KR20130021182A - Anti-glare/anti-reflective coating composition and anti-glare/anti-reflective film using the same - Google Patents

Abstract

PURPOSE: An anti-glare and anti-reflective coating composition is provided to provide an image display device with excellent visibility. CONSTITUTION: An anti-glare and anti-reflective coating composition comprises a (meth)acrylate monomer, hollow silica nanoparticles, quaternary ammonium salt, a mixture solvent of an alcohol-based solvent and ketone-based solvent, and a photopolymerization initiator. The average particle diameter of the hollow silica nanoparticle is 1-100 nm and the comprised amount of the hollow silica nanoparticle is 1-25 weight% based on 100 weight% of the anti-glare and anti-reflective coating composition. An anti-glare and anti-reflective film comprises a substrate; and an anti-glare and anti-reflective layer which is formed on the substrate, and has an uneven surface due to an aggregate of hollow silica nanoparticles.

Description

Anti-glare anti-reflective coating composition and anti-glare anti-reflective film using same {ANTI-GLARE / ANTI-REFLECTIVE COATING COMPOSITION AND ANTI-GLARE / ANTI-REFLECTIVE FILM USING THE SAME}

The present invention relates to an anti-glare anti-reflective coating composition which can impart anti-glare and anti-reflective at the same time and an anti-glare anti-reflection film using the same.

The anti-glare film is an optical film having a function of reducing light reflection by using light scattering due to surface irregularities, and includes various display panel such as liquid crystal display (LCD), plasma display (PDP), cathode ray tube (CRT), It is disposed in the organic light emitting diode EL or the like and is used for the purpose of preventing the reduction of contrast due to the reflection of external light or preventing the visibility of the display device from the reflection of the image.

The antiglare film usually comprises an antiglare layer formed of an antiglare coating composition containing translucent fine particles such as silica or polymer beads on a transparent substrate. In order to form the surface unevenness | corrugation of this anti-glare layer easily, translucent microparticles | fine-particles with a large average particle diameter are mainly used. However, in this case, the whitening phenomenon and the shiny scintillation occur on the surface of the antiglare layer, so that the visibility of image information is deteriorated.

In view of this point, in recent years, attempts have been made to further improve visibility by securing both antiglare and antireflection by further forming an antireflection layer on the antiglare layer of the antiglare film. To this end, although the antireflection layer must be formed to a thin thickness on the antiglare layer, it is difficult to form the antireflection layer into a thin and uniform thickness on the antiglare layer having surface irregularities, and thus, the problem of deteriorating the surface visibility due to the thickness nonuniformity is caused. In addition, due to the thin thickness of the antireflection layer, it is difficult to secure sufficient mechanical strength, and thus has a disadvantage of being vulnerable to external damage such as scratches. In addition, since the separate process of the anti-glare layer forming process and the anti-reflective layer forming process must be performed two or more times, there is a disadvantage in that the process time is long and expensive process costs are required.

Publication No. 2006-0097608 (published Sep. 14, 2006)

The present invention can easily form surface irregularities without using translucent fine particles having a large average particle diameter, and anti-glare reflection that can simultaneously provide anti-glare and anti-reflective properties in one coating layer without being restricted by coating thickness. It is an object to provide an anti-coat composition.

Another object of the present invention is to provide an anti-glare antireflection film comprising an anti-glare antireflection layer formed of the anti-glare antireflection coating.

In addition, another object of the present invention is to provide a polarizing plate and an image display device provided with the anti-glare antireflection film.

1. (meth) acrylate monomers; Hollow silica nanoparticles; Quaternary ammonium salts; Mixed solvents of alcohol solvents and ketone solvents; And an anti-reflective coating composition comprising a photopolymerization initiator.

2. In the above 1, the hollow silica nanoparticles have an average particle diameter of 1 to 100nm anti-glare anti-reflective coating composition.

3. In the above 1, the hollow silica nanoparticles anti-glare anti-reflective coating composition comprising 1 to 25% by weight in a total of 100% by weight anti-glare anti-reflective coating composition.

4. In the above 1, the quaternary ammonium salt is anti-reflective anti-reflective coating composition is a polymeric quaternary ammonium salt having a number average molecular weight of 4,000 or more.

5. according to the above 1, the quaternary ammonium salt is anti-glare anti-reflective coating composition comprising 0.01 to 5% by weight in a total of 100% by weight anti-glare anti-reflective coating composition.

6. In the above 1, the weight ratio of the alcohol solvent and ketone solvent is 4: 6 to 6: 4 anti-glare anti-reflective coating composition.

7. In the above 1, the mixed solvent is anti-glare anti-reflective coating composition comprising 40 to 60% by weight in 100% by weight of the anti-glare anti-reflective coating composition.

8. Base material; And an anti-glare antireflection layer formed on the substrate and having surface irregularities formed by aggregates of hollow silica nanoparticles.

9. In the above 8, the anti-glare antireflection layer is anti-glare anti-reflection film formed of the coating composition of any one of the above 1 to 7.

10. The anti-glare antireflection film of claim 8, wherein some of the aggregates are agglomerated quaternary ammonium salts.

11. The anti-glare antireflection film of claim 8, wherein the aggregates are less distributed in the anti-glare antireflection layer as the distance from the substrate increases.

12. Polarizing plate equipped with the anti-glare antireflection film of the above 8.

13. Image display device provided with the polarizing plate of 12 above.

According to the anti-glare antireflective coating composition of the present invention, the surface irregularities can be easily formed without using translucent microparticles having a large average particle diameter, and the anti-glare and anti-reflective property can be simultaneously provided by one coating layer, thereby providing an image display apparatus. When applied to can provide excellent visibility.

In addition, the anti-glare anti-reflective coating composition of the present invention can form the anti-glare anti-reflective layer in one step without being limited by the thickness of the coating layer can shorten the process time and reduce the process cost.

1 is a SEM photograph showing the surface of the anti-glare antireflection film prepared in Example 2 of the present invention,
2 is a SEM photograph showing the surface of the film prepared in Comparative Example 1.

The present invention relates to an antiglare antireflective coating composition and an antiglare antireflective film using the same.

Hereinafter, the present invention will be described in detail.

The anti-glare antireflective coating composition of the present invention comprises a (meth) acrylate monomer; Hollow silica nanoparticles; Quaternary ammonium salts; Mixed solvents of alcohol solvents and ketone solvents; And a photopolymerization initiator.

The (meth) acrylate monomer is a component for improving the surface hardness of the anti-glare antireflection layer, and examples thereof include 1 to 6 functional (meth) acrylate monomers known in the art.

Specific examples of the (meth) acrylate monomers include methyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, isodecyl (meth) acrylate, and 2-dodecylthioethyl. (Meth) acrylate, octyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate , Isooctyl (meth) acrylate, stearyl (meth) acrylate, tetraperfuryl (meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acryl Monofunctional monomers such as acrylate and phenoxybenzyl (meth) acrylate; 1,3-butanedioldi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, ethylene glycoldi (meth) acrylate, bisphenol A-ethylene Glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyldi (meth) acrylate, caprolactone modified dicyclopentenyldi (meth) acrylate, ethylene oxide modified phosphoric acid di (meth) acrylate, Bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, di (acryloxyethyl) isocyanurate, allylated cyclohexyldi (meth) acrylate, dimethyloldicyclopentanedi (meth) Methacrylate, ethylene oxide modified hexahydrophthalic acid di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, neopentyl glycol modified trimethylolpropanedi (meth) acrylate, adamantanedi (meth) acrylate, etc. Difunctional monomers of; (Meth) acrylate such as trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri Trifunctional monomers such as tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, glycerol tri ; Tetrafunctional monomers such as diglycerin tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylol propane tetra (meth) acrylate; Pentafunctional monomers such as dipentaerythritol penta (meth) acrylate and propionic acid-modified dipentaerythritol penta (meth) acrylate; Hexafunctional monomers, such as dipentaerythritol hexa (meth) acrylate and caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. are mentioned. These can be used individually or in mixture of 2 or more types.

The (meth) acrylate monomer may be included in 0.1 to 60% by weight in 100% by weight of the total anti-glare antireflective coating composition, preferably 20 to 50% by weight. When the content is less than 0.1% by weight, it may be difficult to secure sufficient surface hardness of the anti-glare antireflection layer, and when the content is more than 60% by weight, the viscosity of the coating composition may be increased to reduce the coating property and to form uniform surface irregularities. .

In the present invention, as the light-transmitting fine particles for forming the surface irregularities of the anti-glare antireflection layer, it is particularly characterized in selecting hollow silica nanoparticles having a small average particle size (nm) unlike the conventional one.

The hollow silica nanoparticles form surface irregularities by agglomerating with each other during the volatilization of the solvent during curing of the coating composition, and unlike the conventional micro-sized (μm) large translucent particles, whitening and scintillation do not occur on the surface of the coating layer.

The hollow silica nanoparticles preferably have an average particle diameter of 1 to 100 nm, more preferably 40 to 70 nm. If the average particle diameter is less than 1 nm, it may be difficult to obtain sufficient anti-glare property due to the weak coagulation effect and difficult formation of surface irregularities, and it may be difficult to give desired anti-glare property by excessive aggregation when it exceeds 100 nm. And worsen the surface state of the coating layer.

The hollow silica nanoparticles may be spherical, hollow, porous or intangible, and are preferably spherical.

The hollow silica nanoparticles may be coated with a silane coupling agent. Specific examples of the silane coupling agent include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane and diphenyldiee. Methoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl -3,3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltri Ethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxymethoxy) propyltrimethoxysilane, γ- (meth) acryloxymethyltrimethoxysilane, γ- (meth) acryloxymethyltriethoxysilane, γ- (meth) acryloxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxy Silane, γ- (meth) acryloxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, butyltriethoxy Silane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluoro Octylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Ropil trimethoxysilane, and the like γ- mercaptopropyl trimethoxysilane, trimethyl silanol, silane, methyl trichloro, these may be used alone or in mixture of two or more.

The hollow silica nanoparticles can be used in the form of a dried powder or a dispersion in which the powder is dispersed in water, an organic solvent or a mixed solvent thereof. As this dispersion, what is known as colloidal hollow silica in the art can also be used. When the dispersion medium is water, the pH is preferably 2 to 10, more preferably acidic colloidal hollow silica having a pH of 3 to 7. Moreover, when a dispersion medium is an organic solvent, methanol, isopropyl alcohol, ethylene glycol, butanol, ethylene glycol monopropyl ether, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, dimethylformamide, etc. are mentioned among these, methanol , Isopropyl alcohol, methyl ethyl ketone or xylene is preferred.

Hollow silica nanoparticles are commercially available colloidal silicas, such as THRULYA 2320 (average particle diameter 50 nm, refractive index 1.3, solid content 20% by weight, dispersion medium: methyl isobutyl ketone, isopropyl alcohol), THRULYA 4320 (average) 60 nm in particle diameter, refractive index 1.25, solid content 20 weight%, a dispersion medium: methyl isobutyl ketone), THRULYA 4110 (average particle diameter 60 nm, refractive index 1.25, solid content 20 weight%, a dispersion medium: isopropyl alcohol, methanol), etc. can be used. These can be used individually or in mixture of 2 or more types.

The hollow silica nanoparticles may be included in an amount of 1 to 60% by weight, preferably 1 to 25% by weight, and more preferably 1 to 10% by weight, in 100% by weight of the antiglare antireflective coating composition. If the content is less than 1% by weight, it is difficult to expect the aggregation effect on the surface of the anti-glare antireflection layer, so that it may be difficult to obtain sufficient anti-glare property, and when the content is more than 60% by weight, the transmittance may be lowered.

In the present invention, the quaternary ammonium salt is used together with gastric hollow silica nanoparticles to form surface irregularities of the anti-glare antireflection layer.

The quaternary ammonium salts serve to promote the flotation and flocculation of the hollow silica nanoparticles, and together with the hollow silica nanoparticles, they form an aggregate. Specifically, the quaternary ammonium salt is dissolved in an alcoholic solvent in a mixed solvent to be described later, and floats to the top of the anti-glare antireflective layer during the volatilization of the mixed solvent during curing. When the alcoholic solvent is volatilized, the hollow silica nanoparticles are floated to the top. To help. Due to this, the hollow silica nanoparticles floated upwardly aggregate to form aggregates or aggregate together with quaternary ammonium salts to form aggregates. These aggregates form the surface irregularities of the anti-glare antireflection layer. That is, unlike the conventional art, surface irregularities can be formed even by small particles having a nano size instead of translucent fine particles having a large average particle diameter.

The kind of quaternary ammonium salt is not specifically limited, For example, a low molecular type and a polymeric quaternary ammonium salt etc. are mentioned. Of these, polymeric quaternary ammonium salts having a number average molecular weight of 4,000 or more are preferable.

As the quaternary quaternary ammonium salt, commercially available products such as PQ-10, PQ-50 and the like can be used.

The quaternary ammonium salt may be included in an amount of 0.01 to 15% by weight, preferably 0.01 to 10% by weight, more preferably 0.01 to 5% by weight in 100% by weight of the antiglare antireflective coating composition. If the content is less than 0.01% by weight, it is difficult to secure anti-glare because irregularities are not formed on the surface of the anti-glare antireflection layer. If the content is more than 15% by weight, the transmittance may decrease due to whitening.

In the present invention, the solvent is particularly characterized by using a mixed solvent in which an alcohol solvent and a ketone solvent are mixed.

Alcohol-based solvents dissolve quaternary ammonium salts and are components that promote the action of quaternary ammonium salts by volatilization during curing.

The type of alcohol solvent is not particularly limited. For example, methanol, ethanol, isopropyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate etc. can be mentioned, These can be used individually or in mixture of 2 or more types.

Ketone-based solvents are volatilized with alcohol-based solvents during drying, reducing the compatibility of the quaternary ammonium salts, thereby agglomerating hollow silica nanoparticles and quaternary ammonium salts as well as agglomeration between the hollow silica nanoparticles disposed on the surface of the anti-glare antireflection layer. It is a component that promotes aggregation between them to form surface irregularities.

The type of the ketone solvent is not particularly limited, and examples thereof include methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl amyl ketone, diethyl ketone, dipropyl ketone, acetone, and the like. It can mix and use the above.

The weight ratio of the alcohol solvent and the ketone solvent may be 2: 8 to 8.5: 1.5, preferably 4: 6 to 6: 4. At this time, the weight ratio is based on the total weight ratio 10. If the weight ratio is less than 2: 8, that is, if the weight ratio of the alcohol solvent is less than 2 or the weight ratio of the ketone solvent is more than 8, compatibility between the components included in the coating composition may be poor, resulting in poor stability and uniform quaternary ammonium salts. May not be dissolved. In addition, when the weight ratio is more than 8.5: 1.5, that is, the weight ratio of the alcohol solvent is more than 8.5 or the weight ratio of the ketone solvent is less than 1.5, it is difficult to form irregularities on the surface of the antiglare antireflection layer and the adhesion between the antiglare antireflection layer and the substrate is lowered. Can be.

The mixed solvent may be included in 20 to 90% by weight in 100% by weight of the total anti-glare antireflective coating composition, preferably 40 to 60% by weight. In the case of this content range, compatibility between the components included in the coating composition is good, and surface irregularities may be effectively formed by the action of the quaternary ammonium salt and the hollow silica nanoparticles.

A photoinitiator is a component for improving hardening efficiency, The kind is not specifically limited. For example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, hydroxydimethylacetophenone, dimethylaminoacetophenone, 3 -Methylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 4-chronoacetophenone, 4,4-dimethoxyacetophenone, 2-hydride Hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 4-hydroxycyclophenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2- Morpholino-propane-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4-diaminobenzo Phenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, 2-methylthione Oxanthone, 2-ethyl thioxanthone, 2- Chlorothioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, benzyl dimethyl ketal, diphenyl ketone benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoic acid ester, oligo [2 -Hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone], 2,4,6-trimethylbenzoyldiphenylphosphine oxide, fluorene, triphenylamine, carbazole and the like Can be mentioned. Moreover, as a commercially available product, brand names Darocur 1173, Igacure 184, Igacure 907, Igacure 1700 (Ciba company), etc. can also be used. These can be used individually or in mixture of 2 or more types.

The photopolymerization initiator is preferably included in an amount of 0.05 to 5% by weight in a total of 100% by weight anti-glare antireflective coating composition. When the content is less than 0.05% by weight, the curing speed may be slow, and when the content is more than 5% by weight, cracks may occur in the anti-glare antireflection layer due to overcuring.

The anti-glare antireflective coating composition together with the above components may further include one or more additives such as antioxidants, ultraviolet absorbers, light stabilizers, surfactants, leveling agents, lubricants, antifouling agents and the like.

The anti-glare anti-reflective coating composition of the present invention configured as described above has an anti-glare anti-reflective layer having surface irregularities that can simultaneously provide anti-glare and anti-reflective properties in one coating layer without using translucent particles having a large average particle diameter. It can be formed easily. This can shorten the process time and reduce the process cost.

The present invention provides an antiglare antireflection film using the antiglare antireflective coating composition.

Anti-glare antireflection film is a substrate; And an anti-glare antireflection layer formed on the substrate and having surface irregularities formed by aggregates of hollow silica nanoparticles.

A base material will not be specifically limited if it is a film excellent in transparency. Specifically, polyester-based resins such as polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, polybutylene terephthalate; Cellulose resins such as diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, isobutyl ester cellulose, propionyl cellulose, butyryl cellulose and acetyl propionyl cellulose; Polycarbonate resin; Acrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Styrene resins such as polystyrene and acrylonitrile-styrene copolymer; Polyolefin resins such as polyethylene, polypropylene, cycloolefin, or polyolefin having a norbornene structure, and an ethylene-propylene copolymer; Vinyl chloride resin; Amide resins such as nylon and aromatic polyamides; Imide resins such as polyetherimide and polyimide; Polyether sulfone type resin; Sulfone resins; Polyether ketone resins; Polyether ether ketone resins; Sulfided polyphenylene resins; Ethylene-vinylacetate resins; Polyvinyl acetal resins; Polyvinyl alcohol-based resins; Vinylidene chloride resins; Vinyl butyral resin; Allylate series resin; Polyoxymethylene type resin; And films composed of thermoplastic resins such as epoxy resins. These may be unstretched, uniaxially or biaxially stretched films. Among them, a monoaxial or biaxially stretched polyester film having excellent transparency and heat resistance, and a triacetyl cellulose film having good transparency and no optical anisotropy are preferable.

The thickness of the substrate is not particularly limited, and may be, for example, 8 to 1,000 μm, preferably 40 to 100 μm.

The anti-glare antireflection layer is a layer having both anti-glare and anti-reflection layers, and is a layer having surface irregularities formed by aggregates of hollow silica nanoparticles on a surface which is not bonded to the substrate. In addition, some of the above aggregates may be those in which quaternary ammonium salts are aggregated together. In addition, the aggregates may be less distributed as the distance from the substrate in the anti-glare antireflection layer.

The size of the aggregate, ie the average diameter, may be 0.5 to 5 μm.

The formation method of an anti-glare antireflection layer is not specifically limited. Specifically, the anti-glare antireflective coating composition may be applied to a substrate and then formed through a process of drying and curing. The application may use known methods such as die coaters, air knives, meyer bars, reverse rolls, sprays, blades, casting, gravure, spin coating and the like. The coating thickness can be 3 to 50 µm after drying, preferably 5 to 30 µm, more preferably 10 to 25 µm. Drying may be carried out by volatilizing the volatile components for 10 seconds to 1 hour, preferably 30 seconds to 10 minutes at a temperature of 30 to 150 ℃. As the solvent is volatilized during the drying process, the hollow silica nanoparticles float to the top of the coated layer by interaction with the quaternary ammonium salt, and the hollow silica nanoparticles floated to the top aggregate together to form aggregates or quaternary Aggregates with ammonium salts to form aggregates, through which surface irregularities are formed. When drying is complete, ultraviolet rays are cured by irradiation. For curing, a high pressure mercury lamp, an electrodeless lamp, a xenon lamp, a metal halide lamp, or the like may be used, and the irradiation amount may be about 0.01 to 10 J / cm 2, preferably 0.1 to 2 J / cm 2.

The anti-glare antireflection film configured as described above may have an internal haze value Hi due to internal diffusion of 0 ≦ Hi ≦ 0.5, and a total haze value Ha of 0.5 ≦ Ha ≦ 20. In addition, it is preferable that ratio (Hi / Ha) of internal haze value and total haze value is 0.01 <= H / Ha <= 1.

The anti-glare antireflection film may have an arithmetic mean surface roughness Ra of 0.02 μm ≦ Ra ≦ 0.2 μm and a 10-point average surface roughness Rz of 0.1 μm ≦ Rz ≦ 1 μm. In addition, the average interval Sm of the surface irregularities may be 30 μm ≦ Sm ≦ 150 μm, and the average inclination angle θa of the surface irregularities may be 0.1 ° ≦ θa ≦ 1.5 °.

The anti-glare antireflection film preferably has a transmittance of 200% or more, preferably 250% or more, and more preferably 300% or more, measured according to JIS K 7105. When the transmission sharpness becomes small, for example, when it is less than 200%, there is a tendency that the image becomes unclear and the glitter tends to occur when applied to an image display device.

The anti-glare antireflection film may have an average surface reflectance at 450 to 650 nm of 1 to 1.5%.

In addition, the anti-glare antireflection film may have a contrast reduction ratio of 10% or less when applied to a polarizing plate as compared to a conventional antireflection film.

The present invention provides a polarizing plate and an image display device provided with the anti-glare antireflection film.

The flat plate may have a conventional structure in which a polarizer protective film is laminated on at least one surface of the polarizer, and the anti-glare antireflection film is provided on at least one surface of the polarizing plate of this structure, that is, the polarizer or the polarizer protective film. It features.

The polarizing plate having the anti-glare antireflection film may be provided in a manner embedded in the image display device or attached to the window surface.

Polarizing plate equipped with anti-glare antireflection film can drive various kinds of image display devices such as reflective, transmissive and transflective liquid crystal display (LCD), TN type, STN type, OCB type, HAN type, VA type, IPS type, etc. It can be preferably used for a liquid crystal display (LCD) of the type. In addition, the present invention can be preferably used for an image display device such as a plasma display device (PDP), a field emission device (FED), an organic light emitting diode device, an inorganic light emitting diode device, and an electronic paper.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.

Example

Example  One

(1) coating composition

45% by weight of mixed monomer of pentaerythritol triacrylate and pentaerythritol tetraacrylate (M340, Miwon Corporation), 4% by weight of hollow silica nanoparticles (THRULYA 2320), quaternary ammonium salt (PQ-10, Soken Chemical Co., Ltd.) 0.1 Wt%, 48.9 wt% of a solvent in which isopropyl alcohol and methyl ethyl ketone are mixed in a weight ratio of 4.9: 5.1, and 2 wt% of a photopolymerization initiator 1-hydroxycyclohexylphenyl ketone (I-184, Shiba Corporation) are mixed for 1 hour. To produce an anti-glare antireflective coating composition.

(2) film

After coating the coating composition prepared in (1) on one side of the triacetyl cellulose (TAC) film having a thickness of 80㎛ using a Meyer Bar to apply a thickness of 5㎛ and dried at 80 ℃ for 1 minute. Subsequently, an anti-glare antireflection film was prepared by irradiating ultraviolet rays with an irradiation dose of 500 mJ / cm 2 to form an anti-glare antireflection layer.

Example  2-13, Comparative example  1-6

The same procedure as in Example 1, except that the ingredients and contents of Table 1 were used. At this time, the content is% by weight.

division acryl
Monomer Hollow silica Grade 4
Ammonium salt Mixed solvent Photopolymerization
Initiator M340 Type (particle size) content PQ-10 IPA / MEK content I-184 Example 1 45 I (50 nm) 4 0.1 4.9: 5.1 48.9 2 Example 2 45 I (50 nm) 8 0.1 5.4: 4.6 44.9 2 Example 3 45 I (50 nm) 12 0.1 5.4: 4.6 40.9 2 Example 4 45 I (50 nm) 16 0.1 4.9: 5.1 36.9 2 Example 5 45 I (50 nm) 20 0.1 4.9: 5.1 32.9 2 Example 6 27 I (50 nm) 50 0.1 4.9: 5.1 20.9 2 Example 7 45 I (50 nm) 2 0.1 4.9: 5.1 50.9 2 Example 8 45 I (50 nm) 8 0.5 4.9: 5.1 44.5 2 Example 9 45 I (50 nm) 8 One 4.9: 5.1 44 2 Example 10 45 I (50 nm) 8 3 4.9: 5.1 42 2 Example 11 45 I (50 nm) 8 5 4.9: 5.1 40 2 Example 12 45 I (50 nm) 8 10 4.9: 5.1 35 2 Example 13 45 I (50 nm) 8 0.1 7.8: 2.2 44.9 2 Comparative Example 1 45 I (50 nm) 6 - 4.9: 5.1 47 2 Comparative Example 2 45 - - 0.1 5.4: 4.6 52.9 2 Comparative Example 3 37.9 I (50 nm) 60 0.1 - - 2 Comparative Example 4 45 II (3.9 µm) 1.6 0.1 4.9: 5.1 51.3 2 Comparative Example 5 45 I (50 nm) 8 0.1 10: 0 44.9 2 Comparative Example 6 45 I (50 nm) 8 0.1 0:10 44.9 2 M340: mixed monomer of pentaerythritol tri / tetraacrylate (Miwon Corporation)
Hollow silica I: THRULYA 2320 (average particle diameter 50 nm, refractive index 1.3, solid content 20% by weight, dispersion medium: MEK, IPA)
Hollow silica II: Sylysia 350 (average particle diameter 3.9 mu m, refractive index 1.46)
PQ-10: Polymeric quaternary ammonium salt having a number average molecular weight of 4,000 or more, solid content 50% by weight (Soken Chemical Co., Ltd.)
IPA: Isopropyl Alcohol
MEK: methyl ethyl ketone
I-184: 1-hydroxycyclohexylphenyl ketone (Shiba Corporation)

Test Example

The physical properties of the anti-glare antireflection films prepared in Examples and Comparative Examples were measured by the following method, and the results are shown in Tables 2 and 3 below.

1.transmittance (%), Hayes

Total light transmittance, total haze value (Ha), and internal haze value (Hi) were measured using a spectrophotometer (HZ-1, Suga, Japan) with the TAC plane facing the light source D65.

2. pencil hardness

The pencil hardness was measured using a pencil hardness tester (PHT, Seokbo Science Co., Ltd.) on the surface of the anti-glare antireflection film, that is, the anti-glare antireflection layer. The pencil was manufactured by Mitsubishi Corporation and measured five times per pencil hardness. If the number of cigarettes is two or more, it is judged to be defective, and the pencil hardness is indicated by a pencil before the defective.

3. Scratch resistance

Scratch resistance was tested by reciprocating 10 times under 1 kg / (2 cm × 2 cm) using a steel wool tester (WT-LCM100, Protec Korea), and evaluated according to the following criteria. At this time, steel wool used # 0000.

<Evaluation Criteria>

A: 0 scratches

A ': 1 to 10 scratches

B: 11 to 20 scratches

C: 21 to 30 scratches

D: 31 or more scratches

4. Adhesiveness Peeling off  Square / 100)

After the 11 anti-glare anti-reflective film surface was drawn 11 straight lines at 1 mm intervals, respectively, to make 100 squares, a peel test was carried out using a tape (CT-24, Nichi Nishiba). It is represented by the ratio (n / 100) of the number n of squares not peeled out of the total 100 squares. That is, if any one of them is not peeled off, it becomes 100/100. This test was repeated three times and then evaluated by the average value.

5. Surface Roughness

The prepared anti-glare antireflection film was bonded to glass using a transparent optical pressure-sensitive adhesive to prepare a bonded body. Arithmetic mean surface roughness (Ra, μm), 10-point average surface roughness (measuring a 1.5 mm, measuring speed of 0.1 mm / sec using a surface roughness measuring instrument (SE4000, manufactured by Kosaka Institute) in accordance with JIS B 0601-1994) Rz, µm), the average spacing Sm (µm) of the unevenness, and the average inclination angle (θa, °) were measured.

6. Surface reflectance (%)

An adapter (MPC2200, Shimazu, Japan) was mounted on a spectrophotometer (UV2450, Shimazu) to measure the specular reflectance at an angle of incidence of 5 ° at an angle of incidence of 5 ° in a wavelength range of 380-780 nm, and a 450-650 nm The average reflectance in the wavelength range was calculated.

7. Transmission sharpness

After manufacturing the conjugate in the same manner as in the above 5, the transmission sharpness was measured using a filamentous measuring device (ICM-IDP, Suga Shijanki Co., Ltd.) according to JIS K 7105 standard. In this standard, four types of optical combs used for measuring image sharpness are specified, in which the ratio of the width of the dark portion to the width of the light is 1: 1, and the widths are 0.125 mm, 0.5 mm, 1.0 mm, and 2.0 mm. The sum of the image clarity measured using these four types of optical combs was made into transmission sharpness. The maximum value of the transmission sharpness in this case is 400%, and it is preferable that the value is large, for example, 250% or more.

8. Contrast Of Scintillation (Cotton twinkle)

The anti-glare antireflection film thus prepared was bonded to one surface of a conventional iodine-based absorption dichroic polarizing plate, and then bonded to a 32-inch liquid crystal panel using a double-sided adhesive tape. Then, contrast was measured using the spectroradiometer under liquid crystal drive. At this time, compared with the contrast value measured using the anti-reflective polarizing plate in which the anti-glare layer was not formed, the reduction ratio (%) was expressed.

In addition, the presence or absence of visibility of scintillation (surface glitter) was observed visually under liquid crystal driving.

9. Fluorescent lamp Reflection

After the prepared anti-glare antireflection film was bonded to a black acrylic plate, the presence or absence of anti-glare was confirmed through reflection visibility of fluorescent lamps.

division Example One 2 3 4 5 6 7 8 9 10 11 12 13 Transmittance
(%) 94.0 93.6 93.5 93.5 93.4 93.0 94.2 93.3 93.2 93.3 93.2 93.3 93.3 He
this
The Hi (%) 0.2 0.2 0.2 0.3 0.2 0.4 0.2 0.2 0.3 0.3 0.3 0.3 0.4 Ha (%) 0.8 1.2 2 2.4 3.6 19.5 0.5 2.3 2.8 4.3 5 5.5 10 Hi / Ha 0.25 0.17 0.1 0.13 0.06 0.02 0.4 0.09 0.11 0.07 0.06 0.05 0.04 Hardness 2H 2H 2H 2H 2H 2H 2H 2H 2H 2H 2H 2H 2H Scratch resistance A ' A A A A A A A A A A ' A B Adhesiveness (/ 100) 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 Surface roughness Ra (μm) 0.06 0.06 0.07 0.07 0.14 0.18 0.04 0.07 0.07 0.15 0.16 0.16 0.17 Rz (μm) 0.3 0.31 0.32 0.33 0.36 0.56 0.3 0.33 0.34 0.38 0.38 0.42 0.46 Sm (㎛) 132 103 86 74 68 32 143 77 70 63 59 49 46 Θa (°) 0.37 0.41 0.53 0.62 0.64 1.48 0.33 0.58 0.6 0.66 0.76 0.87 1.16 reflectivity(%) 1.12 1.16 1.1 1.03 1.13 1.17 1.15 1.2 1.1 1.13 1.04 1.20 1.19 Transmission Clarity (/ 400) 320 318 310 306 303 261 322 308 304 301 300 295 281 Contrast reduction rate (%) -0.1 -0.1 -1.6 -2.1 -2.4 -9.9 -0.1 -2 -2.4 -2.4 -2.9 -2.9 -6.3 Scintillation radish radish radish radish radish radish radish radish radish radish radish radish radish Fluorescent light reflection U U U U U U U U U U U U U

division Comparative example One 2 3 4 5 6 Transmittance
(%) 91.9 91.8 89.8 90.1 90.1 89.9 He
this
The Hi (%) 0.2 0.2 0.6 3.5 0.2 0.6 Ha (%) 0.3 0.3 32.4 8.2 3.2 2.6 Hi / Ha 0.67 0.67 0.02 0.43 0.06 0.23 Hardness 2H 2H 2H 2H 2H 2H Scratch resistance A ' A ' A ' A ' A ' A ' Adhesiveness (/ 100) 100 /
100 100 /
100 100 /
100 100 /
100 0/
100 100 /
100 Surface roughness Ra (μm) 0.03 0.2 0.27 0.21 0.03 0.43 Rz (μm) 0.025 0.03 1.38 0.18 0.03 0.16 Sm (㎛) 320 342 34 113 52 38 Θa (°) 0.08 0.07 2.49 0.1 0.12 0.2 reflectivity(%) 4.26 4.51 2.54 4.18 4.23 4.02 Transmission Clarity (/ 400) 329 324 52 268 240 235 Contrast reduction rate (%) -0.03 -0.04 -14.5 -13.4 -9.6 -10.3 Scintillation radish radish U U U U Fluorescent light reflection radish radish U U radish U

As shown in Tables 2 and 3 above, Examples 1 to 13 including (meth) acrylate monomers, hollow silica nanoparticles, quaternary ammonium salts, mixed solvents of alcohol solvents and ketone solvents, and photopolymerization initiators according to the present invention. Compared with the films of Comparative Examples 1 to 6, the film using the anti-glare anti-reflective coating composition has excellent transmittance, haze and surface roughness characteristics, and has a good surface hardness, which is resistant to scratches and excellent adhesion to the substrate. The coating layer was able to secure anti-glare and anti-reflection simultaneously. That is, excellent anti-glare property, no scintillation and low contrast reduction rate can provide excellent visibility. In particular, when the content of the hollow silica nanoparticles is 1 to 25% by weight and the content of the quaternary ammonium salt is 0.01 to 5% by weight, it is preferable to obtain a better effect.

1 is a scanning electron microscope (SEM) photograph showing the surface of the anti-glare antireflection film prepared in Example 2 of the present invention, it was confirmed that the surface irregularities were formed.

FIG. 2 is a scanning electron microscope (SEM) photograph showing the surface of the film prepared in Comparative Example 1, and it was found that surface irregularities were not well formed without using a quaternary ammonium salt.

Claims (13)

(Meth) acrylate monomers; Hollow silica nanoparticles; Quaternary ammonium salts; Mixed solvents of alcohol solvents and ketone solvents; And an anti-reflective coating composition comprising a photopolymerization initiator.
The anti-glare antireflective coating composition of claim 1, wherein the hollow silica nanoparticles have an average particle diameter of 1 to 100 nm.
The anti-glare antireflective coating composition of claim 1, wherein the hollow silica nanoparticles comprise 1 to 25% by weight in 100% by weight of the anti-glare antireflective coating composition.
The anti-glare anti-reflective coating composition according to claim 1, wherein the quaternary ammonium salt is a polymeric quaternary ammonium salt having a number average molecular weight of 4,000 or more.
The anti-glare anti-reflective coating composition according to claim 1, wherein the quaternary ammonium salt is included in an amount of 0.01 to 5% by weight in 100% by weight of the anti-glare anti-reflective coating composition.
The anti-glare antireflective coating composition according to claim 1, wherein the weight ratio of the alcohol solvent and the ketone solvent is 4: 6 to 6: 4.
The anti-glare antireflective coating composition of claim 1, wherein the mixed solvent comprises 40 to 60% by weight in 100% by weight of the anti-glare antireflective coating composition.
materials; And
An anti-glare antireflection film formed on the substrate and including an anti-glare antireflection layer having surface irregularities formed by aggregates of hollow silica nanoparticles.
The anti-glare antireflection film according to claim 8, wherein the anti-glare antireflection layer is formed of the coating composition of any one of claims 1 to 7.
The anti-glare antireflection film according to claim 8, wherein quaternary ammonium salts are aggregated in some of the aggregates.
The anti-glare antireflection film of claim 8 wherein the aggregates are less distributed in the anti-glare antireflection layer as the distance to the substrate is closer.
Polarizing plate provided with an anti-glare antireflection film of claim 8.
An image display device provided with a polarizing plate of claim 12.

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