hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, nusamethylene diisocyanate, trimethyl propane It may be at least one member selected from the group consisting of meth) acrylate, and trimethylolpropane 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 is in the molecule It may be a compound having one or more quaternary ammonium bases, and low molecular or polymer types may be used without limitation. 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, methacryloxypropyl It may be at least one compound selected from the group consisting of trimethoxysilane, glycidoxypropyl trimethoxysilane, and glycidoxypropyl trioxysilane.

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

【Effects of the Invention】

According to the present invention, there is provided a photopolymerizable coating composition capable of providing a low refractive index layer having both low reflectance and high light transmittance and simultaneously providing high alkali resistance and scratch resistance, and a low refractive layer obtained from such a photopolymerizable coating composition. ， Anti-reflection film may be provided that can increase the sharpness of the screen of the display device and yet exhibit excellent mechanical properties.

The low refractive index layer does not significantly reduce the appearance properties such as reflectance or light transmittance and the mechanical properties such as abrasion resistance or scratch resistance even when exposed to alkali, so that the application of an additional protective film for external surface protection 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.

Preparation Example 1 Preparation of Hard Coating Film 1 (HD1)

Pentaerythritol 13 g of triacrylate, urethane acryl oligomer (3061, Kyoeish) 10 g, urethane acryl oligomer (306T, Kyoeish) 10 g, isopropyl alcohol 20 g, photoinitiator (Irgacure 184, ciba) 2 g and leveling agent (BYK 300) Acryl-styrene copolymer resin fine particles having a refractive index of 1.555 after uniform mixing of 0.5 g (Techpolymer, volume average particle diameter: 3 im, Manufacturer: Sekisui Plastic) 2.3 g and nano silica dispersion (volume average particle size about 12 nm, Optisol-LSM, Lenco) were added 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. 150 mJ / cirf was irradiated to the dried material to prepare a hard coat film having a thickness of 6. Preparation Example 2 Preparation of Hard Coating Film 2 (HD2)

13 g of triacrylate, 10 g of urethane acryl oligomer (3061, Kyoeish), 10 g of photopolymerizable urethane acryl polymer (250,000, Daesung Chemical Co., Ltd. 8BR-500), 20 g of isopropyl alcohol, photoinitiator (Irgacure 184, ciba) ) After uniform mixing of 2 g and 0.5 g of leveling agent (BYK 300), acrylic-styrene copolymer resin fine particles (Techpolymer, volume average particle diameter: 2 / m, manufacturer: Sekisui Plastic) with refractive index of 1.555, refractive index 1.3g of acrylic-styrene copolymer resin fine particles (Techpolymer, volume average particle diameter: 2 m, manufacturer: Sekisui Plastic) and 0.03 g of nano silica dispersion (volume average particle size about 12 ran, Optisol-LSM, Lenco) To prepare a hard coating composition.

The hard coating solution composition thus obtained was applied to a triacetyl cellulose film.

Coated with # 10 mayer bar and dried at 90 ^° C for 1 min. The dried material was irradiated with ultraviolet light of 150 mJ / crf to prepare a hard coat film having a thickness of 6. Preparation Example 3 Preparation of Hard Coating Film 3 (HD3)

13 g of triacrylate, 10 g of urethane acryl oligomer (3061, Kyoeish), 10 g of photopolymerizable urethane acryl polymer (丽 250,000, Daesung Chemical, 8BR-500), 20 g of isopropyl alcohol, photoinitiator (Irgacure 184, ciba) ) Acryl-styrene copolymer resin having a refractive index of 1.555 after uniformly mixing 2 g and 0.5 g of rebalancing agent (BYK 300) 0.3 g of styrene resin spherical particles (Techpolymer, volume average particle diameter: 3.5, manufactured by Sekisui Plastic) having a refractive index of 1.0 g, a refractive index of 1.60, and a nano silica dispersion A hard coating composition was prepared by adding 0.03 g (volume average particle diameter of about 100 nm, X24-9600A, Shinetsu).

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 / cuf to prepare a hard coating film having a thickness of 6 kPa. Preparation Example 4 Preparation of Hard Coating Film 4 (HD4)

Pentaerythritol triacrylate 30 g, high molecular weight co-polymer (BEAMSET 371, Arakawa, Epoxy Acrylate, molecular weight 40,000) 2.5 g, methyl ethyl ketone 20 g, photoinitiator (Irgacure 184, ciba) 2 g and leveling agent (Tego wet 270) ) After uniformly mixing 0.5 g), 2 g of acrylic-styrene copolymer resin fine particles (Techpolymer, average particle diameter: 2 ^ m, manufacturer: Sekisui Plastic) having a refractive index of 1.544 were added 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. 150 mJ / ciif was irradiated to the dried material to prepare a hard coat film having a thickness of 6 kPa. Preparation Example 5 Preparation of Hard Coating Film 5 (HD5)

15 g of triacrylate, 10 g of urethane acryl oligomer (3061, Kyoeish), 30 g of methyl ethyl ketone, 30 g of toluene, 2 g of photoinitiator (Irgacure 184, ciba) and 0.5 g of leveling agent (Tego 410) After mixing, 1 g of styrene resin spherical particles having a refractive index of 1.59 (volume average particle diameter: 3.5, SX series, Soken) and an acryl-styrene copolymer resin fine particles having a refractive index of 1.525 (Techpolymer, volume average particle diameter: About 3 iM, manufacturer: Sekisui Plastic) Prepared.

Coated with # 10 mayer bar and dried at 90 ^° C for 1 min. The dried material was irradiated with ultraviolet light of 150 mJ / cuf to prepare a hard coat film having a thickness of 6. Preparation Example 6 Preparation of Hard Coating Film 6HD6)

Pentaerythritol 30g triacrylate, high molecular weight copolymer (BEAMSET 371, Arakawa, Epoxy Aery late, molecular weight 40,000) 2.5g, photoinitiator (Irgacure 184, ciba) 2g, methyl ethyl ketone 20g and leveling agent (Tego wet 270) After uniformly mixing 0.5 g, 2 g of acrylic-styrene copolymer resin fine particles (volume average particle diameter: 2 /, manufacturer: Sekisui Plastic) having a refractive index of 1.525 and a nano silica dispersion (volume average particle diameter about 12 nm, Optisol-LSM, Lenco) O.lg was added to prepare a hard coating composition.

Coated with # 10 mayer bar and dried at 90 ^° C for 1 min. The dried material was irradiated with ultraviolet light of 150 mJ / cuf to prepare a hard coat film having a thickness of 4. <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 MIBKCmethyl isobutyl ketone) and diacetone alcohol (DAA) were diluted in a weight ratio of 1: 1 so that the solid content was 3% by weight.

Table 1

Trimethylolpropane 41 62 _. 47 67 1 Triacrylate (1H, 1H, 6H, 6 H-perfluoro— 1, 6-nucleic acid diol diacrylate) polysilsesquioxane 6 5 0 0 4

(MA0701) (MA0701) (AC-SQ-F) Fluorine-based compound containing a photoreactive functional group 13.33 6.667 13.333 6.667 0. 1001

RS907

Photoinitiator 5 5 5 5 0.25 (Irgacure-127,

Ciba company)

1) THRULYA 4320 (catalyzed product): hollow silica dispersion (solids 20 weight D 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%, refraction 1.39) (2) Preparation of low refractive index layer and antireflection film

On the hard coat film described 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 180 mJ / citf of ultraviolet rays 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. Alkaline Pretreatment

The antireflection films obtained in Examples and Comparative Examples were soaked for 30 seconds in a 55 ^° C. aqueous NaOH solution diluted with 10% of distilled water, washed with water, and then wiped dry.

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

Average reflectance and color coordinate values in the wavelength range of 380 nm to 780 nm using the 100T mode of Sol idspec 3700 (SHIMADZU) after darkening the back surface of the film before and after the pretreatment with respect to the antireflection films obtained in Examples and Comparative Examples. (b *) was measured.

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 27 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 observed with the naked eye was observed was measured.

4. Surface roughness measurement

The ten-point average roughness of the surface irregularities of the antireflection film obtained in each of the above Examples and Comparative Examples was measured using a white light three-dimensional optical interference profile (3D opt i cal prof iler, model name: NewView 7300, Zygo). . At this time, the lens magnification used measured the area | region of 3.00 * 0.52 mm <^{2> on} 10x and 1x zoom measurement conditions.

Specifically, the antireflection film to be measured is placed on the sample stage in a flat state, and then proceeded after obtaining an opt i cal prof i ler image. At this time, the measurement was performed by setting the horizontal length to 3mm, and 10-point average roughness was calculated by obtaining two to three line prof iles from the image obtained here. 5. Haze measurement

About the antireflection film obtained in each of the above Examples and Comparative Examples

Using the HAZEMETER D-150 instrument of the Murakami color Research Laboratory, the average values of three hazes were measured according to J IS K7105.

(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: Pentaerythride is mixed with triacrylate and Ebecryl 220 (oligomer of SK cytec) in a weight ratio of 6: 1, and solid content 60 in a 2: 1 weight ratio mixed solvent of methyl ethyl ketone and toluene. Diluted to a weight%, and applied to the dry film thickness mi using wi re bar, and then the surface irregularities were flattened after drying and curing. 6. Sharpness Measurement

The image sharpness was measured using an ICM-1T of Sugar Test Instrument. The sharpness values of the slits of 1.125 s and the values of the sharpness of 0,125 s, 0.5 s, 1.0 s and 2.0 mm slit were added to compare the image sharpness.

Table 2

Average Reflectivity 1.20 1.15 1.16 2.1 1.18 1.2 1.16 2.1 1.1 (%)

Scratch Resistant 350 350 350 600 350 350 150 500 300 G (g)

Total Haze 2.678 2.514 2.721 2.707 3.124 10.028 2.667 2.719 3.138

(Ha,)

Internal haze 2.527 2.329 2.607 2.589 2.761 7.347 2.528 2.581 2.515 (Hi,%)

Hi / Ha () 94.36 92.64 95.81 95.64 88.38 73.265 94.788 94.925 80.146 Alkaline 0.34 0.41 0.38 0.3 0.28 0.4 0.9 1.08 1.3 After pretreatment

Color coordinate value (b *

) Variation

10 point average 0.141 0.127 0.167 0.171 0.473 1.121 0.146 0.168 0.632 Roughness (Rz)

Sharpness 91.6 90.9 92 91.2 74.1 64.8 92 90.9 71.2 (0.125 mm)

Image Sharpness 376.9 374.7 380 377.8 326.1 303.1 377.9 378.3 322.7 (Sum) 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. It was confirmed that it has more excellent scratch resistance compared with.

Specifically, the 10-point average roughness (Rz) of the concave-convex shape of the surface of the low refractive layer included in the anti-reflection film of the embodiment is 0.0 zm to 0. an, and the anti-reflection film has a color coordinate value (b) after alkali pretreatment. It was confirmed that the variation of *) was in the range of 0.25 to 0.45. It was also confirmed that the total haze of the antireflection film was 3% or less and the internal haze was 2.7 ¾> or less, and the ratio of the internal haze (Hi) to the total haze (Ha) of the antireflection film was 97% or less.

Meanwhile, in the image sharpness measurement result, the value in the narrow slit may be high and the image is clear, and the image sharpness measurement result for the antireflection film is 0.125. It is applicable to the high resolution display when the image sharpness in the mm slit is 80% or more and the sum of the image sharpness values excluding the 0.25 mm slit is 350% or more. It was confirmed that the numerical values of the image sharpness and the image sharpness of the 125 mm slit satisfy all of the above-mentioned ranges.

On the contrary, it was confirmed that the antireflection film of the comparative example had a relatively large variation in color coordinate values or low scratch resistance after alkali treatment. In addition, the antireflective film of the comparative example exhibits relatively high total haze (Ha) and internal haze (Hi) values, and also has a relatively low image sharpness in the 0.125 匪 slit, thus having a relatively low light transmittance and a thermal optical It is confirmed that the characteristics are shown.

Claims

[Claim]

[Claim 1]

A binder resin comprising a crosslinked polymer between a photopolymerizable compound and a polysilsesquioxane in which at least one semi-functional group is substituted; And a low refractive index layer and a hard coating layer including; inorganic fine particles dispersed in the binder resin;

10-point average roughness (Rz) of the uneven | corrugated shape of the surface of the said low refractive layer is 0.05-0.2 zm,

Anti-reflection film.

[Claim 2]

According to claim 1,

The total haze of the antireflection film is 5% or less,

The ratio of the internal haze (Hi) to the total haze (Ha) of the antireflection film is 97% or less, antireflection film.

[Claim 3]

The method of claim 1,

The antireflection film whose variation in the color coordinates (b *) of the said antireflection film is 0.7 or less before and after an alkali treatment.

[Claim 4]

The method of claim 1,

10-point average roughness (Rz) of the concave-convex shape of the surface of the low refractive index layer is a result of measuring using a non-contact surface shape measuring instrument (3D Opt i cal Prof i ler), anti-reflection film.

[Claim 5]

In U,

From the photopolymerizable compound of the binder resin contained in the low refractive index layer The weight ratio of the part derived from the polysilsesquioxane in which the semi-ungsung functional group is substituted with one or more derivatives is 0.005 to 0.50.

Anti-reflection film.

[Claim 6]

The method of claim 1,

In the group consisting of alcohol, amine, carboxylic acid, epoxide, imad, (meth) acrylate, nitrile, norbornene, olefin, polyethylene glycol, thiol and vinyl group, the reactive functional groups substituted in the polysilsesquioxane An antireflection film comprising at least one functional group selected.

[Claim 7]

The method of claim 1,

The polysilsesquioxane substituted with at least one semi-functional functional group includes a polyhedral oligomeric silsesquioxane (Polyhedral Ol igomeric Si l sesquioxane) having at least one semi-functional functional group substituted with a cage structure. ， Anti-reflection film.

[Claim 8]

According to claim 7,

At least one or more of the silicone of the polyhedral oligomeric silsesquioxane having a cage structure is substituted with a reactive functional group, the remaining non-asymmetric functional groups are substituted with a non-acyclic functional group, the anti-reflective film .

[Claim 9]

The method of claim 1,

The photopolymerizable compound comprises a (meth) acrylate or a monomer or oligomer containing a vinyl group, antireflection film.

[Claim 10]

According to claim 1,

The binder resin further comprises a crosslinked polymer between a photopolymerizable compound, a fluorine-based compound including a photoreactive functional group, and a polysilsesquioxane (po lys i sesqui oxane) in which at least one reactive functional group is substituted.

[Claim 11]

The method of claim 10,

The photoreactive functional group contained in the fluorine-based compound is at least one selected from the group consisting of a (meth) acrylate group, an epoxide group, a vinyl group (Vinyl), and a thi group, an antireflection film.

[Claim 12]

The method of claim 10,

The fluorine-based compound including the photo-banung functional group has a fluorine content of 1% by weight to 60% by weight, antireflection film.

[Claim 13]

The method of claim 10,

The fluorine-containing compound including the photo-banung functional group is i) an aliphatic compound or an aliphatic ring compound in which at least one photo-banung functional group is substituted and at least one fluorine is substituted for at least one carbon; ii) hetero aliphatic 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) a polydialkylsiloxane polymer in which at least one photoreactive functional group is substituted and at least one fluorine is substituted 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 Anti-reflection film.

[Claim 14]

The method of claim 10,

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

Anti-reflection film having a weight average molecular weight of 200, 000.

[Claim 15]

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 200nm, anti-reflection film.

[Claim 16]

According to claim 1,

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

[Claim 17]

According to claim 1,

And the hard coat film comprises a binder resin containing a photopolymerizable resin and organic or inorganic fine particles dispersed in the binder resin. [Claim 18]

The method of claim 17,

The binder resin of the hard coat film further comprises a high molecular weight (co) polymer having a weight average molecular weight of 10, 000 or more, anti-reflection film. [Claim 19]

The method of claim 1,

The antireflective film has an average reflectance of 2.5% or less in a region of 380 nm to 780 nm.