KR102055928B1

KR102055928B1 - Photosesitive coating compositoin, low reflection film, and anti-reflective film

Info

Publication number: KR102055928B1
Application number: KR1020160030391A
Authority: KR
Inventors: 김부경; 김혜민; 김헌; 장석훈; 변진석
Original assignee: 주식회사 엘지화학
Priority date: 2016-03-14
Filing date: 2016-03-14
Publication date: 2019-12-13
Also published as: KR20170106803A

Abstract

The present invention, a photopolymerizable compound; Inorganic fine particles; Fluorine-based compounds including photoreactive functional groups; Silane compounds containing at least one reactive functional group selected from the group consisting of vinyl groups and (meth) acrylate groups; Curing accelerators; And a photopolymerization initiator; and a low refractive index layer comprising a photocurable and thermosetting coating composition for producing a low refractive index layer, and a cured product of the photocurable and thermosetting coating composition, and the low refractive index layer. It relates to a prevention film.

Description

Photocurable and thermoset coating compositions, low refractive layers and antireflective films {PHOTOSESITIVE COATING COMPOSITOIN, LOW REFLECTION FILM, AND ANTI-REFLECTIVE FILM}

The present invention has a low light reflectance and a high light transmittance while at the same time can implement a high scratch resistance and antifouling resistance and can provide a anti-reflective film that can increase the clarity of the screen of the display device and the photocurable and thermosetting coating composition having a low High reflectivity and high anti-reflective, high scratch resistance and antifouling properties at the same time, and a low refractive index layer that can increase the sharpness of the screen of the display device and an anti-reflection film that exhibits excellent mechanical properties while also increasing the sharpness of the screen of the display device It is about.

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 a filler such as inorganic fine particles in a resin is coated on a base film and imparts irregularities (anti-glare: AG coating); There are a method of forming a plurality of layers having different refractive indices on the base film to use interference of light (anti-reflection: AR coating), or a method of mixing them.

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 may be obtained by reducing the amount of light entering the eye by scattering 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, the method of forming a plurality of layers as described above has a disadvantage in that scratch resistance is inferior due to weak adhesion between the layers (interfacial adhesion) as the process of forming each layer separately.

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

The present invention provides a coating composition having a photocurability and a thermosetting property capable of simultaneously providing high anti-scratch and antifouling properties while having a low reflectance and a high light transmittance and providing an antireflection film capable of increasing the sharpness of a screen of a display device. It is to.

In addition, the present invention is to provide a low refractive index layer that can implement a high scratch resistance and antifouling properties at the same time while having a low reflectance and a high light transmittance and can increase the sharpness of the screen of the display device.

In addition, the present invention is to provide an anti-reflection film that can increase the sharpness of the screen of the display device while showing excellent mechanical properties.

In the present specification, a photopolymerizable compound; Inorganic fine particles; Fluorine-based compounds including photoreactive functional groups; Silane compounds containing at least one reactive functional group selected from the group consisting of vinyl groups and (meth) acrylate groups; Curing accelerators; And it provides a coating composition having a photocurable and thermosetting for the low refractive index layer comprising a photoinitiator.

In addition, in the present specification, a low refractive layer including a cured product of the coating composition having the photocurable and thermosetting properties is provided.

In addition, in the present specification, the low refractive layer; And a hard coating layer formed on one surface of the low refractive layer.

Hereinafter, a coating composition, a low refractive index layer, and an antireflection film having photocurable and thermosetting properties according to specific embodiments of the present invention will be described in more detail.

In the present specification, the photopolymerizable compound is collectively referred to as a compound that causes a 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, (co) polymer is meant to include both co-polymers and homo-polymers.

Further, silica hollow particles are silica particles derived from a silicon compound or an organosilicon compound, and mean particles having a void space on the surface and / or inside of the silica particles.

According to one embodiment of the invention, a photopolymerizable compound; Inorganic fine particles; Fluorine-based compounds including photoreactive functional groups; Silane compounds containing at least one reactive functional group selected from the group consisting of vinyl groups and (meth) acrylate groups; Curing accelerators; And a photopolymerization initiator; comprising, a coating composition having a photocurable and thermosetting for low refractive layer production can be provided.

The present inventors have conducted research on the low refractive index layer and the antireflection film, and the photocurable and thermosetting compounds including a silane-based compound containing at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group. When using the coating composition having a low reflectance and a high light transmittance, it is possible to increase the clarity of the screen of the low refractive index layer and the display device that can achieve excellent wear resistance or scratch resistance, but also exhibits excellent mechanical properties Experiments confirmed that it can provide and completed the invention.

The low refractive index layer provided from the photocurable and thermosetting coating composition of the embodiment can increase the sharpness of the screen of the display device and has excellent scratch resistance, and thus can be easily applied to the display device or the polarizing plate manufacturing process without great limitation. .

Previously, in order to improve the scratch resistance of the low refractive layer included in the antireflection film, a method of adding various nanometer-sized particles (eg, particles of silica, alumina, zeolite, etc.) has been mainly attempted. According to the present invention, it is difficult to greatly increase scratch resistance, and the nanometer-sized particles make it difficult to control the surface properties of the low refractive layer.

In contrast, the photocurable and thermosetting coating composition of the embodiment includes a silane-based compound including at least one reactive functional group selected from the group consisting of vinyl groups and (meth) acrylate groups, and thus has low reflectance and high light transmittance. In addition, the present invention can provide a low refractive index layer having high scratch resistance at the same time, and can also improve the performance or quality of an antireflection film or a display device to which such an antireflection film is applied.

Specifically, the silane-based compound including at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group is thermoset and photocurable of the coating composition having the photocurable and thermosetting properties due to the reactive functional group. Mechanical properties of the coating film or binder resin formed during the coating, for example, scratch resistance can be improved. In addition, the coating composition having a photocurable and thermosetting of the embodiment includes a silane-based compound including at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group, the coating composition When the additional heat curing after heat curing and photocuring can be improved more scratch resistance.

In addition, the coating composition having the photocurable and thermosetting properties of the embodiment due to the silane functional group or silicon atom included in the silane compound including at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group. It is possible to improve the internal characteristics of the low refractive index layer formed from. More specifically, as the silane functional groups or silicon atoms included in the silane-based compound are uniformly distributed in the low refractive layer, a lower average reflectance may be realized, and due to the silane functional groups or silicon atoms, The uniformly distributed inorganic fine particles may be uniformly combined with the photopolymerizable compound to improve scratch resistance of the antireflective film to be manufactured.

As described above, as the silane-based compound including at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group has a chemical structure simultaneously containing the reactive functional group and the silicon atom In addition, the low refractive index internal properties formed from the photocurable and thermosetting coating compositions of the embodiment may be optimized for lowering the refractive index, and thus the low refractive index layer may realize low reflectance and high light transmittance, and uniformity. It is possible to secure a more crosslinking density to ensure better wear resistance or scratch resistance.

Specifically, the silane compound including at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group may contain 100 to 1000 g / mol equivalents of the reactive functional group.

If the content of the reactive functional group is too small in the silane compound containing at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group, the coating composition having the photocurable and thermosetting of the embodiment It may be difficult to sufficiently increase the scratch resistance or mechanical properties of the low refractive index layer formed from.

On the other hand, if the content of the reactive functional group is too high in the silane compound containing at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group, having the photocurable and thermosetting of the embodiment The homogeneity or dispersibility of the inorganic fine particles in the low refractive index layer formed from the coating composition may be lowered, and thus the light transmittance of the low refractive index layer may be lowered.

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

Specifically, the silane compound containing at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group is at least one reactive functional group 1 selected from the group consisting of a vinyl group and a (meth) acrylate group. As described above, an organic functional group including at least one trialkoxysilane group having an alkylene group having 1 to 10 carbon atoms and a urethane functional group may be included. The trialkoxysilane group may be a functional group in which three alkoxy having 1 to 3 carbon atoms are substituted with a silicon compound.

Although the specific chemical structure of the silane compound including at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group is not limited, specific examples thereof include the compounds of the following Chemical Formulas 1 to 3 have.

[Formula 1]

[Formula 2]

[Formula 3]

The photocurable and thermosetting coating composition of the embodiment is a silane-based compound 2 to one or more containing at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group relative to 100 parts by weight of the photopolymerizable compound It may include 40 parts by weight.

When the content of the silane-based compound including at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group in the photocurable and thermosetting coating composition compared to the photopolymerizable compound is too small, It may be difficult to sufficiently secure the scratch resistance of the coating film or binder resin formed during curing of the coating composition having photocurability and thermosetting. In addition, when the content of the silane-based compound containing at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group compared to the photopolymerizable compound in the photocurable and thermosetting coating composition is too large The compatibility with other components included in the photocurable and thermosetting coating composition is greatly reduced, so that haze occurs in the low refractive index layer or the antireflection film prepared from the photocurable and thermosetting coating composition, or the transparency thereof. May be lowered and scratch resistance may be lowered.

On the other hand, the photocurable and thermosetting coating composition of the embodiment may include a fluorine-based compound including a photoreactive functional group. As the fluorine-based compound including the photoreactive functional group is included, the low refractive index layer and the antireflection film prepared from the photocurable and thermosetting coating composition may have lower reflectance and improved light transmittance, and also have alkali and scratch resistance. Can be made higher.

The fluorine-based compound may include or replace one or more photoreactive functional groups, and the photoreactive functional group means a functional group capable of participating in a 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 a polymerization reaction by irradiation of light, and specific examples thereof may include (meth) acrylate groups, epoxide groups, vinyl groups, or thiol groups ( Thiol).

The fluorine-based compound including the photoreactive functional group may have a fluorine content of 1 to 60% by weight. When the content of fluorine is too small in the fluorine-based compound including the photoreactive functional group, the fluorine component may not be sufficiently arranged on the surface of the final resultant obtained from the photocurable and thermosetting coating composition of the embodiment, so that the physical properties such as alkali resistance are sufficient. It can be difficult to secure. In addition, if the content of fluorine in the fluorine-based compound including the photoreactive functional group is too large, the surface properties of the final product obtained from the photocurable and thermosetting coating composition of the embodiment is reduced or defective rate during the post process to obtain the final product This can be high. On the other hand, in order to minimize the problems caused by the peeling voltage that may occur during the post-process to produce the final product (for example, TV or monitor) to which the anti-reflection film is applied, the low refractive index layer is 1% by weight to 25 Fluorine-based compounds including photoreactive functional groups having a fluorine content of weight percent.

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, and specifically, the content of silicon in the fluorine-based compound including the photoreactive functional group may be 0.1 wt% to 20 wt%. .

Silicon contained 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 obtained from the photocurable and thermosetting coating composition of the embodiment. On the other hand, when the content of silicon in the fluorine-based compound including the photoreactive functional group is too large, alkali resistance of the low refractive layer obtained from the photocurable and thermosetting coating composition of the embodiment 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 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 layer obtained from the photocurable and thermosetting coating composition of the embodiment may not have sufficient alkali resistance. In addition, when the weight average molecular weight of the fluorine-based compound including the photoreactive functional group is too large, the low refractive layer obtained from the photocurable and thermosetting coating composition of the embodiment may not have sufficient durability or scratch resistance.

Specifically, the fluorine-based compound including the photoreactive functional group includes: i) an aliphatic compound or an aliphatic ring compound in which one or more photoreactive functional groups are 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 silicone; iv) polyether compounds substituted with one or more photoreactive functional groups and at least one hydrogen substituted with fluorine, or mixtures of two or more of the above i) to iv) or copolymers thereof.

The photocurable and thermosetting coating composition 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 an excessive amount to the photopolymerizable compound, the coating property of the photocurable and thermosetting coating composition of the embodiment is lowered, or the low yield obtained from the photocurable and thermosetting coating composition of the embodiment. The 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 layer obtained from the photocurable and thermosetting coating composition of the embodiment may not have sufficient alkali resistance.

Meanwhile, the photopolymerizable compound may include a monomer or oligomer including a (meth) acrylate or a vinyl group. Specifically, the photopolymerizable compound may include a monomer or oligomer containing (meth) acrylate or vinyl group of one or more, two or more, or three or more.

Specific examples of the monomer or oligomer containing the (meth) acrylate include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth). ) Acrylate, tripentaerythritol hepta (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxy tri (meth) acrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacryl Latex, butanediol dimethacrylate, hexaethyl methacrylate, butyl methacrylate or mixtures of two or more thereof, or urethane modified acrylate oligomers, epoxide acrylate oligomers, etheracrylate oligomers, dendritic acrylates Oligomers, or two kinds thereof The above mixture is mentioned. At this time, the molecular weight of the oligomer is preferably 1,000 to 10,000.

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

Although the content of the photopolymerizable compound in the photocurable and thermosetting coating composition is not significantly limited, considering the mechanical properties of the low refractive index layer or the anti-reflection film to be produced, the coating composition having the photocurable and thermosetting properties The content of the photopolymerizable compound in solids may be 20% by weight to 80% by weight. Solid content of the photocurable and thermosetting coating composition means only a solid component of the photocurable and thermosetting coating composition except for components such as liquid components, for example, organic solvents that may be optionally included as described below. .

On the other hand, the photopolymerizable compound may further include a fluorine-based (meth) acrylate compound in addition to the monomer or oligomer described above. 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 10% 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 an alkyl group having 1 to 6 carbon atoms, 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.

The photocurable and thermosetting coating composition of the embodiment may include inorganic fine particles, and may include inorganic nanoparticles commonly known in consideration of properties of a low refractive index layer or an antireflection film.

The photocurable and thermosetting coating composition may include 10 to 350 parts by weight of the inorganic fine particles, or 50 to 300 parts by weight, based on 100 parts by weight of the photopolymerizable compound. When the inorganic fine particles are added in an excessive amount, scratch resistance or abrasion resistance of the coating film may decrease due to a decrease in the content of the binder.

Specifically, the inorganic fine particles may include at least one member selected from the group consisting of hollow inorganic nanoparticles having a diameter of 200 nm or less and solid inorganic nanoparticles having a diameter of 100 nm or less.

The hollow inorganic nanoparticles refer to particles having a maximum diameter of 200 nm or less and having a void space on the surface and / or inside thereof. The hollow inorganic nanoparticles may have a diameter of 1 to 200 nm, or 10 to 100 nm.

In addition, the inorganic fine particles may include solid inorganic nanoparticles having a diameter of 100 nm or less. The solid inorganic nanoparticles refer to particles having a maximum diameter of 100 nm or less and having no empty space therein. The solid inorganic nanoparticles may have a diameter of 0.5 nm to 100 nm, or 1 nm to 50 nm.

In addition, each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles may each have at least one reactive group selected from the group consisting of (meth) acrylate groups, epoxide groups, vinyl groups (Vinyl), and thiol groups (Thiol) It may contain functional groups.

In addition, as the hollow inorganic nanoparticles, the surface of the hollow inorganic nanoparticles may be used alone or mixed 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, and thus the hollow inorganic nanoparticles may be more uniformly distributed in the coating composition having the photocurable and thermosetting properties of the embodiment. And the durability and scratch resistance of the film obtained from the coating composition having the photocurability and the thermosetting property can be further improved.

Particle coating methods or polymerization methods commonly known as coating the fluorine-based compound on the surface of the hollow inorganic nanoparticles can be used without any significant limitation. For example, the hollow inorganic nanoparticles and the fluorine-based compound may be reacted with water and a catalyst. By sol-gel reaction in the presence of the fluorine-based compound can be bonded to the surface of the hollow inorganic nanoparticles through hydrolysis and condensation reaction.

Specific examples of the hollow inorganic nanoparticles include hollow silica particles. In addition, the hollow silica particles may be included in the composition in the form of a colloid dispersed in a predetermined dispersion medium. The colloidal phase including the hollow silica particles may include an organic solvent as a dispersion medium.

In this case, the hollow silica may include a predetermined functional group maximized on the surface in order to be more easily dispersed in the organic solvent. Examples of the organic functional group that can be substituted on the surface of the hollow silica particles are not particularly limited, and for example, a (meth) acrylate group, a vinyl group, a hydroxy group, an amine group, an allyl group, an epoxy group, a hydroxy group, an isocyanate group, an amine Groups, or fluorine and the like may be substituted on the hollow silica surface.

The solid content of the hollow silica particles in the colloidal phase of the hollow silica particles may be determined in consideration of the content range of the hollow silica in the photocurable and thermosetting coating composition or the viscosity of the photocurable and thermosetting coating composition. For example, the solid content of the hollow silica particles in the colloidal phase may be 5% by weight to 60% by weight.

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

On the other hand, the photocurable and thermosetting coating composition may include a curing accelerator that can promote thermosetting. The specific example of the said hardening accelerator is not limited, Usually, a well-known hardening accelerator can be used 1 type or in mixture of 2 or more.

Specifically, examples of the curing accelerator include organic acid metal salts such as Cu, Fe, Co, Mn, Al, Ti, Zr, Ni, such as octylic acid, stearic acid, naphthenic acid, and acetylacetonate, Ti, Sn, and Bi. Metal alkoxides such as, Zr and Al; Phenol compounds such as octylphenol and nonylphenol; Aliphatic alcohols such as 1-butanol and 2-ethylhexanol; 2-methyl imidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methyl Imidazole derivatives such as -imidazole, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole; Amine compounds such as dicyandiamide, benzyldimethylamine and 4-methyl-N, N-dimethylbenzylamine; Phosphine- or phosphonium-based phosphorus compounds can be used. Among the above curing accelerators, metal complex compounds of cobalt, aluminum, copper, manganese, zirconium or nickel can be preferably used, for example, copper octylate, octylate cobalt, aluminum octylate, octylate manganese, copper stearate, Cobalt stearate, aluminum stearate, copper naphthenate, cobalt naphthenate, aluminum naphthenate, manganese naphthenate, acetylacetone copper (II), acetylacetone cobalt (II), acetylacetone cobalt (III), acetylacetone iron ( III), acetylacetone manganese (II), acetylacetone manganese (III), acetylacetone aluminum (III), acetylacetone zirconium (IV), acetylacetone (II) nickel, tetrabutoxyzirconium, tetrakis (2-ethyl- 1,3-hexanediol rato) titanium, tetraisopropoxytitanium, tetra-n-butoxytitanium and the like can be preferably used.

The coating composition having a photocurable and thermosetting composition for producing a low refractive index layer of the embodiment is based on 100 parts by weight of the silane compound including at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group 0.01 to 30 parts by weight, or 0.05 to 20 parts by weight of a curing accelerator.

When the content of the curing accelerator is too small compared to the silane-based compound, the silane-based compound does not sufficiently crosslink in the coating composition or the low refractive index layer formed from the coating composition has sufficient mechanical properties or scratch resistance. May not have

In addition, when the content of the curing accelerator is too excessive compared to the silane-based compound, some of the curing accelerator may remain as an impurity, rather the cross-linking of the silane-based compound in the coating composition is inhibited or from the coating composition The low refractive index layer formed may have sufficient mechanical properties and scratch resistance.

Meanwhile, the photopolymerization initiator may be used without any limitation as long as it is a compound known to be used in the photocurable resin composition. Specifically, a benzophenone compound, acetophenone compound, biimidazole compound, and triazine compound , Oxime compounds or mixtures of two or more 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 0.1 to 100 parts by weight. If the amount of the photopolymerization initiator is too small, an uncured material remaining in the photocuring step of the photocurable and thermosetting 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.

On the other hand, the coating composition having a photocurable and thermosetting may further include an organic solvent.

Non-limiting examples of the organic solvent include ketones, alcohols, acetates and ethers, or mixtures 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 a mixture of two or more thereof.

The organic solvent is added at the time of mixing each component included in the photocurable and thermosetting coating composition or included in the photocurable and thermosetting coating composition while each component is added in a dispersed or mixed state in an organic solvent. Can be. If the content of the organic solvent in the photocurable and thermosetting coating composition is too small, defects may occur such as streaks in the final manufactured film due to the deterioration in flowability of the photocurable and thermosetting coating composition. In addition, when the excessive amount of the organic solvent is added, the solid content is lowered, coating and film formation is not enough, the physical properties and surface properties of the film may be lowered, and defects may occur in the drying and curing process. Accordingly, the photocurable and thermosetting 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, according to another embodiment of the invention, a low refractive index layer comprising a cured product of the coating composition having the photocurable and thermosetting may be provided.

As described above, the low refractive index layer provided from the coating composition having a photocurable and thermosetting composition comprising a silane compound containing at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group is low. Reflectance and high light transmittance can be realized, excellent wear resistance or scratch resistance can be secured, and can be easily applied to a display device or polarizing plate manufacturing process.

The low refractive index layer is characterized in that the silane compound includes at least one reactive functional group selected from the group consisting of vinyl groups and (meth) acrylate groups included in the photocurable and thermosetting coating compositions of the above-described embodiments. Will follow. Specifically, the silane-based compound including at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group includes the reactive functional groups, and thus the mechanical properties of the low refractive layer, for example, scratch resistance. It is possible to improve the properties and improve the alkali resistance of the low refractive index layer, unlike the case of using fine particles such as silica, alumina, zeolite and the like previously known.

Specifically, the silane-based compound including at least one reactive functional group has a more uniform and wider range of reactive functional groups than the photopolymerizable compound, compared to fine particles such as silica, alumina, and zeolite, which are commonly known due to their chemical structure. As a result, external characteristics such as average reflectance and color of the low refractive index layer and scratch resistance show a small change rate even when exposed to alkali, and the physical-chemical change due to alkali exposure is relatively small. Is confirmed.

In addition, as described above, the internal characteristics of the low refractive index layer may be improved due to the silane functional groups or silicon atoms included in the silane-based compound including at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group. More specifically, as the silane functional groups or silicon atoms included in the silane-based compound are uniformly distributed in the low refractive layer, a lower average reflectance may be realized, and the low refractive index may be due to the silane functional groups or silicon atoms. Inorganic fine particles uniformly distributed in the layer may be uniformly combined with the components constituting the binder resin of the low refractive index layer to improve scratch resistance of the antireflection film to be finally produced.

The low refractive layer is a photopolymerizable compound; Fluorine-based compounds including photoreactive functional groups; And a silane compound containing at least one reactive functional group selected from the group consisting of a vinyl group and (meth) acrylate group; It may include a binder resin containing a crosslinked polymer of the liver and inorganic fine particles dispersed in the binder resin.

In addition, as described above, the low refractive index layer may include a portion derived from a fluorine-based compound including a photoreactive functional group. As the fluorine-based compound including the photoreactive 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.

The photopolymerizable compound; Inorganic fine particles; Fluorine-based compounds including photoreactive functional groups; Silane compounds containing at least one reactive functional group selected from the group consisting of vinyl groups and (meth) acrylate groups; Curing accelerators; And about the photoinitiator includes all the above-mentioned information in one embodiment of the invention.

The low refractive layer may be obtained by applying the photocurable and thermosetting coating composition on a predetermined substrate and thermosetting and photocuring the applied resultant. The specific kind and thickness of the substrate are not particularly limited, and a substrate known to be used for the production of a low refractive index layer or an antireflection film can be used without any significant limitation. Although the order of the thermosetting and photocuring is not limited, it is preferable to first photocure after the thermal curing (heat treatment) of the coating composition.

Methods and apparatuses conventionally used for applying the photocurable and thermosetting coating compositions may be used without particular limitations, for example, bar coating methods such as Meyer bar, gravure coating methods, 2 roll reverse coating methods, Vacuum slot die coating and 2 roll coating can be used.

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

As the photocurable and thermosetting coating composition includes a silane-based compound comprising at least one reactive functional group selected from the group consisting of vinyl groups and (meth) acrylate groups, the photocurable and The coating composition having thermosetting may be heat treated or dried in a state where it is applied on a predetermined substrate. Specifically, the photocurable and thermosetting coating composition may be heat-treated or dried for 1 minute to 30 minutes at a temperature of 40 ℃ to 150 ℃ at a relative humidity of 30RH% to 90RH% prior to the photocuring.

In the step of photocuring the coating composition having a photocurable and thermosetting properties can be irradiated with ultraviolet light or visible light having a wavelength of 200 ~ 400nm, the exposure dose is preferably 100 to 4,000 mJ / ㎠. Exposure time is not specifically limited, either, According to the exposure apparatus used, wavelength of an irradiation light, or exposure amount, it can change suitably.

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

The low refractive layer of the embodiment may have an average reflectance of 2.0% or less, or 1.30% or less, or 1.23% or less, or 1.07% or less.

On the other hand, according to another embodiment of the invention, the low refractive layer; And a hard coating layer formed on one surface of the low refractive index layer may be provided.

The low refractive index layer includes all the details described in the above-described embodiment.

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 photocurable resin and a high molecular weight (co) polymer having a weight average molecular weight of 10,000 or more, and organic or inorganic fine particles dispersed in the binder resin. have.

The high molecular weight (co) polymer may be one or more selected from the group consisting of cellulose polymers, acrylic polymers, styrene polymers, epoxide polymers, nylon polymers, urethane polymers, and polyolefin polymers.

The photocurable resin included in the hard coating layer is a polymer of a photocurable compound that may cause a polymerization reaction when light such as ultraviolet rays is irradiated, and may be conventional in the art. Specifically, the photocurable resin is a reactive acrylate oligomer group consisting of urethane acrylate oligomer, epoxide acrylate oligomer, polyester acrylate, and polyether acrylate; And dipentaerythritol hexaacrylate, dipentaerythritol hydroxy pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylene propyl triacrylate, propoxylated glycerol triacrylate, trimethylpropane ethoxy tri At least one member selected from the group of polyfunctional acrylate monomers consisting of acrylate, 1,6-hexanediol diacrylate, propoxylated glycero triacrylate, tripropylene glycol diacrylate, and ethylene glycol diacrylate It may include.

Although the particle diameter of the organic or inorganic fine particles is not specifically limited, for example, the organic fine particles may have a particle diameter of 1 to 10 μm, and the inorganic particles may have a particle size of 1 nm to 500 nm, or 1 nm to 300 nm. Can have.

In addition, specific examples of the organic or inorganic fine particles 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 may be silicon oxide, titanium dioxide, or indium oxide. And inorganic fine particles consisting of tin oxide, zirconium oxide and zinc oxide.

The hard coat film may be formed from an anti-glare coating composition comprising organic or inorganic particulates, photocurable resins, photoinitiators and high molecular weight (co) polymers having a weight average molecular weight of at least 10,000.

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

The photocurable resin included in the hard coating layer is a polymer of a photocurable compound that may cause a polymerization reaction when light such as ultraviolet rays is irradiated, and may be conventional in the art. However, preferably, the photocurable compound may be a polyfunctional (meth) acrylate-based monomer or oligomer, wherein the number of (meth) acrylate-based functional groups is 2 to 10, preferably 2 to 8, more preferably Preferably 2 to 7 is advantageous in terms of securing physical properties of the hard coating layer. More preferably, the photocurable compound is pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipenta At least one selected from the group consisting of erythritol hepta (meth) acrylate, tripentaerythritol hepta (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane polyethoxy tri (meth) acrylate Can be.

The antistatic agent may be a quaternary ammonium salt compound, a conductive polymer or a mixture thereof. Here, the quaternary ammonium salt compound may be a compound having one or more quaternary ammonium salt groups in a molecule, and may use a low molecular type or a polymer type without limitation. In addition, the conductive polymer may be a low molecular type or a polymer type without limitation, the kind thereof may be conventional in the art to which the present invention pertains, and is not particularly limited.

Binder resin of the photocurable resin; And an antistatic agent dispersed in the binder resin may further include one or more compounds selected from the group consisting of alkoxy silane oligomers and metal alkoxide oligomers.

The alkoxy silane compound may be conventional in the art, but preferably tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methacryloxypropyl It may be one or more compounds selected from the group consisting of trimethoxysilane, glycidoxypropyl trimethoxysilane, and glycidoxypropyl triethoxysilane.

In addition, the metal alkoxide-based oligomer may be prepared through a sol-gel reaction of a 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 with water rapidly, the sol-gel reaction may be performed by diluting the metal alkoxide compound in an organic solvent and slowly dropping water. At this time, in consideration of the 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 be a transparent film having 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.

According to the present invention, the present invention has a low reflectance and a high light transmittance while at the same time can implement a high scratch resistance and antifouling properties and can provide a light-curing and thermosetting properties that can provide an anti-reflection film that can increase the sharpness of the screen of the display device Its coating composition and low reflectance and high light transmittance can simultaneously achieve high scratch resistance and antifouling properties, and a low refractive index layer that can increase the sharpness of the screen of the display device and excellent mechanical properties while increasing the sharpness of the screen of the display device. An antireflection film may be provided.

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 : Manufacturing of Hard Coating Films>

Preparation Example 1

KYOEISHA salt type antistatic hard coating solution (50 wt% solids, product name: LJD-1000) was coated on a triacetyl cellulose film with # 10 mayer bar and dried at 90 ° C for 1 minute, followed by 150 mJ / ㎠ Irradiation produced a hard coat film having a thickness of about 6 μm.

Preparation Example 2

After uniformly mixing 30 g of pentaerythritol triacrylate, 2.5 g of high molecular weight copolymer (BEAMSET 371, Arakawa, Epoxy acrylate, molecular weight of about 40,000), 20 g of methyl ethyl ketone and 0.5 g of leveling agent (Tego wet 270), A hard coating composition was prepared by adding 2 g of acrylic-styrene copolymer resin fine particles (volume average particle diameter: about 2 μm, manufacturer: Sekisui Plastic) having a refractive index of 1.525.

The hard coating composition thus prepared was coated on a triacetyl cellulose film with # 10 mayer bar and dried at 90 ° C. for 1 minute, thereby irradiating 150 mJ / cm 2 of ultraviolet light to prepare a hard coating film having a thickness of about 6 μm. It was.

< Example And Comparative example : Manufacturing of Antireflection Films>

(1) Preparation of coating composition (LR) having photocurability and thermosetting for low refractive layer production

The components shown in Table 1 were mixed, and the mixture was diluted with 5% by weight of solids in a solvent in which MIBK (methyl isobutyl ketone) and diacetone alcohol (DAA) were mixed at a weight ratio of 1: 1.

(Unit: g) LR 1 LR 2 LR 3 LR 4 Hollow Silica
(THRULYA 4320) 250 250 220 220 Silane-Based Compounds Including Reactive Functional Groups X-12-1048 X-12-1050 4 8 3 6 Trimethylol prefilled triacrylate 39 35 39 36 Irgacure-127 4.8 4.6 3.85 3.7 Fluorine-based compound including photoreactive functional group RS537 5 5 25 25 Tetrabutoxytitanium 0.2 0.4 0.15 0.3

(Unit: g) LR 5 LR 6 LR 7 Hollow Silica
(THRULYA 4320) 250 250 220 Silane-Based Compounds Including Reactive Functional Groups - - - Trimethylol prefilled triacrylate 45 43 42 Irgacure-127 5 5 4 Fluorine-based compound including photoreactive functional group RS537 0 5 25 Tetrabutoxytitanium - - -

1) THRULYA 4320 (catalytic product): hollow silica dispersion (20 wt% solids in MIBK solvent)

2) X-12-1048: Silane compound containing a reactive functional group ((meth) acrylate group equivalent: 300 g / mol, weight average molecular weight about 480 (GPC measurement), manufactured by Shin-Etsu)

3) X-12-1050: Silane compound containing a reactive functional group ((meth) acrylate group equivalent: 150 g / mol, weight average molecular weight about 2470 (measured by GPC), manufactured by Shin-Etsu)

4) RS537 (manufactured by DIC Corporation): Fluorine compound containing photoreactive functional group and containing a small amount of silicon, diluted to 40% by weight of solids in MIBK solvent

5) MIBK-SD (manufactured by Nissan Chemical): Nanosilica dispersion diluted to 30% solids in MIBK solvent

(2) Low refractive layer And production of antireflective films

On the hard coating film described in Table 3 above, the coating composition having photocurable and thermosetting properties obtained in Tables 1 and 2, respectively, at 50% humidity was coated with # 3 mayer bar and dried at 90 ° C. for 5 minutes. . In addition, an antireflection film was prepared by irradiating 180 mJ / cm 2 ultraviolet rays to the dried material under nitrogen purge to form a low refractive layer having a thickness of 110 nm.

< 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.

One. Average reflectance measurement of antireflective film

The average reflectance which the antireflective films obtained by the Example and the comparative example show in visible region (380-780 nm) was measured in 100T mode using the Solidspec 3700 (SHIMADZU) apparatus.

2. Scratch resistance Measure

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 the examples and the comparative examples. The scratch resistance was evaluated by confirming the maximum load of less than one scratch of less than 1cm observed by the naked eye.

Hard coating
film Low refractive layer Average reflectance
(%) Scratch resistance
(g) Example 1 HD1 LR1 1.01 400 Example 2 HD2 LR1 1.04 400 Example 3 HD1 LR2 1.00 400 Example 4 HD1 LR3 1.23 500 Example 5 HD1 LR4 1.19 500 Example 6 HD2 LR4 1.21 500 Comparative Example 1 HD1 LR5 1.12 50 Comparative Example 2 HD1 LR6 1.10 200 Comparative Example 3 HD1 LR8 1.32 400

As confirmed in Table 3, it was confirmed that the antireflection film of the example exhibits a relatively low level of reflectance, specifically, 1.23% or less, or 1.04% or less, and at the same time, may realize high scratch resistance. That is, since the anti-reflection film of the above embodiment does not significantly reduce the mechanical properties such as scratch resistance in the manufacturing process of the display device, it is possible to omit the application of an additional protective film for protecting the outer surface, thereby simplifying the production process and producing the You can save money.

On the contrary, it was confirmed that the antireflection film of the comparative example exhibited relatively high reflectance and relatively poor level of scratch resistance compared to the examples.

3. After additional heat treatment Scratch resistance Measure

After the antireflection films obtained in Examples 3 and 5 were further heat treated at 90 ° C. for one hour, scratch resistance was again evaluated. Specifically, the load of the steel wool (# 0000) with respect to the surface of each of the additional heat-treated anti-reflection film and reciprocating 10 times at a speed of 24 rpm, the maximum of 1 cm or less scratches observed with the naked eye The scratch resistance was evaluated by checking the load.

Scratch resistance (g) Example 3 500 Example 5 600

As confirmed in Table 4, it is confirmed that the antireflection films of Examples 3 and 5 can further improve scratch resistance when thermally cured. Accordingly, the anti-reflection film of the embodiment can be easily improved and adjusted the scratch resistance while maintaining a low level of reflectance and mechanical properties.

Claims

Photopolymerizable compounds; Inorganic nanoparticles; Fluorine-based compounds including photoreactive functional groups; Silane compounds containing at least one reactive functional group selected from the group consisting of vinyl groups and (meth) acrylate groups; Curing accelerators; And a photopolymerization initiator;
Coating composition having photocurable and thermosetting for low refractive layer production.

The method of claim 1,
The silane-based compound including at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group contains the reactive functional groups in an amount of 100 to 1,000 g / mol equivalents, and a sight for producing a low refractive index layer. Coating composition having chemical and thermosetting properties.

The method of claim 1,
The silane-based compound including at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group has a weight average molecular weight of 100 to 5,000, and has photocurability and thermosetting for low refractive index production. Coating composition.

The method of claim 1,
The silane compound containing at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group
Low refractive index comprising at least one reactive functional group selected from the group consisting of vinyl groups and (meth) acrylate groups, at least one trialkoxysilane group bonded with an alkylene group having 1 to 10 carbon atoms and an organic functional group including a urethane functional group Coating composition having photocurable and thermoset for layer preparation.

The method of claim 1,
Comprising 2 to 40 parts by weight of the silane-based compound containing at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group with respect to 100 parts by weight of the photopolymerizable compound, a view for producing a low refractive index layer Coating composition having chemical and thermosetting properties.

The method of claim 1,
The photopolymerizable compound includes a monomer or oligomer comprising a (meth) acrylate or a vinyl group, a coating composition having a photocurable and thermosetting for low refractive index production.

The method of claim 1,
The photoreactive functional group contained in the fluorine-based compound is at least one member selected from the group consisting of (meth) acrylate group, epoxide group, vinyl group (Vinyl) and thiol group (Thiol), photocurability and Coating composition having thermosetting.

The method of claim 1,
The fluorine-based compound including the photoreactive functional group has a fluorine content of 1% by weight to 60% by weight, the coating composition having a photocurable and thermosetting for low refractive index manufacturing.

The method of claim 1,
The fluorine-based compound including the photoreactive functional group includes: i) an aliphatic compound or an aliphatic ring compound in which one or more photoreactive functional groups are 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) at least one photoreactive functional group and a polydialkylsiloxane polymer substituted with at least one fluorine in at least one silicon; And iv) a polyether compound substituted with at least one photoreactive functional group and at least one hydrogen is substituted with fluorine; and at least one selected from the group consisting of
Coating composition having photocurable and thermosetting for low refractive layer production.

The method of claim 1,
The fluorine-based compound including the photoreactive functional group has a weight average molecular weight of 2,000 to 200,000, a coating composition having a photocurable and thermosetting for low refractive index manufacturing.

The method of claim 1,
1 to 75 parts by weight of the fluorine-based compound including the photoreactive functional group with respect to 100 parts by weight of the photopolymerizable compound, a coating composition having a photocurable and thermosetting for the low refractive layer production.

The method of claim 1,
The inorganic nanoparticles include at least one member selected from the group consisting of hollow inorganic nanoparticles having a diameter of 200 nm or less and solid inorganic nanoparticles having a diameter of 100 nm or less, and photocurable for low refractive layer manufacturing. And a coating composition having thermosetting.

The method of claim 1,
The photopolymerization initiator comprises at least one selected from the group consisting of benzophenone compounds, acetophenone compounds, biimidazole compounds, triazine compounds and oxime compounds, photocurable for low refractive layer production And a coating composition having thermosetting.

The method of claim 1,
Per 100 parts by weight of the photopolymerizable compound,
10 to 350 parts by weight of the inorganic nanoparticles and 0.1 to 100 parts by weight of the photopolymerization initiator, the coating composition having a photocurable and thermosetting for low refractive index manufacturing.

The method of claim 1,
A coating composition having a photocurable and thermosetting composition for producing a low refractive index layer, wherein the content of the photopolymerizable compound in a solid content of the photocurable and thermosetting coating composition is 20% by weight to 80% by weight.

The method of claim 1,
The curing accelerator includes a coating composition having a photocurable and thermosetting for the production of a low refractive index layer comprising at least one selected from the group consisting of organic acid metal salts, metal alkoxides, phenolic compounds, aliphatic alcohols, imidazoles, amines and phosphorus compounds .

The method of claim 1,
The photocurable and thermosetting coating composition for producing the low refractive index layer is the curing accelerator compared to 100 parts by weight of the silane compound containing at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group Including 0.01 to 30 parts by weight,
Coating composition having photocurable and thermosetting for low refractive layer production.

A low refractive index layer comprising a cured product of the coating composition having a photocurable and thermosetting properties for producing the low refractive index layer of claim 1.

The method of claim 18,
Photopolymerizable compounds; Fluorine-based compounds including photoreactive functional groups; And a silane-based compound comprising at least one reactive functional group selected from the group consisting of a vinyl group and a (meth) acrylate group; A low refractive index layer comprising a binder resin comprising a crosslinked polymer of the liver and inorganic nanoparticles dispersed in the binder resin.

The method of claim 18,
The low refractive layer has a thickness of 1 nm to 300 nm.

A low refractive layer of claim 18; And a hard coating layer formed on one surface of the low refractive layer.

The method of claim 21,
The hard coat layer includes a binder resin including a photocurable resin and a high molecular weight (co) polymer having a weight average molecular weight of 10,000 or more, and organic or inorganic fine particles dispersed in the binder resin;
The organic fine particles have a particle diameter of 1 to 10 ㎛,
The inorganic fine particles have a particle size of 1 nm to 500 nm, antireflection film.

The method of claim 21,
The hard coating layer is a binder resin of photocurable resin; And an antistatic agent dispersed in the binder resin.

The method of claim 23, wherein
The hard coating layer further comprises one or more compounds selected from the group consisting of alkoxy silane oligomers and metal alkoxide oligomers, anti-reflection film.