WO2017155358A1 - Anti-reflective film and method for producing same - Google Patents

Abstract

The present invention relates to an anti-reflective film and a method for producing the anti-reflective film which comprises: a hard coating layer; and a low-refraction layer which is formed on one surface of the hard coating layer and comprises a binder resin and porous inorganic nanoparticles having diameters of 5 nm to 70 nm and comprising micropores having diameters of 0.5 nm to 10 nm.

Description

 【Specification】

 [Name of invention]

 Anti-reflective film and manufacturing method thereof

 Technical Field

 Cross Citation with Related Application (s)

 This application claims the benefit of priority based on Korean Patent Application No. 10-2016-0029338 dated March 11, 2016 and Korean Patent Application No. 10-2017-0030172 dated March 9, 2017. All content disclosed in the literature is included as part of this specification.

 The present invention relates to an antireflection film and a method of manufacturing the same, and more particularly, to have a high reflectance and antifouling property while having a low reflectance and a high light transmittance, and an antireflection film capable of increasing the sharpness of a screen of a display device. And a production method for providing the antireflection film.

 [Technique to become background of invention]

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

 As a method for minimizing the reflection of light, a method of dispersing a filler such as inorganic fine particles in a resin is coated on a base film and imparts irregularities (ant i-glare: AG coating); There are a method of forming a plurality of layers having different refractive indices on the base film to use interference of light (ant i-reflect ion: AR coating), or a method of using them in common.

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

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

 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 lowering the reflectance of the low refractive index layer, and the antifouling property of the low refractive layer surface is large due to the nanometer size particles. Degraded.

 Accordingly, many studies have been conducted to reduce the absolute reflection of light incident from the outside and to improve the stain resistance along with scratch resistance of the surface, but the degree of improvement of physical properties due to beauty 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. Moreover, this invention relates to the manufacturing method which provides the antireflection film which has the above-mentioned characteristic.

 [Measures of problem]

 In the present specification, the hard coating layer; And a low refractive index layer formed on one surface of the hard coating layer, the porous inorganic nanoparticles including the fine pores having a diameter of 0.5 nm to 10 ran and the binder resin.

In addition, in the present specification, the formation of a low refractive index layer including a photopolymerizable compound or a (co) polymer thereof, a fluorine-containing compound including a photoreactive functional group, a photoinitiator and porous inorganic nanoparticles including micropores having a diameter of 0.5 nm to 10 ran. Applying and drying the resin composition for the hard coating layer; And photocuring the dried material of the resin composition. Hereinafter, an antireflection film and a method of manufacturing the 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 light is irradiated, for example, visible light or ultraviolet light. In addition, a fluorine-containing compound means the compound containing at least 1 or more fluorine elements among the compounds.

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

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

In addition, the hollow silica particles (si l ica hol low part icles) is a silica particle derived from a silicon compound or an organosilicon compound, means a particle in the form of an empty space on the surface and / or inside of the silica particles. do . According to one embodiment of the invention, the hard coating layer; And a low refractive layer formed on one surface of the hard coating layer and including porous inorganic nanoparticles and a binder resin including micropores having a diameter of 0.5ran to 10nm. ^'

Previously, a method of using an excessive amount of hollow silica having a low refractive index to reduce the reflectance of an antireflection film has been known. However, when an excessive amount of hollow silica is used, scratch resistance and antifouling properties are greatly reduced. Accordingly, the present inventors proceed with a study on the antireflection film, when the porous inorganic nanoparticles including micropores having a diameter of 0.5nm to 10nm in the low refractive layer included in the antireflection film is known in the art It was confirmed through experiments that the anti-reflective film can realize a low reflectance of a level that was difficult to implement, and that the anti-reflective film has high light transmittance and high scratch resistance and antifouling at the same time, and completed the invention. As described above, the porous inorganic nanoparticles may include micropores having a diameter of 0.5 nm to 10 nm, or lnm to 8 nm, or 2 nm to 6 ran.

 As the porous inorganic nanoparticles include fine pores of the above-described diameter, the antireflection film can ensure lower refractive index and improved mechanical properties of the surface as compared with the case of using a commonly known inorganic particle. Accordingly, when the porous inorganic nanoparticles are used, the reflectance is significantly lower than the antireflection film to which the low refractive layer including the solid inorganic nanoparticles or the hollow inorganic nanoparticles previously known, for example, 0.40% or less The reflectance can be realized, and the surface strength can be greatly improved, and the scratch and antifouling properties can be simultaneously realized.

 More specifically, the reflective ring film is 0.40% or less, or 0.1 to 0.40%, or 0.15 to 0.35%, or 0.20% to 0.30%, or 0.21 to 0.29 in the visible light wavelength range of 380ιιιη to 780ran. It can represent the average reflectance of%.

 The size of the micropores formed in the porous inorganic nanoparticles can be confirmed through a device such as TEM or SEM or BET analysis. For example, the size of the micropores can be measured and defined quantitatively, and the BET surface area of the target is measured by measuring the amount of nitrogen gas adsorbed on the sample surface using BET (Brunaur, Emutte, Tel ler). The size of the micropores can be measured and defined based on Barrett-Joyner-Halendar (BJH) analysis. The diameter of the micropores may refer to the longest diameter of the micropores identified in the cross section of the porous inorganic nanoparticles.

 In addition, the shape of the micropores formed on the porous inorganic nanoparticles is not limited to a great extent, and the cross section of the micropores formed on the porous inorganic nanoparticles may have a shape such as a circle, an ellipse or a polygon.

The porous inorganic nanoparticles may include micropores having a diameter of 0.5 nm to 10 nm, lnm to 8 ran, and also pores having a diameter of less than 0.5 nm and / or micropores having a diameter of more than 10 nm. Can contain have. In this case, the porous inorganic nanoparticles may include micropores having a diameter of 0.5 nm to 10 ran, Iran to 8 nm in an amount of 75 vol% or more, or 90 vol% or more of the total pores.

 The porous inorganic nanoparticles include pores having a diameter of 0.5 nm to 10 nm, Iran to 8 nm, and may have a BET surface area of 250 to 2,000 mVg.

 The porous inorganic nanoparticles may have a diameter of 5 nm to 100 nm, or 5 nm to 70 ran, or 10 nm to 60 nm. The diameter of the porous inorganic nanoparticles may mean the longest diameter found in the cross section of the porous inorganic nanoparticles.

 When the diameter of the porous inorganic nanoparticles is too large, the average reflectance or haze value of the low refractive index layer or the antireflection film to be produced may be greatly increased, or the cloudyness of the antireflection film may occur.

In addition, when the diameter of the porous inorganic nanoparticles is too small, the porous inorganic nanoparticles _. Since the micropores are hard to form, the refractive index of the low refractive index layer is high and the average reflectance of the antireflection film is excessively high. In addition, if the diameter of the porous inorganic nanoparticles is too small, it is easy to uniformly distribute the porous inorganic particles in the low refractive index layer, thereby reducing the mechanical properties of the low refractive index layer or the anti-reflection film including the same Can be.

 On the other hand, the surface of the porous inorganic nanoparticles may be introduced with a photoreactive functional group or a compound including a photoreactive functional group. The photo-reflective functional group may include various functional groups known to be able to participate in the polymerization reaction by irradiation of light, specific examples thereof

(Meth) acrylate group, an epoxide group, a ^"vinyl group (Vinyl) or thiol group (Thiol).

More specifically, the surface of the porous inorganic nanoparticles may be combined with a silane compound, a hydroxyl compound, or the like including the above-described light semi-functional functional groups. Examples of the silane compound containing the photoreactive functional group include vinylchlorosilane, vinyltrimethoxysilane, vinyltriespecial silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycid Doxypropyltrimethoxysilane, 3-glycidoxypropylmethyldieoxysilane, 3-glycidoxypropyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, P-styryltrimethoxysilane, 3- Methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldieespecial silane, 3-acryloxypropyltrimeth Roxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N— 2- (aminoethyl) -3-aminopropyltrimethicsilane, N-2- (aminoethyl) -3 Aminopropylmethyltriethoxysilane, 3-aminopropyltrimethoxysil , 3-Aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethylbutylidene) propylamine, Nphenyl— 3-aminopropyltrimethicsilane, 3-chloropropyltrime Methoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (trieoxysilylpropyl) tetrasulfide, ₃ -isocyanatopropyltriespecial silane, etc. are mentioned. They can be used alone or

Two or more kinds can be mixed and used.

 As the photo-reflective functional group is introduced to the surface of the porous inorganic nanoparticles, the photo-reflective functional group may form a crosslink with the binder resin in the process of forming the low refractive index layer. Mechanical properties of the surface of the antireflection film may be improved.

 As described above, the low refractive layer includes a porous inorganic nanoparticles and a binder resin including fine pores having a diameter of 0.5 ηιη to 10 ran, the content of the porous inorganic nanoparticles in the low refractive layer is 15 to 80 Weight percentage, or from 20 to 65 weight%. Even if the porous inorganic nanoparticles are included in the low refractive index layer in a relatively high content, the reflectivity of the anti-reflection film can be greatly lowered and higher scratch resistance and antifouling property can be simultaneously realized.

On the other hand, the low refractive index layer may further include inorganic particles other than porous inorganic nanoparticles, in consideration of the characteristics of the low refractive index layer or the anti-reflection film Conventionally known inorganic particles may be further included.

 Specifically, the low refractive layer may further include one or more inorganic nanoparticles selected from the group consisting of hollow inorganic nanoparticles and solid inorganic nanoparticles. The content of the at least one inorganic nanoparticle selected from the group consisting of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the low refractive layer may be 1 to 60% by weight, or 5 to 50% by weight.

 The solid inorganic nanoparticles refer to particles having a maximum diameter of less than 100 nm and having no empty space therein. The solid inorganic nanoparticles may have a diameter of 0.5 to 100 nm, or 1 to 30 nm.

 In addition, the hollow inorganic nanoparticles mean a particle having a maximum diameter of less than 200 nm and 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.

 The diameter of each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles may refer to the longest diameter found in the cross section of each nanoparticle.

 Each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles may have at least one semi-ungsung functional group selected from the group consisting of a (meth) acrylate group, an epoxide group, a vinyl group (Vinyl), and a thiol group (Thiol) on a surface thereof. It may contain.

 On the other hand, the above-described low refractive layer may be prepared from a photocurable coating composition comprising a photopolymerizable compound, a ambleo compound containing a photo-banung functional group, porous inorganic nanoparticles including micropores having a diameter of 0.5nm to 10 ran and a photoinitiator have.

 Accordingly, the binder resin included in the low refractive index layer may include a cross-linked (co) polymer between the (co) polymer of the photopolymerizable compound and the fluorine-containing compound including the photoreactive functional group.

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

 As a specific example of the monomer or oligomer containing the said (meth) acrylate, a pentaerythri is tri (meth) acrylate, a pentaerythri tetra (meth) acrylate, a dipentaerythrene penta (meth) acrylic acid Latent, dipentaerythride, nucleated (meth) acrylate, tripentaerythrone, hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, nucleamethylene diisocyanate, trimethylolpropane tri (meth) acrylic Latex, trimethylolpropane polyhydroxy tri (meth) acrylate, trimethyl propane trimethacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, nuxaethyl methacrylate, butyl methacrylate or two of these With the above mixtures or with urethane modified acrylate oligomers, Side acrylate oligomers, ether acrylate oligomers, the dendritic acrylate oligomer, or there may be mentioned those of the two or more kinds of common compounds. At this time, the molecular weight of the oligomer is preferably 1,000 to 10,000.

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

 Although the content of the photopolymerizable compound in the photocurable coating composition is not particularly limited, the content of the photopolymerizable compound in the solid content of the photocurable coating composition in consideration of the mechanical properties of the low refractive index layer or the anti-reflection film to be produced finally May be from 20% by weight to 80% by weight. Solid content of the photocurable coating composition means only the components of the solid except the components of the liquid, for example, an organic solvent that may be optionally included as described below in the photocurable coating composition.

On the other hand, the photopolymerizable compound may further include a fluorine-based (meth) acrylate monomer or oligomer in addition to the above-described monomer or oligomer. Further comprising the fluorine (meth) acrylate monomer or oligomer In this case, the weight ratio of the fluorine-based (meth) acrylate monomer or oligomer to the monomer or oligomer containing the (meth) acrylate or vinyl group may be 0.1% to 10%.

 Specific examples of the fluorine-based (meth) acrylate monomers or oligomers may include at least one compound selected from the group consisting of the following Chemical Formulas 1 to 5.

 [Formula 1]

In Formula 1, 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 2]

In Formula 2 c is an integer of 1 to 10.

 [Formula 3]

 In Formula 3, d is an integer of 1 to 11.

[Formula 4]

In Chemical Formula 4, e is an integer of 1 to 5.

 5]

 In Formula 5, f is an integer of 4 to 10.

 On the other hand, the low refractive index layer may include a portion derived from the fluorine-containing compound including the photoreactive functional group.

 One or more photoreactive functional groups may be included or substituted in the fluorine-containing compound including the photoreactive functional group, and the photoreactive functional group may participate in the polymerization reaction by irradiation of light, for example, by irradiation of visible light or ultraviolet light. Means functional groups. The photo-reflective functional group may include various functional groups known to be able to participate in the polymerization reaction by irradiation of light, and specific examples thereof include (meth) acrylate groups, eside groups, vinyl groups, or thiol groups ( Thiol).

 Each of the fluorine-containing compounds including the photo-banung functional group is 2,000 to

It may have a weight average molecular weight (weight average molecular weight in terms of polystyrene measured by the GPC method) of 200,000, preferably 5,000 to 10,000.

Weight average molecular weight of the fluorine-containing compound containing the photo-banung functional group If too small, the fluorine-containing compounds in the photocurable coating composition may not be uniformly and effectively arranged on the surface, and may be located inside the final low refractive layer to be manufactured, thereby reducing the antifouling property of the surface of the low refractive layer. Since the crosslinking density of the low refractive layer is lowered, mechanical properties such as overall strength and scratch resistance may be reduced.

 In addition, if the weight average molecular weight of the fluorine-containing compound including the photo-reflective functional group is too high, the compatibility with other components in the photocurable coating composition may be lowered, thereby increasing the haze of the low refractive layer to be produced Light transmittance may be lowered, and the strength of the low refractive index layer may also be lowered.

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

 The photocurable coating composition may include 20 to 300 parts by weight of the fluorine-containing compound including the photobanung functional group based on 100 parts by weight of the photopolymerizable compound.

When the fluorine-containing compound containing the photoreactive functional group is added in excess of the photopolymerizable compound, the coating property of the photocurable coating composition of the embodiment is reduced or the low refractive layer obtained from the photocurable coating composition has sufficient durability or scratch resistance. May not have In addition, if the amount of the fluorine-containing compound containing the photo-banung functional group relative to the photopolymerizable compound is too small, the low refractive layer obtained from the photocurable coating composition It may not have mechanical properties such as poor antifouling or scratch resistance. The fluorine-containing compound including the photobanung functional group may further include silicon or a silicon compound. That is, the fluorine-containing compound including the photoreactive functional group may optionally contain a silicon or silicon compound therein, and specifically, the content of silicon in the fluorine-containing compound including the photoreactive functional group is 0.1% by weight to 20% by weight. May be%.

 Silicon contained in the fluorine-containing compound including the photo-banung functional group can increase the compatibility with other components included in the photocurable coating composition of the embodiment, and thus it is observed that haze is generated in the final refractive layer. It can play a role of increasing transparency by preventing. On the other hand, when the content of silicon in the fluorine-containing compound containing the photo-banung functional group is too large, the compatibility between the other components included in the photocurable coating composition and the fluorine-containing compound may be rather lowered, thereby resulting in low Since the refractive layer or the antireflection film does not have sufficient light transmittance or antireflection performance, the antifouling property of the surface may also be reduced.

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

 When the content of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the low refractive layer becomes excessive, phase separation between the hollow inorganic nanoparticles and the solid inorganic nanoparticles does not occur in the low refractive layer manufacturing process. It is common to increase the reflectance, and excessive surface irregularities may occur, leading to deterioration of antifouling properties. Also, when the content of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the low refractive index layer is too small, many of the solid inorganic nanoparticles are located in a region close to the interface between the hard coating layer and the low refractive layer. It may be difficult to, and the reflectance of the low refractive index layer may be greatly increased.

 The low refractive layer may have a thickness of lnm to 300 ran, or 50nm to 200 nm.

On the other hand, the hard coating layer is generally known as a large hard coating layer Can be used without limitation.

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

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

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

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

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

The photocurable resin included in the hard coat layer is a polymer of a photopolymerizable compound that can cause polymerization reaction when irradiated with light such as ultraviolet rays, and may be conventional in the art. However, preferably, the photopolymerizable compound may be a polyfunctional (meth) acrylate monomer or oligomer, wherein the number of (meth) acrylate functional groups is 2 to 10, preferably 2 to 8, more preferably Preferably, 2 to 7 is advantageous in terms of securing physical properties of the hard coating layer. More preferably, the photopolymerizable compound is pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythride (Meth) acrylate, dipentaerythritol hepta (meth) acrylate, tripentaerythritol hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, nusamethylene diisocyanate, trimethylolpropane tri ( It may be at least one member selected from the group consisting of meth) acrylate, and trimethylolpropane polyethoxy tri (meth) acrylate. The antistatic agent is a quaternary ammonium salt compound; Pyridinium salts; Cationic compounds having from 1 to 3 amino groups; Anionic compounds such as sulfonic acid base, sulfate ester base, phosphate ester base and phosphonic acid base; Positive compounds, such as an amino acid type or amino sulfate ester type compound; Nonionic compounds such as imino alcohol compounds, glycerin compounds, and polyethylene glycol compounds; Organometallic compounds such as metal alkoxide compounds including tin or titanium; Metal chelate compounds such as acetylacetonate salts of the organometallic compounds; Two or more semi-ungmuls or polymerized compounds of these compounds; It may be a combination of two or more of these compounds. Here, the quaternary ammonium salt compound may be a compound having one or more quaternary ammonium salt groups in the molecule, it can be used without limitation low molecular type or polymer type. In addition, a conductive polymer and metal oxide fine particles may also be used as the antistatic agent. Examples of the conductive polymer include aromatic conjugated poly (paraphenylene), polypyrrole of heterocyclic conjugated system, polythiophene, polyacetylene of aliphatic conjugated system, polyaniline of conjugated example containing hetero atom, poly of conjugated conjugated system ( Phenylene vinylene), a double-chain conjugated compound that is a conjugated system having a plurality of conjugated chains in a molecule, and a conductive composite obtained by grafting or block copolymerizing a conjugated polymer chain to a saturated polymer. Further, the metal oxide fine particles include zinc oxide, antimony oxide, tin oxide, cerium oxide, indium tin oxide, indium oxide, aluminium oxide, antimony doped tin oxide, aluminum doped zinc oxide, and the like.

 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-based compound may be conventional in the art, but preferably tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methacryl It may be at least one compound selected from the group consisting of oxypropyltrimethoxysilane, glycidoxypropyl trimethoxysilane, and glycoxy propyl propyl 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 with water rapidly, the sol-gel reaction may be performed by diluting the metal alkoxide compound in an organic solvent and slowly dropping water. At this time, in consideration of reaction efficiency, the molar ratio of the metal alkoxide compound to water (based on metal ions) is preferably adjusted within the range of 3 to 170. Here, the metal alkoxide-based compound may be at least one compound selected from the group consisting of titanium tetra-isopropoxide, zirconium isopropoxide, and aluminum isopropoxide.

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

 It may further include a substrate bonded to the other side of the hard coating layer. 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. On the other hand, according to another embodiment of the invention, a photopolymerizable compound or

Applying and drying a resin composition for forming a low refractive index layer including a (co) polymer, a fluorine-containing compound including a photoreactive functional group, a photoinitiator, and porous inorganic nanoparticles including micropores having a diameter of 0.5 nm to 10 nm on a hard coating layer. Doing; And photocuring the dried material of the resin composition. A method of manufacturing an anti-reflection film may be provided.

 Through the manufacturing method of such an anti-reflection film may be provided an anti-reflection film of one embodiment described above.

 As described above, in the case of distributing porous inorganic nanoparticles including micropores having a diameter of 0.5 nm to 10 ran in the low refractive layer included in the antireflective film, the level of hardly realized in the known antireflective film It is possible to implement a low reflectance, and at the same time it is possible to implement a high scratch resistance and antifouling resistance while having a high light transmittance.

 More specifically, the anti-reflection film provided according to the manufacturing method is a hard coating layer; and formed on one surface of the hard coating layer, and the fine pores having a diameter of 0.5nm to 10nm dispersed in the binder resin and the binder resin It includes; low refractive index layer comprising a porous inorganic nanoparticles including.

The low refractive index layer may be a photopolymerizable compound or a (co) polymer thereof, a fluorine-containing compound including a photoreactive functional group, a photoinitiator, hollow inorganic nanoparticles, and The resin composition for forming a low refractive index layer including the solid inorganic nanoparticles may be formed by applying on a hard coating layer and drying at a temperature of 35 ° C to 100 ° C, or 40 ° C to 80 ° C.

When the temperature for drying the low refractive index layer-forming resin composition applied on the hard coating layer is less than 35 ⁰ C, antifouling property of the low refractive index layer may be greatly reduced. In addition, when the temperature of drying the resin composition for forming the low refractive index layer applied on the hard coating layer is more than 100 ^o C, erosion of the substrate occurs during the low refractive layer manufacturing process, the scratch resistance and antifouling property of the low refractive index layer In addition to deterioration, haze may occur in the final antireflection film.

On the other hand, the step of drying the resin composition for forming the low refractive index layer applied on the hard coating layer at a temperature of 35 ° C to 100 ⁰ C may be performed for 10 seconds to 5 minutes, or 30 seconds to 4 minutes.

 When the drying time is too short, the dispersion of the porous inorganic nanoparticles including the fine pores having a diameter of 0.5 nm to 10 nm may not occur sufficiently. In contrast, when the drying time is too long, the formed low refractive index layer may erode the hard coating layer.

 On the other hand, the low refractive index layer may be prepared from a photocurable coating composition comprising a photopolymerizable compound or a (co) polymer thereof, a fluorine-containing compound including a photoreactive functional group, hollow inorganic nanoparticles, solid inorganic nanoparticles and a photoinitiator. .

 The low refractive layer can be obtained by applying the photocurable coating composition on a predetermined substrate and photocuring the applied resultant. 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.

Methods and apparatus conventionally used to apply the photocurable coating composition may be used without particular limitation, for example, Meyer bar Bar coating method, gravure coating method, 2 roll reverse coating method, vacuum slot die coating method, 2 roll coating method and the like can be used.

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

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

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

 Details of the photopolymerizable compound, porous inorganic nanoparticles including micropores having a diameter of 0.5 nm to 10 nm, and a fluorine-containing compound including a photoreactive functional group include the aforementioned contents with respect to the antireflection film of the embodiment. do.

 The resin composition for forming the low refractive index layer may further include at least one inorganic nanoparticle selected from the group consisting of hollow inorganic nanoparticles and solid inorganic nanoparticles. Details of the hollow inorganic nanoparticles and the solid inorganic nanoparticles include the above-described contents with respect to the anti-reflection film of the embodiment.

 Each of the hollow inorganic nanoparticles and the solid inorganic nanoparticles may be included in the composition in the form of a colloid dispersed in a predetermined dispersion medium. Each colloidal phase including the hollow inorganic nanoparticles and the solid inorganic nanoparticles may include an organic solvent as a dispersion medium.

The colloidal phase of each of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in consideration of the content range of the hollow inorganic nanoparticles and the solid inorganic nanoparticles or the viscosity of the photocurable coating composition in the photocurable coating composition Heavy content can be determined, for example, The solid content of each of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the colloidal phase may be 5% by weight to 60% by weight.

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

 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, triazine compound, oxime compound or Two or more kinds thereof can be used. With respect to 100 parts by weight of the photopolymerizable compound, the photopolymerization initiator may be used in an amount of 1 to 100 parts by weight. If the amount of the photopolymerization initiator is too small, an uncured material remaining in the photocuring step of the photocurable coating composition may be issued. If the amount of the photopolymerization initiator is too large, the non-aqueous initiator may remain as an impurity or have a low crosslinking density, thereby lowering mechanical properties or reflectance of the film.

 Meanwhile, the photocurable coating composition may further include an organic solvent. Non-limiting examples of the organic solvents include ketones, alcohols, acetates and ethers, or combinations of two or more thereof. Specific examples of such organic solvents include ketones such as methyl ethyl kenone, methyl isobutyl ketone, acetylacetone or isobutyl ketone; Alcohols such as methanol, ethanol, diacetone alcohol, n-propanol, i-propanol, n-butanol, i_butanol, or t_butanol; Acetates such as ethyl acetate, i-propyl acetate, or polyethylene glycol monomethyl ether acetate; Ethers such as tetrahydrofuran or propylene glycol monomethyl ether; Or two or more kinds thereof.

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

 The hard coating layer may be used without any limitation as long as it is a material known to be used for the antireflection film.

 As described above, examples of the hard coating layer include a binder resin containing a photocurable resin and a hard coating layer containing organic or inorganic fine particles dispersed in the binder resin.

 Accordingly, the method of manufacturing the antireflection film may further include applying a photopolymerizable compound or a (co) polymer thereof, a photoinitiator, and a polymer resin composition for forming a hard coating layer including organic or inorganic fine particles on a substrate and photocuring the same. It can be, through this step can form a hard coating layer.

 In addition, 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.

 Accordingly, the method of manufacturing the antireflection film may further include applying a photopolymerizable compound or a polymer resin composition for forming a hard coating layer including a (co) polymer, a photoinitiator, and an antistatic agent on a substrate and photocuring the same. Through the above steps, a hard coating layer may be formed.

The components used to form the hard coat layer are the same as described above with respect to the antireflection film of the embodiment. In addition, the polymer resin composition for forming the hard coating layer is one selected from the group consisting of alkoxy silane oligomer and metal alkoxide oligomer. It may further comprise a compound.

Methods and apparatuses commonly used to apply the polymer resin composition for forming the hard coating layer may be used without particular limitation, for example, a bar coating method such as Meyer bar, gravure coating method, 2 roll l reverse coating method, Vacuum slot die coating and 2 roll coating can be used. In the step of photocuring the polymer resin composition for forming the hard coating layer may be irradiated with ultraviolet light or visible light having a wavelength of 200 ~ 400nm, the exposure dose is preferably 100 to 4, 000 mJ / cin ² . Exposure time is not specifically limited, either, The exposure apparatus used can be changed suitably according to the wavelength or exposure amount of irradiation light. In addition, in the step of photocuring the polymer resin composition for forming a hard coating layer may be purged with nitrogen in order to apply nitrogen atmospheric conditions.

 【Effects of the Invention】

 According to the present invention, an anti-reflection film and a method of manufacturing the anti-reflection film can be provided 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 the screen of the display device. .

 [Specific contents to carry out invention]

 The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

<Production example>

 Preparation Example: Preparation of Hard Coating Film

 KY0EISHA salt type antistatic hard coating solution (50 wt% solids, product name: LJD-1000) was coated on a triacetyl cellulose film with # 10 mayer bar.

After drying at 90 ^o C for 1 minute, it is irradiated with ultraviolet light of 150 mJ / cu to about 5 to

A hard coat film having a thickness of 6 was prepared. <Example 1 to 5: Preparation of an antireflection film>

 Example 1

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

 Pentaerythritol triacrylate (PETA) 25.5% by weight, fluorine-containing compound (RS-537, DIC) 5% by weight, initiator (Irgacure 127, Ciba) 4.5% by weight>, porous inorganic nanoparticles (BJH analysis Size of micro pores by about 4.1 ran, BET surface area: about 917.5 mVg, particle diameter about 20 ran, surface treated with 3-methacryloyloxypropyldimethoxysilane) and solids containing 65% by weight of MIBK methyl isobutyl ketone) Dilute to 3.2 wt% solids concentration.

 (2) Preparation of low refractive layer and antireflection film

 On the hard coat film of the above preparation, the photocurable coating composition obtained above was coated with a # 4 mayer bar so as to have a thickness of about 110 to 120 nm,

It was dried and cured for 1 minute at a temperature of 60 ⁰ C. At the time of curing, the dried coating was irradiated with ultraviolet light of 252 mJ / cuf under nitrogen purge. Example 2

 Pentaerythritol triacrylate (PETA) 27% by weight, fluorine-containing compound (RS-537, DIC) 5% by weight, initiator (Irgacure 127, Ciba) 4.5% by weight, porous inorganic nanoparticles (by BJH analysis Size of fine pores about 4.5 ran, BET surface area: about 941.7 mVg, particle diameter about 23 ran, surface-treated with 3-methacryloyloxypropyldimethoxysilane) Diluted to a concentration of 3.2 wt%.

 Then, a low refractive index layer and an antireflection film were prepared in the same manner as in Example 1. Example 3

Pentaerythritol triacrylate (PETA) 20% by weight, fluorine-containing compound (RS-537, DIC) 5% by weight, initiator (Irgacure 127, Ciba) 4.5% by weight, porous inorganic nanoparticles (size of micropores by BJH analysis about 3.9 ran, BET surface area: about 933. 1 mVg, The solids, including about 21 nm in diameter, surface treated with 3-methacryloyloxypropyldimethoxysilane) 70.5% by weight, were diluted in MIBKGnethyl i sobutyl ketone) to a solids concentration of 3.2% by weight.

 Then, a low refractive index layer and an antireflection film were prepared in the same manner as in Example 1. Example 4

 Pentaerythritol triacrylate (PETA) 30% by weight, fluorine-containing compound (RS-537, DIC Corporation) 5% by weight>, initiator (Irgacure 127, Ciba) 4.5% by weight, porous inorganic nanoparticles (BJH analysis Size of fine pores by about 4.2 ran, BET surface area: about 923.3 m7g, particle diameter about 22 ran, surface treated with 3-methacryloyloxypropyldimethoxysilane) solids containing 60.5% by weight of MIBKGnethyl i sobutyl ketone) To a solid content concentration of 3.2% by weight.

 Then, a low refractive index layer and an antireflection film were prepared in the same manner as in Example 1.

Comparative Example: Preparation of Antireflection Film

 Comparative Example 1

 Instead of 65% by weight of porous inorganic nanoparticles used in Example 1, 65% by weight of hollow silica nanoparticles (diameter: about 50 to 60 ran, density: 1.96 g / cirf, manufactured by JSC catalyst and chemi cal s) Except for the above, a photocurable coating composition for preparing a low refractive index layer was prepared in the same manner as in Example 1, and an antireflection film was prepared in the same manner as in Example 1. Comparative Example 2

Instead of 65% by weight of the porous inorganic nanoparticles used in Example 1 Hollow silica nanoparticles (diameter: about 60 to 70 ran, manufactured by JSC catalyst and chemi cal s) 65 weight ¾>, except that the photocurable coating composition for low refractive layer production in the same manner as in Example 1 To prepare a, antireflection film was prepared in the same manner as in Example 1. Comparative Example 3

 Instead of 65% by weight of porous inorganic nanoparticles used in Example 1, 65% by weight of porous inorganic nanoparticles (size of micropores by BJH analysis about 4.8 ran, BET surface area: about 945.5 mVg, diameter of particles about 85 ran) A photocurable coating composition for preparing a low refractive index layer was prepared in the same manner as in Example 1 except for the use thereof, and an antireflection film was prepared in the same manner as in Example 1.

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.Measure the average reflectance of the antireflective film

 The average reflectance which the antireflective film obtained by the Example and the comparative example shows in visible region (380-780 nm) was measured using the Sol idspec 3700 (SHIMADZU) apparatus.

2. Antifouling measurement

 A 5 cm long straight line was drawn with a black name pen on the surface of the antireflective film obtained in Examples and Comparative Examples, and the antifouling properties were measured by checking the number of times erased when rubbed using a dust-free cloth.

 <Measurement standard>

 0: erase time is 10 times or less

Δ: 11-20 times X: Cleared more than 20 times

3. Scratch resistance measurement

 The steel wool 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. Haze measurement

 The haze of the antireflection film obtained in the Example and the comparative example was measured by the A light source using the 丽 -150 equipment.

[Table 1]

As confirmed in Table 1, the antireflection film of Examples 1 to 4 has a significantly lower reflectance than the reflectance of the level of the known antireflection film, specifically, it is confirmed that the low reflectance of less than 0.30% It became. In addition, it has been confirmed that the antireflection films of Examples 1 to 4 may simultaneously implement high scratch resistance and antifouling resistance together with the low reflectance.

In contrast, the antireflective films of Comparative Examples 1 to 3 were relatively high. While showing average reflection, it shows low scratch resistance and antifouling resistance.

It was confirmed that the antireflection film of 3 exhibits a relatively high haze value.

Claims

[Claim]

 [Claim 1]

 Hard coating insects; And

 Formed on one surface of the hard coating layer, a low refractive index layer containing porous inorganic nanoparticles of 5 nm to 70 nm in diameter including a fine pores having a diameter of 0.5 nm to 10 ran and a binder resin;

Anti-reflection film.

[Claim 2]

 According to claim 1,

The porous inorganic nanoparticles have a diameter of 10 nm to 60 nm, antireflection film.

[Claim 3]

 According to claim 1,

BET surface area of the porous inorganic nanoparticles is 250 to 2,000 m7g, anti-reflection film.

[Claim 4]

 According to claim 1,

The reflective ring film exhibits an average reflectance of 0.40% or less in the visible light wavelength range of 380 nm to 780 nm.

[Claim 5]

 The method of claim 1,

The content of the porous inorganic nanoparticles in the low refractive layer is 15 to 80% by weight, anti-reflection film.

[Claim 6]

The method of claim 1 The low refractive index layer further comprises at least one inorganic nanoparticles selected from the group consisting of hollow inorganic nanoparticles and solid inorganic nanoparticles, anti-reflection film.

[Claim 7]

 The method of claim 1,

The binder resin included in the low refractive index layer comprises a cross-linked (co) polymer between the (co) polymer of the photopolymerizable compound and the fluorine-containing compound including the photo-banung functional group, antireflection film.

[Claim 8]

 The method of claim 7,

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

[Claim 9]

 According to claim 7,

The fluorine-containing compound containing the photo-banung functional group each has a weight average molecular weight of 2,000 to 200,000, anti-reflection film.

[Claim 10]

 The method of claim 7, wherein

The binder resin comprises an anti-reflection film containing 20 to 300 parts by weight of a fluorine-containing compound containing the photoreactive functional group based on 100 parts by weight of the (co) polymer of the photopolymerizable compound.

[Claim 11]

 The method of claim 7,

In the group consisting of (meth) acrylate group, epoxide group, vinyl group (Vinyl) and thiol group (Thiol) contained in the fluorine-containing compound At least one selected, antireflection film.

[Claim 12]

 The method of claim 7,

The fluorine-containing compound including the photo-reflective functional group includes: i) an aliphatic compound or an aliphatic ring compound in which one or more photo-reflective functional groups are substituted, and at least one fluorine is substituted for at least one carbon; i i) a heteroaliphatic compound or a heteroaliphatic ring compound substituted with one or more photocyclic functional groups, at least one hydrogen substituted with fluorine, and one or more carbons substituted with silicon; i i i) a polydialkylsiloxane polymer substituted with at least one photoreactive functional group and substituted with at least one fluorine in at least one silicon; And iv) a polyether compound substituted with at least one photoreactive functional group and at least one hydrogen is substituted with fluorine.

[Claim 13]

 In U,

The hard coating layer is a binder resin including a photocurable resin; And an antistatic agent dispersed in the binder resin.

[Claim 14]

 The method of claim 13,

The hard coating layer further comprises at least one compound selected from the group consisting of alkoxy silane oligomer and metal alkoxide oligomer, antireflection film.

[Claim 15]

 The method of claim 1,

On the surface of the porous inorganic nanoparticles, an anti-reflective functional group is introduced or a compound including a photo-reflective functional group is combined.

[Claim 16]

 A photopolymerizable compound or a (co) polymer thereof, a fluorine-containing compound containing a photoreactive functional group, a photoinitiator and a low inorganic porous nanoparticle having a diameter of 5 ran to 70 ran including micropores having a diameter of 0.5 ran to 10 ran Applying and drying the resin composition for forming a refractive layer on the hard coating layer; Photocuring the dried material of the resin composition; a method of manufacturing an antireflection film comprising a.

[Claim 17]

 The method of claim 16,

The resin composition for forming the low refractive index layer applied on the hard coating layer is dried at a temperature of 35 ° C to 100 ^o c, method of manufacturing an antireflection film.

[Claim 18]

 The method of claim 17,

 Drying the resin composition for forming a low refractive index layer applied on the hard coating layer at a temperature of 35 ° C to 100 ° C is performed for 10 seconds to 5 minutes, a method for producing an anti-reflection film.

[Claim 191

 The method of claim 16,

 Applying a photopolymerizable compound or a (co) polymer thereof, a polymer resin composition for forming a hard coating layer including a photoinitiator, and an antistatic agent on a substrate and photocuring; or

A photopolymerizable compound or a (co) polymer thereof, a photoinitiator, and a polymer resin composition for forming a hard coating layer containing organic or inorganic fine particles on a substrate A method of making an antireflection film, further comprising applying and photocuring.