KR20120128734A - Coating composition for low refractive layer, anti-reflection film using the same, polarizing plate and image displaying device including the film - Google Patents

Abstract

PURPOSE: A composition for forming a low refractive layer, a reflection preventing film, a polarizing plate, and a displaying device are provided to include an excellent inside antifouling property and an excellent inside anti-finger printing property when the reflection preventing film is applied. CONSTITUTION: A composition for forming a low refractive layer includes hollow silica particles, a fluorine acrylate compound, an acrylate monomer, a photoinitiatior and a solvent. The fluorine acrylate compound is obtained by reacting on a compound with three or more isocyanates in a molecule, fluorine alcohol and 2- hydroxyethyl acrylate. A refractive index of the hollow silica particles is between 1.17 and 1.40.

Description

Composition for forming low refractive index layer, anti-reflection film, polarizing plate and display device using same {COATING COMPOSITION FOR LOW REFRACTIVE LAYER, ANTI-REFLECTION FILM USING THE SAME, POLARIZING PLATE AND IMAGE DISPLAYING DEVICE INCLUDING THE FILM}

The present invention relates to a composition for forming a low refractive index layer, an antireflection film, a polarizing plate, and a display device using the same.

Recently, displays such as CRT, LCD, PDP have been developed, and various display devices using these displays have been used in various fields. When these display devices are used in a relatively bright place such as outdoors, the use of external light such as solar light or fluorescent light is increasingly problematic, and thus the display surface is prevented from reflecting outside light, that is, preventing reflection. The demand for is also growing.

Accordingly, antireflection films have been widely developed to prevent the external appearance of the display device from being easily reflected. As the antireflection film, an antireflection film having a multilayer structure is known (PCT JP2003-008535). The anti-reflection film of the multilayer structure is a two-layer structure consisting of a high refractive index layer and a low refractive index layer, a three-layer structure consisting of a medium refractive index layer, a high refractive index layer and a low refractive index layer, and a high refractive index layer, a low refractive index layer, a high refractive index layer And a four-layer structure composed of a low refractive index layer is known.

In recent years, the antireflection film is required to have additional functions such as scratch resistance, abrasion resistance, antifouling property as well as the function of antireflection. To this end, an antireflection film using a material having antifouling property in the low refractive index layer is used. However, the materials that can be used for the above anti-reflective film are limited, and the materials used in the past are expensive, thereby increasing the manufacturing cost, and the addition of such additional functions results in optical properties such as reflection properties, transmittance, and haze. There was a problem that the back is lowered.

SUMMARY OF THE INVENTION An object of the present invention is to provide a composition for forming a low refractive index layer having excellent antifouling resistance and fingerprint resistance and excellent antireflection performance such as reflectance when applied to an antireflection film as a solution to the conventional problems as described above. .

Another object of the present invention is to provide an antireflection film having excellent antifouling resistance and fingerprint resistance and excellent antireflection performance such as reflectance formed by using the composition for forming a low refractive index layer.

Still another object of the present invention is to provide a polarizing plate of excellent quality provided with the antireflection film.

Still another object of the present invention is to provide a display device of excellent quality provided with the antireflection film.

The present invention for achieving the above object, the reaction of the hollow silica particles (A), a compound having three or more isocyanate groups in the molecule, fluoro alcohol and 2-hydroxyethyl (meth) acrylate represented by the following formula (1) A fluorine (meth) acrylate compound (B), a (meth) acrylate monomer (C), a photoinitiator (D), and a solvent (E) obtained by the above are provided.

 [Formula 1]

(Y in Formula 1 is each independently H or F, n and m are each an integer from 0 to 200.)

The fluorine (meth) acrylate compound (B) preferably comprises at least one selected from the compounds represented by the following formulas (2) to (9).

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Chemical Formula 9]

(In Formulas 2 to 9, X is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Rf is represented by the following formula (10).)

[Formula 10]

(Y in formula 10 is each independently H or F, n and m are each an integer from 0 to 200.)

It is preferable that the refractive index of the said hollow silica particle is 1.17-1.40.

The composition for forming the low refractive layer is 0.1 to 20 parts by weight of the hollow silica particles (A), 0.1 to 30 parts by weight of the fluorine (meth) acrylate compound (B), and the (meth) acrylate based on 100 parts by weight of the total. 0.1 to 30 parts by weight of the monomer (C), 0.05 to 5 parts by weight of the photoinitiator (D) and 50 to 98 parts by weight of the solvent (E). In order to achieve the another object of the present invention, the present invention, the antireflection characterized in that it comprises a transparent substrate and a low refractive index layer formed on the upper surface of the transparent substrate using the composition for forming the low refractive index layer according to the present invention Provide a film.

The reflective film may further include a hard coating layer formed between the transparent substrate and the low refractive layer.

The refractive index of the low refractive index layer is preferably 1.2 to 1.49 at 25 ℃.

In order to achieve another object of the present invention, the present invention provides a polarizing plate characterized in that the anti-reflection film according to the present invention is provided.

In order to achieve another object of the present invention, the present invention provides a display device characterized in that the anti-reflection film according to the present invention is provided.

The composition for forming a low refractive index layer according to the present invention includes hollow silica particles and a fluorine (meth) acrylate compound having a predetermined structure, thereby providing excellent antifouling resistance and fingerprint resistance and excellent antireflection properties such as reflectance. You can get it. Accordingly, the anti-reflection film manufactured using the composition for forming the low refractive index layer has excellent antifouling resistance, anti-fingerprint resistance, and anti-reflection property, and may be usefully applied to polarizing plates and display devices.

Hereinafter, the present invention will be described in more detail.

The composition for forming a low refractive index layer according to the present invention comprises hollow silica particles (A), a fluorine (meth) acrylate compound (B), a (meth) acrylate monomer (C), a photoinitiator (D) and a solvent (E). do.

Hollow Silica Particles (A)

The hollow silica particles are used to lower the refractive index to increase antireflection properties and to increase scratch resistance.

The refractive index of the hollow silica particles is preferably 1.17 to 1.40, more preferably 1.17 to 1.35, and most preferably 1.17 to 1.30. Here, the refractive index does not mean the refractive index of the silica, that is, the refractive index of the outer portion forming the hollow particles, but rather the refractive index of the entire particle.

At this time, the porosity in the hollow silica particles is preferably in the range of 10 to 60%, more preferably in the range of 20 to 60%, and most preferably in the range of 30 to 60%.

When trying to achieve low refractive index and high porosity of hollow silica particles, the thickness of the outer edge is reduced and the strength of the particles is weakened. Therefore, from the viewpoint of scratch resistance, any particles having a refractive index of less than 1.17 of the hollow silica particles are not preferable because of their poor scratch resistance. In addition, when the refractive index of the hollow silica particles exceeds 1.40, the refractive index is high, and thus the antireflection property is not preferable. The refractive index of the hollow silica particles is measured using an Abbe refractive index meter (manufactured by ATAGO).

The hollow silica particles can be easily produced by a known production method. For example, the hollow silica particles can be prepared by the methods described in JP-A-2001-233611 and JP-A-2002-79616.

The average particle diameter of the hollow silica particles is preferably 30 to 150% of the low refractive index layer, more preferably 35 to 80%, particularly preferably 40 to 60%. That is, when the thickness of the low refractive index layer is 100 nm, the average particle diameter of the hollow silica particles is preferably 30 nm to 150 nm, more preferably 35 nm to 80 nm, particularly preferably 40 nm to 60 nm. When the hollow silica fine particles are in the above-described range, the ratio of the cavities becomes high so that a low refractive index can be achieved. Moreover, the formation of fine unevenness on the surface of the low refractive index layer does not cause the problem of lowering the reflectance. The hollow silica particles may be crystalline particles or amorphous particles, with monodisperse particles being preferred. In consideration of the shape, spherical particles are most preferred, but amorphous particles can be used without problems. The average particle diameter of the hollow silica fine particles is also measured by using an electron micrograph.

The hollow silica particles (A) may be a surface treated with a silane coupling agent, in this case, the dispersibility with the solvent is improved and participates in the curing during the curing process to improve the durability of the coating layer by forming a network with the binder Let's go.

The silane coupling agent is specifically methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldie 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) acrylooxymethyltrimethoxysil , γ- (meth) acrylooxymethyltriethoxysilane, γ- (meth) acryloxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acrylo Oxypropyltrimethoxysilane, γ- (meth) acrylooxypropyltrimethoxysilane, γ- (meth) acryloxyoxytriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltrie Oxysilaoctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, Perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, tripleuropropyltrimethoxysilane, N-β- (aminoethyl) γ- Aminopropylmethyldimethoxysilane, N-β- (aminoethyl) γ-a At least one selected from the group consisting of nopropyltrimethoxysilane, N-phenyl-γ- (aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, and methyltrichlorosilane Can be.

The content of the hollow silica is not necessarily limited, but may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the total composition for forming the low refractive index layer. If the content of the hollow silica is less than 0.1 parts by weight, the sufficient refractive index reduction effect is not obtained, and if it exceeds 20 parts by weight, there is a problem in that scratch resistance is lowered.

Fluoro (meth) acrylate  The compound (B)

The fluorine (meth) acrylate compound is added to ensure excellent pollution prevention and anti-fingerprint, according to the present invention, a compound having three or more isocyanate groups in the molecule, and a fluoro alcohol and 2-hydride represented by the following formula (1) What was obtained by making oxyethyl (meth) acrylate react is used.

[Formula 1]

(Y in Formula 1 is each independently H or F, n and m are each an integer from 0 to 200.)

The compound having three or more isocyanate groups in the molecule is preferably an isocyanurate type trifunctional isocyanate derived from 1,4-diisocyanatobutane, an isocyanurate type trifunctional isocyanate derived from 1,6-diisocyanatohexane , Isocyanurate-type trifunctional isocyanates derived from 1,8-diisocyanatooctane, isocyanurate-type trifunctional isocyanates derived from 1,12-diisocyanatodecane, 1,5-diisocyanato-2 Isocyanurate-type trifunctional isocyanate derived from methylpentane, isocyanurate-type trifunctional isocyanate derived from trimethyl-1,6-diisocyanatohexane, 1,3-bis (isocyanatomethyl) cyclohexane Isocyanurate type trifunctional isocyanate derived from trans-1,4-cyclohexane diisocyanate, isocyanurate type trifunctional isocyanate derived from trans- Isocyanurate trifunctional isocyanate derived from 4,4'-methylenebis (cyclohexyl isocyanate), isocyanurate trifunctional isocyanate derived from isophorone diisocyanate, toluene-2,4-diisocyanate Isocyanurate trifunctional isocyanate, isocyanurate trifunctional isocyanate derived from toluene-2,6-diisocyanate, isocyanurate trifunctional isocyanate derived from xylene-1,4-diisocyanate Isocyanurate trifunctional isocyanate derived from tetramethylxylene-1,3-diisocyanate, isocyanurate trifunctional isocyanate derived from 1-chloromethyl-2,4-diisocyanate, 4,4 Isocyanurate trifunctional isocyanate derived from '-methylenebis (2,6-dimethylphenylisocyanate), 4,4'-oxybi Isocyanurate type trifunctional isocyanate derived from (phenyl isocyanate), trifunctional isocyanate derived from hexamethylene diisocyanate, trimethane propanol adduct toluene diisocyanate, 1,6-diisocyanatohexane trifunctional biuret compound, etc. Compounds selected from the group consisting of can be used.

Preferably is a trifunctional isocyanate derived from hexamethylene diisocyanate, trimethanepropanol adduct toluene diisocyanate, isocyanurate type trifunctional isocyanate derived from isophorone diisocyanate with a compound having three or more isocyanate groups in the molecule, One selected from hexamethylene diisocyanate biuret isocyanate can be used.

Fluoro alcohol represented by the formula (1) is specifically 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol, 2,2,3,3,3-pentafluoro-1 -Propanol, 2,2,3,4,4,4-hexafluoro-1-butanol, 2,2,3,3,4,4,4-heptafluoro-1-butanol, 2,2,3,3 , 4,4,5,5-octafluoro-1-pentanol, 2,2,3,3,4,4,5,5,5-nonanfluoro-1-pentanol, 2,2,3,3 And compounds selected from the group consisting of 4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol and the like.

The reaction of the compound having three or more isocyanate groups in the molecule, and the fluoro alcohol and 2-hydroxyethyl (meth) acrylate represented by the formula (1) is preferably reacted in the presence of a solvent.

The solvent is not particularly limited, but ether, ketone, etc. may be preferably used in consideration of compatibility. More preferably, a fluorine-based solvent may be used in combination with the above-mentioned solvent. Specifically, hydrofluorocarbons and hydrofluoroethers can be used. Commercial products such as BARTEL XF (CF ₃ CHFCHFCF ₂ CF ₃ ) from DuPont, At least one selected from the group consisting of zeolol H (heptafluorocyclopentane), HFE-7100 (C ₄ F ₉ OCH ₃ ) and 7200 (C ₄ F ₉ OC ₂ H ₅ ) of 3M, etc. may be used.

Preferably, the fluoro (meth) acrylate compound (B) may include at least one selected from compounds represented by the following Chemical Formulas 2 to 9.

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Chemical Formula 9]

(In Formulas 2 to 9, X is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Rf is represented by the following formula (10).)

[Formula 10]

(Y in formula 10 is each independently H or F, n and m are each an integer from 0 to 200.)

The fluorine (meth) acrylate compound (B) is preferably used 0.1 to 30 parts by weight based on 100 parts by weight of the total hard coating composition. When the content of the fluorine compound (B) is less than 0.1 parts by weight based on the above standards, it is difficult to produce an antifouling and fingerprint wiping effect.

( Meta ) Acrylate Monomer (C)

The (meth) acrylate monomer is added to improve the hardness of the cured layer.

The (meth) acrylate monomers can be used without limitation those generally used in the art. Specifically, the (meth) acrylate monomers include dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, Ditrimethylolpropane tetra (meth) acrylate, (meth) acrylic ester, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tree (meth ) Acrylate, ethylene glycol di (meth) acrylate, propylene glycol (meth) acrylate, 1,3-butanedioldi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6- Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene Recall di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth ) Acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornol At least one compound selected from the group consisting of (meth) acrylates and the like can be used.

The content of the (meth) acrylate monomer is not limited, but is preferably included 0.1 to 30 parts by weight based on 100 parts by weight of the total composition for forming the low refractive index layer. If the content of the (meth) acrylate monomer is less than 0.1 parts by weight based on the above standard, there is a problem in the surface hardening of the low refractive index layer, and if it exceeds 30 parts by weight, the antireflection effect may be reduced by increasing the refractive index of the low refractive layer.

Photoinitiator (D)

The photoinitiator can be used without limitation those used in the art.

The photoinitiator is specifically 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinepropanone-1, diphenylketone benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-1 -One, 4-hydroxycyclophenylketone, dimethoxy-2-phenylatetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3-methylacetophenone, 4-knoloacetophenone, 4,4 At least one selected from the group consisting of -dimethoxyacetophenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexylphenylketone, and benzophenone can be used.

The photoinitiator is preferably contained in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the total composition for forming the low refractive layer. When the content of the photoinitiator is less than 0.05 parts by weight based on the above, the curing rate of the low refractive index layer-forming composition is slow, and when the content exceeds 5 parts by weight, cracking may occur in the low refractive layer.

Solvent (E)

The solvent can be used without limitation as long as it is known as a solvent of the composition for forming a low refractive index layer in the art.

For example, the solvent may be at least one selected from the group consisting of alcohols (methanol, ethanol, isopropanol, butanol, methylcellulose, ethylsulosorb), ketones (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, Ketone, cyclohexanone, etc.), hexane (hexane, heptane, octane etc.), benzene (benzene, toluene, xylene and the like) The solvents exemplified above may be used alone or in combination of two or more.

The solvent may be included in an amount of 50 to 98 parts by weight based on 100 parts by weight of the total composition for forming the low refractive layer. If the solvent is less than 50 parts by weight based on the above standard, the viscosity is high, the coating is difficult, and when it exceeds 98 parts by weight, it takes a long time in the curing process and there is a problem of low economic efficiency.

In addition to the above components, the composition for forming a low refractive index according to the present invention may be used with photo-stimulating agents, antioxidants, UV absorbers, light stabilizers, thermal polymerisation inhibitors, levling agents, surfactants, lubricants, and the like.

The present invention provides an anti-reflection film including a low refractive layer manufactured by using the composition for forming a low refractive layer described above.

More specifically, the anti-reflection film includes a transparent substrate and a low refractive layer formed by using the composition for forming a low refractive index layer according to the present invention on one or both surfaces of the transparent substrate.

In this case, the anti-reflection film of the present invention may further include a hard coating layer between the transparent substrate and the low refractive index layer to impart the physical strength of the film. That is, a preferred example of the anti-reflection film according to the present invention is a hard coating layer is formed on the upper surface of the transparent substrate, the low refractive index layer formed by curing the composition for forming the low refractive index layer on the upper surface.

The transparent substrate may be any film as long as it is a transparent plastic film. For example, a cycloolefin derivative having a unit of a monomer containing a cycloolefin such as norbornene or a polycyclic norbornene monomer, or a diacetyl cellulose Cellulose selected from triacetyl cellulose, acetyl cellulose butyrate, isobutyl ester cellulose, propionyl cellulose, butyryl cellulose, or acetyl propionyl cellulose , Polyacryl, polyimide, polyether sulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, poly Ether sulfone, paul One selected from dimethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyurethane, and epoxy may be used, and an unstretched uniaxial or biaxially oriented film may be used.

Of these, preferred are monoaxially or biaxially oriented polyester films which are excellent in transparency and heat resistance, cycloolefin-based derivative films which are excellent in transparency and heat resistance and capable of coping with the enlargement of the film, transparency and optical anisotropy, An acetylcellulose film may suitably be used.

The thickness of the transparent base film is 8 ~ 1000㎛, preferably 40 ~ 100㎛.

The hard coating layer formed on the transparent substrate preferably has a refractive index in the range of 1.48 to 2.00 at 25 ° C, more preferably 1.50 to 1.90, and more preferably from an optical design for obtaining a good antireflection film. Is 1.50 to 1.80. Since the antireflection film according to the present invention includes at least one low refractive index layer on the hard coating layer, when the refractive index is smaller than the above range, the antireflection property is lowered, and when the refractive index is larger than the above range, the color of the reflected light becomes stronger. There are disadvantages.

The hard coating layer is preferably formed by a crosslinking reaction or a polymerization reaction of the photocurable compound. These compounds are not particularly limited, and are formed by, for example, applying a composition for forming a hard coating layer containing a polyfunctional monomer or a polyfunctional oligomer onto a transparent support, and then crosslinking or polymerizing the polyfunctional monomer or polyfunctional oligomer. can do.

It is preferable that the functional group of the said polyfunctional monomer and a polyfunctional oligomer is light, an electron beam, and radiation polymerization property, and a photopolymerizable functional group is especially preferable.

As said photopolymerizable functional group, unsaturated polymerizable functional groups, such as a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group, etc. are mentioned, Especially, a (meth) acryloyl group is preferable.

Specific examples of the photopolymerizable polyfunctional monomer having the photopolymerizable functional group include alkylene glycols such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, and propylene glycol di (meth) acrylate. Meta) acrylic acid diesters; Polyoxyalkylene glycol (meth) acrylic acid di, such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate Esters; (Meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate; Ethylene oxide or propylene oxide adducts such as 2,2-bis {4- (acryloxydiethoxy) phenyl} propane and 2,2-bis {4- (acryloxypolypropoxy) phenyl} propane And meta) acrylic acid diesters. In addition, epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates can also be preferably used as the photopolymerizable polyfunctional monomer.

Among the photopolymerizable polyfunctional monomers exemplified above, esters of a polyhydric alcohol and (meth) acrylic acid can be preferably used.

As for the said photopolymerizable polyfunctional monomer, it is more preferable to use the polyfunctional monomer which has three or more (meth) acryloyl groups in 1 molecule. As a specific example of the polyfunctional monomer which has three or more (meth) acryloyl groups in the said molecule | numerator, a trimethylol propane tri (meth) acrylate, a trimethylol ethane tri (meth) acrylate, and 1,2, 4- cyclo Hexanetetra (meth) acrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate, tripentaerythritol hexatriacrylate, and the like.

The photopolymerizable polyfunctional monomer mentioned above can be used individually or in combination of 2 or more types, respectively.

It is preferable to use a photoinitiator for the polymerization reaction of the photopolymerizable polyfunctional monomer. As said photoinitiator, an optical radical initiator and a photocationic initiator are preferable, and an optical radical initiator is especially preferable.

As the photoradical initiator, those generally used in the art can be applied, and examples thereof include acetophenones, benzophenones, Michler's benzoylbenzoate, α-amyl oxime ester and tetramethylthiuram monosulfur. Those selected from pits and thioxanthones can be used.

In the anti-reflection film according to the present invention, the hard coating layer and the low refractive layer, which are sequentially formed on the transparent substrate, may be formed in a suitable manner such as die coater, air knife, reverse roll, spray, blade, casting, gravure, and spin coating. It can form by apply | coating the composition for forming and the composition for low refractive layer formation which concerns on this invention.

The coating thickness of the composition for forming a hard coat layer is usually 3 to 50 µm, preferably 5 to 40 µm, and more preferably 5 to 35 µm. After applying the composition for forming the hard coat layer and dried for 10 seconds to 1 hour, preferably 30 seconds to 10 minutes at a temperature of 30 ~ 150 ℃. When the drying is complete, UV light is irradiated to harden the composition for forming a hard coat layer to form a hard coat layer. The irradiation amount of UV light is about 0.01-10 J / cm ² , preferably 0.1-2 J / cm ² .

The coating thickness of the said composition for low refractive layer formation is 0.01-2 micrometers, Preferably it is 0.05-0.3 micrometers. After applying the composition for forming the low refractive layer is dried for 10 seconds to 1 hour, preferably 30 seconds to 10 minutes at a temperature of 30 ~ 150 ℃. When the drying is complete, UV light is irradiated to photocur the composition for forming the low refractive layer to form a low refractive layer. The irradiation amount of UV light is about 0.01-10 J / cm ² , preferably 0.1-2 J / cm ² .

When the coating thickness of the composition for forming the low refractive index layer is within the above range, more excellent antifouling properties can be obtained and good durability can be maintained.

The refractive index of the low refractive index layer has a relatively low refractive index compared to the above-described hard coating layer. It is preferable that the refractive index in 25 degreeC exists in the range of 1.20-1.49 from the optical design for obtaining the said low refractive layer from an antireflection film. If the refractive index of the low refractive index layer is smaller than the above range, the antireflection property is lowered. If the refractive index is higher than the above range, the color of the reflected light is strong.

The antireflective film prepared as described above has excellent scratch resistance, antireflection properties and excellent adhesion.

In the present invention, a polarizing plate including the antireflection film described above is provided.

The polarizing plate is not particularly limited, but various kinds may be used. As said polarizing plate, the film poly which uniaxially stretched by adsorb | sucking dichroic substances, such as iodine and a dichroic dye, to hydrophilic polymer films, such as a polyvinyl alcohol-type film and an ethylene-vinyl acetate copolymerization partial saponification film, for example And polyene-based alignment films such as dehydration products of vinyl alcohol and dehydrochlorination products of polyvinyl chloride. Among these, the polarizing plate which consists of dichroic substances, such as a polyvinyl alcohol-type film and iodine, is preferable. Although the thickness of these polarizing plates is not specifically limited, Generally, it is about 5-80 micrometers.

The present invention also provides a display device to which the above-described antireflection film is applied.

For example, various display devices excellent in visibility can be manufactured by embedding the polarizing plate on which the antireflection film of the present invention is formed in the display device. In addition, the antireflection film of the present invention may be attached to a window of the display device. The antireflection film of the present invention can be suitably used in reflective, transmissive, transflective LCDs or LCDs of various driving methods such as TN type, STN type, OCB type, HAN type, VA type, and IPS type. Moreover, the antireflection film of this invention can be used suitably also in various display apparatuses, such as a plasma display, a field emission display, an organic EL display, an inorganic EL display, an electronic paper.

The present invention will be further illustrated by the following examples, which are only specific examples of the present invention, and are not intended to limit or limit the protection scope of the present invention.

Synthesis Example 1 Fluorine (meth) acrylate compound

20 parts by weight of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI), 20 parts by weight of isophorone diisocyanate , 24 parts by weight of trifunctional isocyanate (Degussa), 6 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (Aldrich), 30 parts by weight of heptafluorocyclopentane (Aldrich) 0.1 part by weight of tin dilaurate was added and the reactor temperature was raised to 50 DEG C and then stirred for 2 hours. When 2260 cm ^-1 , the characteristic peak of isocyanate in the infrared spectral spectrum, disappeared completely, the reaction was terminated to obtain a compound having a solid content of 50 wt%.

Synthesis Example 2 Fluorine (meth) acrylate compound

10 parts by weight of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI), 10 parts by weight of isophorone diisocyanate , 22 parts by weight of trifunctional isocyanate (Degussa), 18 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (Aldrich), 30 parts by weight of heptafluorocyclopentane 0.1 part by weight of butyltin dilaurate was added, the temperature of the reactor was raised to 50 DEG C and the mixture was stirred for 2 hours. When 2260 cm ^-1 , the characteristic peak of isocyanate in the infrared spectral spectrum, disappeared completely, the reaction was terminated to obtain a compound having a solid content of 50 wt%.

Synthesis Example 3 Fluorine (meth) acrylate compound

20 parts by weight of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI), derived from hexamethyldiisocyanate 24 parts by weight of trifunctional isocyanate (BASF), 6 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (Aldrich), 30 parts by weight of heptafluorocyclopentane (Aldrich), dibutyl 0.1 parts by weight of tindilaurate was added and the reactor temperature was raised to 50 ° C. and stirred for 2 hours. When 2260 cm ^-1 , the characteristic peak of isocyanate in the infrared spectral spectrum, disappeared completely, the reaction was terminated to obtain a compound having a solid content of 50 wt%.

Synthesis Example 4 Fluoro (meth) acrylate Compound

13 parts by weight of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI, Inc.), hexamethyl diisocyanate , 22 parts by weight of trifunctional isocyanate (BASF Corp.), 15 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (Aldrich), 30 parts by weight of heptafluorocyclopentane, 0.1 parts by weight of dibutyltin dilaurate 0.1 And the reactor temperature was raised to 50 DEG C, followed by stirring for 2 hours. The reaction was terminated when 2260 cm ^-1 , the characteristic peak of isocyanate in the infrared spectral spectrum, disappeared completely to obtain a solid product of 50 wt%.

Synthesis Example 5 Fluorine (meth) acrylate compound

20 parts by weight of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI), trimethylene propanol adduct toluene , 18 parts by weight of diisocyanate (Aekyung Chemical Industries Co., Ltd.), 6 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (Aldrich), 30 parts by weight of heptafluorocyclopentane and 0.1 parts by weight of dibutyltin dilaurate And the temperature of the reactor was raised to 50 DEG C, followed by stirring for 2 hours. When 2260 cm ^-1 , the characteristic peak of isocyanate in the infrared spectral spectrum, disappeared completely, the reaction was terminated to obtain a product having a solid content of 50 wt%.

Synthesis Example 6 Fluoro (meth) acrylate Compound

15 parts by weight of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI), trimethylene propanol adduct toluene 20 parts by weight of diisocyanate (Ake Kagaku Co., Ltd.), 15 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (Aldrich), 30 parts by weight of heptafluorocyclopentane and 0.1 parts by weight of dibutyltin dilaurate And the temperature of the reactor was raised to 50 DEG C, followed by stirring for 2 hours. The reaction was terminated when 2260 cm ^-1 , the characteristic peak of isocyanate in the infrared spectral spectrum, disappeared completely to obtain a solid product of 50 wt%.

Synthesis Example 7 Fluorine (meth) acrylate compound

20 parts by weight of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI), 20 parts by weight of hexamethylene diisocyanate buret 23 parts by weight of isocyanate (BASF Corp.), 7 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (Aldrich), 30 parts by weight of heptafluorocyclopentane and 0.1 part by weight of dibutyltin dilaurate And the temperature of the reactor was raised to 50 DEG C, followed by stirring for 2 hours. The reaction was terminated when 2260 cm ^-1 , the characteristic peak of isocyanate in the infrared spectral spectrum, disappeared completely to obtain a solid product of 50 wt%.

Synthesis Example 8 Fluorine (meth) acrylate compound

12 parts by weight of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI), 12 parts by weight of hexamethylene diisocyanate buret 23 parts by weight of isocyanate (BASF Corp.), 15 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (Aldrich), 30 parts by weight of heptafluorocyclopentane and 0.1 part by weight of dibutyltin dilaurate And the temperature of the reactor was raised to 50 DEG C, followed by stirring for 2 hours. The reaction was terminated when 2260 cm ^-1 , the characteristic peak of isocyanate in the infrared spectral spectrum, disappeared completely to obtain a solid product of 50 wt%.

 Preparation Example Composition for Hard Coating Layer Formation

70 parts by weight of urethane acrylate (Shin-Nakamura Chemical Co., U-15HA), 30 parts by weight of pentaerythritol triacrylate (Co., Ltd., PE-3A), 3 parts by weight of photoinitiator (Shiba Corporation, D-1173), 150 parts by weight of methyl Ethyl ketone and 100 parts by weight of toluene were combined to prepare a composition having a refractive index of 1.51.

[Examples 1 to 14 and Comparative Examples 1 to 3]

Each component was mixed at the ratios shown in Tables 1 and 2 to prepare a composition for forming a low refractive layer.

Composition Example One 2 3 4 5 6 7 8 9 Polyfunctional fluorine compounds Synthesis Example 1 3 3 Synthesis Example 2 3 Synthesis Example 3 3 Synthesis Example 4 3 Synthesis Example 5 3 Synthesis Example 6 3 Synthesis Example 7 3 Synthesis Example 8 3 Fluoropolymer Hollow Silica Particles 3 3 3 3 3 3 3 3 10 Acrylate monomer (a) 2 2 2 2 Acrylate monomer (b) 2 2 2 2 One menstruum MIBK 86 86 86 86 4 4 4 4 76 MEK 4 4 4 4 86 86 86 86 8 Photoinitiator I-184 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 additive BYK-378 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Refractive Index of Low Refractive Layer 1.37 1.36 1.38 1.37 1.39 1.37 1.36 1.32 1.36

Composition Example Comparative example 10 11 12 13 14 One 2 3 Polyfunctional fluorine compounds Synthesis Example 1 Synthesis Example 2 10 Synthesis Example 3 31 Synthesis Example 4 One Synthesis Example 5 Synthesis Example 6 0.09 Synthesis Example 7 20 Synthesis Example 8 Fluoropolymer 15 10 Hollow Silica Particles 5 5 3 3 15 Acrylate monomer (a) One 2 2 3 2 3 5 Acrylate monomer (b) 2 6 menstruum
MIBK 76 86 70 57 13 86 70 3 MEK 6 4 3 4 68 4 10 80 Photoinitiator I-184 1.5 1.5 1.5 1.5 1.41 1.5 1.5 1.5 additive BYK-378 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Refractive Index of Low Refractive Layer 1.32 1.35 1.31 1.34 1.4 1.45 1.48

Each of the components used in Tables 1 and 2 are as follows.

Fluoropolymer: CC-04 (refractive index 1.41, solid content 50% in butyl acetate, central glass)

Hollow silica particles: refractive index 1.30, average particle diameter 40nm, catalyzed sand

Acrylate monomer (a): dipentaerythritol penta / hexa acrylate (refractive index 1.476, Nippon Synthetic Co., DPHA) acrylate monomer (b): pentaerythritol tri / tetra acrylate (refractive index 1.47, Miwon Corporation, M340)

MIBK: methyl isobutyl ketone

MEK: methyl ethyl ketone

I-184: 1-hydroxycyclohexylphenyl ketone (Shiba Corporation)

BYK-378: Silicone Modified Oil (BYK)

<Experimental Example>

The hard coating layer composition prepared in the above Preparation Example was applied on one side of the transparent substrate made of a triacetyl cellulose film having a thickness of 80 μm to form a hard coating layer having a thickness of 5 μm by heat curing after heat drying. The low refractive index layer forming compositions prepared in Examples and Comparative Examples were applied onto the hard coating layer to form a low refractive index layer having a thickness of 0.1 μm by heat curing after heat drying.

The physical properties of the antireflective film prepared as described above were measured as follows, and the results are shown in Table 3 below.

(1) scratch resistance

The scratch resistance was tested by using a steel wool tester (WT-LCM100, manufactured by Protec Co., Ltd.) for 10 reciprocations at 1 kg / (2 cm × 2 cm). Steel wool used # 0000.

A: 0 scratches

A ': 1 to 10 scratches

B: 11-20 scratches

C: 21-30 scratches

D: 31 or more scratches

(2) adhesion

Eleven straight lines were drawn on the coated surface of the film at intervals of 1 mm each to form 100 squares, and then three peel tests were conducted using a tape (CT-24, Nichi Nippon Corp.). Three 100 squares were tested and averaged.

The adhesion was recorded as follows.

Adhesion = n / 100

n: number of rectangles that do not peel out of the entire rectangle

100: total number of squares

Therefore, when none of the peeling was recorded as 100/100.

(3) surface reflectance

The adapter MPC2200 was attached to the spectrophotometer UV2450 (Shishima Co., Ltd.), the specular reflectance with respect to the exit angle of 5 ° at the incident angle of 5 ° in the wavelength region of 380 to 780 nm was measured, and the average reflectance of 450 to 650 nm was calculated.

(4) haze

Haze was measured using a haze meter (Suga HZ-1).

(5) male contact angle

After dropping water droplets onto the film surface at room temperature (25 ° C.), the contact angle with respect to the water droplets was measured 1 minute later using a contact angle measuring instrument (KSV Co., Ltd. CAM100). The contact angle was measured 5 times with the same sample to the left and right contact angle of the water droplets and used the average value.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Comparative Example 1 Comparative Example 2 Comparative Example 3 Scratch resistance A A A A A A A A A A A A A A C B C Adhesiveness 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 90/100 85/100 Haze (%) 0.2 0.2 0.3 0.3 0.2 0.3 0.2 0.2 0.3 0.3 0.4 0.2 0.3 0.3 0.3 0.5 0.7 reflectivity(%) 0.96 0.97 1.03 0.93 1.04 1.01 0.96 0.97 0.98 0.99 0.92 1.01 0.97 0.92 0.96 1.33 1.35 Water contact angle (°) 109 110 112 115 111 110 109 112 118 115 108 113 113 101 55 75 73

As shown in Table 3, in the case of Examples 1 to 14, in which the fluorine (meth) acrylate compound and the hollow silica particles were included according to the present invention, the number was a measure of fouling resistance compared to Comparative Examples 1 to 3, which did not include the same. It can be seen that the contact angle is high, so that the stain resistance is excellent and the scratch resistance is very excellent. In addition, it can be seen that the excellent reflectivity characteristics can realize an excellent anti-reflection effect.

Claims (9)

A fluoro (meth) acrylate compound (B) obtained by reacting a hollow silica particle (A), a compound having three or more isocyanate groups in a molecule, and a fluoro alcohol and 2-hydroxyethyl (meth) acrylate represented by the following formula (1) ), A (meth) acrylate monomer (C), a photoinitiator (D) and a solvent (E).
[Formula 1]

(Y in Formula 1 is each independently H or F, n and m are each an integer from 0 to 200.) The composition of claim 1, wherein the fluorine (meth) acrylate compound (B) comprises at least one selected from compounds represented by the following Chemical Formulas 2 to 9.
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

(In Formulas 2 to 9, X is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Rf is represented by the following formula (10).)
[Formula 10]

(Y in formula 10 is each independently H or F, n and m are each an integer from 0 to 200.) The composition for forming a low refractive index according to claim 1, wherein the hollow silica particles have a refractive index of 1.17 to 1.40. The composition for forming a low refractive index layer is 0.1 to 20 parts by weight of the hollow silica particles (A), 0.1 to 30 parts by weight of the fluorine compound (B), and the (meth) acrylate. A composition for forming a low refractive index comprising 0.1 to 30 parts by weight of a monomer (C), 0.05 to 5 parts by weight of the photoinitiator (D) and 50 to 98 parts by weight of the solvent (E). An antireflection film comprising a transparent substrate and a low refractive index layer formed on the upper surface of the transparent substrate using the composition for forming a low refractive index layer according to any one of claims 1 to 4. The antireflection film according to claim 5, further comprising a hard coating layer formed between the transparent substrate and the low refractive layer. The antireflection film of claim 5, wherein the low refractive index layer has a refractive index of 1.2 to 1.49 at 25 ° C. 7. The antireflection film of Claim 5 was provided, The polarizing plate characterized by the above-mentioned. Display device characterized in that the anti-reflection film of claim 5 is provided.