KR20110039862A - Coating composition for low refractive layer, anti-reflection film using the same, polarizer and image displaying device comprising said anti-reflection film - Google Patents

Abstract

PURPOSE: A coating composition for forming a low refractive layer is provided to ensure excellent scratch resistance, antifouling property, and anti-reflective property. CONSTITUTION: A coating composition for forming a low refractive layer comprises hollow silica particles(A), hydroxyl group-containing fluorinated polymer(B), (meth)acrylate monomer(C), photoinitiator(D) and solvent(E). The hydroxyl group-containing fluorinated polymer(B) includes a fluorine-containing vinyl monomer polymerization unit(B1) and a fluorine-containing vinyl monomer polymerization unit(B2).

Description

Composition for forming a low refractive index layer, anti-reflection film using the same, polarizing plate and display device including the same TECHNICAL FIELD

The present invention relates to a composition for forming a low refractive index, an antireflection film using the same, a polarizing plate and a display device including 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, there is an increasing problem that the display of the light by the external light such as sunlight or fluorescent light becomes a problem, thereby preventing the reflection of external light on the surface of the display, that is, preventing reflection. The demand for is also growing.

Accordingly, anti-reflective coating, which is a coating technology for preventing the external appearance of the display device from being easily reflected, has been widely developed. In addition to the anti-reflection function, the display device requires more functions such as scratch prevention, anti-pollution, and anti-static in order to protect and enhance the display.

An object of the present invention is to provide a composition for forming a low refractive index layer excellent in scratch resistance, stain resistance and anti-reflection characteristics when applied to the production of an anti-reflection film, excellent in durability.

It is another object of the present invention to provide an antireflection film having excellent scratch resistance and antireflection properties.

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

Another object of the present invention is to provide a display device provided with the anti-reflection film.

The present invention for achieving the above object comprises a hollow silica particle (A), a hydroxyl group-containing fluoropolymer (B), a (meth) acrylate monomer (C), a photoinitiator (D) and a solvent (E). Provided is a composition for forming a low refractive layer.

The hydroxyl group-containing fluoropolymer (B) is a fluorine-containing vinyl monomer polymerization unit (B1); And a fluorine-containing vinyl monomer polymerization unit (B2) containing a hydroxyl group.

The fluorine-containing vinyl monomer polymerization unit (B1) includes a polymerization unit represented by the following Chemical Formula 1, and the fluorine-containing vinyl monomer polymerization unit (B2) including the hydroxyl group includes a polymerization unit represented by the following Chemical Formula 3 desirable.

[Formula 1]

(In Formula 1, X is a hydrogen atom or a methyl group, Rf is a linear or branched hydrocarbon compound having 1 to 50 carbon atoms, and the hydrogen atom in the molecule is substituted with 50% or more of fluorine, and n is a corresponding component in the hydroxyl group-containing fluoropolymer. Mole% of 1 ≦ n ≦ 50.)

(3)

(In Formula 3, Rf is a linear or branched hydrocarbon compound having 1 to 50 carbon atoms, in which a hydrogen atom in a molecule is substituted with 50% or more of fluorine, and p is a mole% of the corresponding component in the hydroxyl group-containing fluoropolymer, where 1 ≦ p ≦ 50.)

The fluorine-containing vinyl monomer polymerization unit (B1) may further include a polymerization unit represented by the following Chemical Formula 2.

[Formula 2]

(In Formula 2, Rf is a linear or branched hydrocarbon compound having 1 to 50 carbon atoms, in which a hydrogen atom in a molecule is substituted with fluorine by 50% or more. 50.)

It is preferable that the said hydroxyl-containing fluoropolymer (B) is contained 0.1-30 weight part with respect to 100 weight part of whole compositions for low refractive layer formation.

In order to achieve another object of the present invention, the present invention, the 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 according to the present invention To provide.

At least one hard coating layer having a higher refractive index than the low refractive layer may be formed between the transparent substrate and the low refractive layer.

The low refractive index layer preferably has a refractive index of 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 is provided.

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

The composition for forming a low refractive index layer according to the present invention includes a hydroxyl group-containing fluoropolymer having a predetermined structure, thereby improving compatibility and obtaining excellent scratch resistance, antifouling property, and antireflection effect. Accordingly, the antireflection film manufactured using the composition for forming the low refractive index layer has excellent scratch resistance and antireflection, and may be usefully applied to a polarizing plate and a display device.

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

The composition for forming a low refractive layer according to the present invention includes hollow silica particles (A), hydroxyl group-containing fluoropolymer (B), (meth) acrylate monomer (C), photoinitiator (D) and solvent (E).

Hollow Silica Particles (A)

The hollow silica particles (A) are used to lower the refractive index to increase antireflection characteristics and to increase scratch resistance.

The refractive index of the hollow silica particles (A) 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 (A) 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 the low refractive index and the high porosity thereof of the hollow silica particles (A), 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).

Said hollow silica particle (A) can be manufactured easily by a well-known manufacturing method. For example, the hollow silica particles (A) may be those produced by the methods described in JP-A-2001-233611 and JP-A-2002-79616.

The average particle diameter of the hollow silica particles (A) is preferably 30 to 150% of the low refractive layer, more preferably 35 to 80%, particularly preferably 40 to 60%. That is, when the thickness of the low refractive layer is 100 nm, the average particle diameter of the hollow silica particles (A) is preferably 30 nm to 150 nm, more preferably 35 nm to 80 nm, and particularly preferably 40 nm to 60 nm. When the average particle diameter of the hollow silica particles (A) is within the above-described range, the ratio of the cavities is increased to achieve a low refractive index. Moreover, fine unevenness is formed on the surface of the low refractive index layer so that the problem of lowering the reflectance is not caused. The hollow silica particles (A) may be crystalline particles or amorphous particles, with monodisperse particles being preferred. In view of the shape, spherical particles are most preferred, but amorphous particles can be used without problems. The average particle diameter of the hollow silica particles (A) 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) acrylooxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acrylic Rooxypropyltrimethoxysilane, γ- (meth) acrylooxypropyltrimethoxysilane, γ- (meth) acryloxyoxytriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyl tree Ethoxy silane octyl triethoxy silane, decyl triethoxy silane, butyl triethoxy silane, isobutyl triethoxy silane, hexyl triethoxy silane, octyl triethoxy silane, 3-ureido isopropyl propyl triethoxy silane , Perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, 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 used. have.

It is preferable that the said hollow silica particle (A) is contained 0.1-30 weight part with respect to 100 weight part of all the said low refractive index formation compositions. When the content of the hollow silica particles (A) is included in the above range on the basis of the above, the refractive index of the composition for forming the low refractive index layer can be adjusted, and antireflection characteristics can be exhibited satisfactorily.

Hydroxyl-containing fluoropolymer (B)

The hydroxyl group-containing fluoropolymer (B) is included to reduce the refractive index, to improve the stain resistance and scratch resistance.

The hydroxyl group-containing fluoropolymer (B) is a fluorine-containing vinyl monomer polymerization unit (B1); And a fluorine-containing vinyl monomer polymerization unit (B2) containing a hydroxyl group.

The fluorine-containing vinyl monomer polymerization unit (B1) may include a polymerization unit represented by the following Chemical Formula 1, and may further include a polymerization unit represented by the following Chemical Formula 2.

[Formula 1]

 (In Formula 1, X is a hydrogen atom or a methyl group, Rf is a linear or branched hydrocarbon compound having 1 to 50 carbon atoms, and the hydrogen atom in the molecule is substituted with 50% or more of fluorine, and n is a corresponding component in the hydroxyl group-containing fluoropolymer. Mole% of 1 ≦ n ≦ 50.)

[Formula 2]

(In Formula 2, Rf is a linear or branched hydrocarbon compound having 1 to 50 carbon atoms, in which a hydrogen atom in a molecule is substituted with fluorine by 50% or more. 50.)

It is preferable that the fluorine-containing vinyl monomer polymerization unit (B2) containing the said hydroxyl group contains the polymerization unit represented by following formula (3).

(3)

(In Formula 3, Rf is a linear or branched hydrocarbon compound having 1 to 50 carbon atoms, in which a hydrogen atom in a molecule is substituted with fluorine by 50% or more, and p is a mole% of a corresponding component in the hydroxyl group-containing fluoropolymer, where 1 ≦ p ≦ 50.)

In the hydroxyl group-containing fluoropolymer (B), n, m, and p, the number of moles of the polymerized units of Formulas 1 to 3, respectively satisfy the ranges of 1 ≦ n ≦ 50, 0 ≦ m ≦ 50, and 1 ≦ p ≦ 50. Its high compatibility with other components provides excellent refractive index lowering effect and improves scratch resistance.

In the above, Rf is a linear or branched hydrocarbon compound having 1 to 50 carbon atoms, and represents a fluoroalkyl group in which a hydrogen atom in the molecule is substituted by 50% or more of fluorine. More specifically, Rf represents a trifluoromethyl group, a perfluoroethyl group, and a perfluoriso Fluoroalkyl groups having 1 to 6 carbon atoms, such as a propyl group, a perfluoropropyl group, a perfluoroisobutyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorocyclohexyl group.

Specific examples thereof include trifluoromethyl group, 1,1,2,2,2-pentafluoroethyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, 1,1,2,2,3, 3,4,4,4-nonanefluorobutyl group, 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecanefluorohexyl group, 1,1,1 , 3,3,3-hexafluoroisopropyl group, 1,1,1,2,3,3,3-heptafluoroisopropyl group, 1,1,2,2,3,3,4,4,5 And a 5,6,6-undecane fluorocyclohexyl group.

The hydroxyl group-containing fluoropolymer (B) is unsaturated represented by the (meth) acrylate compound represented by the following formula (4) to induce the repeating unit of formula (1), and optionally represented by the following formula (5) to induce the repeating unit of the formula (2) It can be easily obtained by polymerizing a compound having a double bond and a compound having an unsaturated double bond with the hydroxyl group represented by the following formula (6) which induces the repeating unit of the formula (3).

[Formula 4]

(In Formula 4, X is a hydrogen atom or a methyl group, Rf is a linear or branched hydrocarbon compound having 1 to 50 carbon atoms, and hydrogen atoms in the molecule are substituted with fluorine by 50% or more.)

The (meth) acrylate compounds represented by the formula (4) can be used alone or in combination of two or more.

Specific examples are 2- (perfluorohexyl) ethyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate , 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl (meth) acrylate, 1H, 1H-pentadecafluorooctyl (meth) Acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, and the like can be used.

[Chemical Formula 5]

(In Formula 5, Rf is a linear or branched hydrocarbon compound having 1 to 50 carbon atoms, in which a hydrogen atom in a molecule is substituted with 50% or more of fluorine.)

Compounds having an unsaturated double bond represented by the formula (5) can be used alone or in combination of two or more.

Specific examples include 3-trifluoromethoxypropene, 3-pentafluoroethyloxypropene, 3- (2,2,2-trifluoro-1-trifluoromethylethoxy) propene, 3- (2,2 , 3,3,4,4,4-heptafluorobutoxy) propene, 3- [1,3,3,3-tetrafluoro-1- (2,2,2-trifluoroethyl) propoxy] prop You can use a pen.

[Formula 6]

(In Formula 6, Rf is a linear or branched hydrocarbon compound having 1 to 50 carbon atoms in which hydrogen atoms in the molecule are substituted with at least 50% of fluorine.)

Compounds having a hydroxyl group and an unsaturated double bond represented by the formula (6) can be used alone or in combination of two or more.

Specific examples include 3-aryloxy-1,1,1,5,5,5-hexafluoropentan-3-ol, 2-aryloxy-1,1,1,3,3,3-hexafluoropropane- 2-ol, 2-aryloxy-1,1,1,4,4,4-hexafluorobutan-2-ol, 3-aryloxy-1,1,1,5,5,6,6,6- Octafluorohexan-3-ol etc. can be used.

The hydroxyl group-containing fluoropolymer (B) may be prepared by a known polymerization method, bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, and the like, and may be prepared using a known polymerization initiator, a known chain transfer agent, or the like during the polymerization process. Can be.

Examples of the polymerization initiator include azo-based polymerization initiators such as azobisisobutyronitrile and azobisisovaleronitrile, peroxide-based polymerization initiators such as benzoyl peroxide, di-t-butyl peroxide, and lauryl peroxide. It is available. In addition, the chain transfer agent may be a chain transfer agent containing a mercapto group. Preferably, the solution may be prepared by a solution polymerization method, and the solvent used in the solution polymerization method is not necessarily limited. Specifically, acetates such as n-butyl acetate and pentyl acetate, aromatic hydrocarbons such as benzene, toluene and xylene Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin, γ-butyrolactone Cyclic ester, such as these, is mentioned.

The molecular weight of the polymer is usually 1000 to 50,000, preferably 3,000 to 20,000, in terms of weight average molecular weight (polystyrene equivalent) by gel permeation chromatography (GPC).

It is preferable that the content of the hydroxyl group-containing fluoropolymer (B) is included in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the total composition for forming the low refractive layer. When the content of the hydroxyl group-containing fluoropolymer (B) is less than 0.1 parts by weight based on the above standard, sufficient refractive index reduction effect and fouling resistance, scratch resistance is not obtained, there is a problem in that the adhesive strength is lowered when it exceeds 30 parts by weight.

(Meth) acrylate monomer (C)

The (meth) acrylate monomer (C) is included to improve the hardness of the cured layer. Specifically, the (meth) acrylate monomer (C) is dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) Acrylate, (meth) acrylic ester, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (Meth) acrylate, propylene glycol (meth) acrylate, 1,3-butanedioldi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate Neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hi Hydroxyethyl) isocyanurate di (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isooctyl (meth) acrylate, iso At least 1 selected from the group consisting of dexyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornol (meth) acrylate, and the like Species compounds can be used.

Although the usage-amount of the said (meth) acrylate monomer (C) is not restrict | limited, It is preferable that 0.1-30 weight part is included with respect to 100 weight part of whole compositions for low refractive layer formation. If the addition amount of the (meth) acrylate monomer (C) is less than 0.1 parts by weight, 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 (D) can be used without limitation to those used in the art. Examples of the photoinitiator (D) include 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinepropanone-1, diphenyl ketone benzyl dimethyl ketal and 2-hydroxy-2-methyl-. 1-phenyl-1-one, 4-hydroxycyclophenylketone, dimethoxy-2-phenylatetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3-methylacetophenone, 4-knoloaceto At least one selected from the group consisting of phenone, 4,4-dimethoxyacetophenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexylphenyl ketone, benzophenone and the like can be used.

The photoinitiator (D) may be used 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 (D) is less than 0.05 parts by weight based on the above criteria, if the curing rate of the low refractive index layer-forming composition is slow and exceeds 5 parts by weight, cracking may occur in the low refractive layer.

Solvent (E)

The solvent (E) 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.

In one example, the solvent (E) is alcohol-based (methanol, ethanol, isopropanol, butanol, methyl cellulose, ethyl solusorb, etc.), ketone-based (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone , Dipropyl ketone, cyclohexanone and the like), hexane-based (hexane, heptane, octane and the like), benzene-based (benzene, toluene, xylene and the like) and the like can be preferably used. The solvents exemplified above may be used alone or in combination of two or more thereof.

The solvent (E) may be added to 50 to 98 parts by weight based on 100 parts by weight of the total composition for low refractive layer formation. 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 antireflection 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 the low refractive layer on one surface 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 antireflection 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.

As the transparent base material, any film can be used 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 and 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 May be used polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyurethane, may be used one selected from among epoxy, non-stretched uniaxially or biaxially stretched film.

Among them, a monoaxial or biaxially stretched polyester film having excellent transparency and heat resistance, but a cycloolefin derivative film capable of coping with an enlargement of the film while being excellent in transparency and heat resistance, and having no transparency and optical anisotropy Acetylcellulose film can be suitably used.

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

The refractive index of the hard coat layer formed on the transparent substrate is preferably in the range of 1.48 to 2.00, more preferably 1.50 to 1.90, more preferably from 25 ° C from the optical design for obtaining the antireflection film. Preferably 1.50-1.80. 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 this range, the antireflection property is lowered, and when the antireflection film is large, the color of the reflected light is strong.

The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of the photocurable compound. These compounds are not particularly limited, and for example, a composition for forming a hard coating layer containing a photocurable polyfunctional monomer or a polyfunctional oligomer is coated on a transparent substrate to crosslink or polymerize a polyfunctional monomer or a polyfunctional oligomer. Can be formed.

As a functional group of the polyfunctional monomer and polyfunctional oligomer of the said photocuring agent, it is preferable that it is light, an electron beam, and a radiation polymerizable, and especially a photopolymerizable functional group is 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 are preferable.

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 trimethyl all 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 above-mentioned photopolymerizable polyfunctional monomer 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 said 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 photoinitiator, those generally used in the art may be generally used. For example, acetophenones, benzophenones, Michler's benzoylbenzoate, α-amyl oxime ester, tetramethylthiuram mono The thing selected from sulfite, thioxanthones, etc. can be used.

In the present invention, the hard coating layer and the low refractive layer, which are sequentially formed on the transparent substrate in the anti-reflection film, are 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 completed, the hard coating layer is formed by curing the composition for forming the hard coat layer by irradiating UV light. 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 composition for forming a low refractive index layer formed on the hard coat layer is 0.01 to 2 µm, preferably 0.05 to 0.3 µm. When the coating thickness of the low refractive index layer is within the above range, more excellent antifouling properties can be obtained, and good durability can be maintained.

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 drying is complete, UV light is irradiated to cure the composition for forming the low refractive layer. The irradiation amount of UV light is about 0.01-10 J / cm ² , preferably 0.1-2 J / cm ² .

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 less than the above range, the antireflection property is lowered. If the refractive index is greater than the above range, the color of the reflected light is strong.

The antireflection film prepared as described above has excellent scratch resistance antireflection effect and excellent antifouling property.

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 an 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 Synthesis of hydroxyl-containing fluoropolymer

A 4-neck jacket reactor (1L) was equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot, and a nitrogen gas inlet tube, 200 parts by weight of n-butyl acetate, 1H, 2H, 2H-heptadecafluoro 5 parts by weight (10 mol) of decyl acrylate (Central Glass), 10 parts by weight (30 mol) of 3-trifluoromethoxypropene (Central Glass), 3-aryloxy-1,1,1,5,5 , 5-hexafluoropentane-3-ol (central glass company) 10 weight part (15 mol) was thrown in, and the reactor external temperature was heated up at 50 degreeC. To 10 parts by weight of n-butyl acetate was added dropwise a solution in which 0.03 parts by weight of 2,2'-azobisisobutyronitrile (AIBN) was completely dissolved. After an additional 5 hours of reaction while maintaining the jacket outside temperature at 50 ° C., n-butyl acetate was added to dilute the solid concentration to 60% to prepare a final polymer. The hydroxyl group containing polymer of 6,000 of weight average molecular weights (polystyrene conversion) by GPC method was obtained.

Synthesis Example 2 Synthesis of hydroxyl-containing fluoropolymer

A 4-neck jacket reactor (1L) was equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping lot, and a nitrogen gas introduction tube, and 100 parts by weight of n-butyl acetate, 1H, 1H, 3H-tetrafluoropropyl 5 parts by weight (5 mol) of methacrylate (Central Glass), 10 parts by weight (20 mol) of 3-trifluoromethoxypropene (Central Glass), 3-aryloxy-1,1,1,5,5 10 parts by weight (10 mol) of, 5-hexafluoropentan-3-ol (Central Glass) was added thereto, and the temperature of the reactor was raised to 50 ° C. To 10 parts by weight of n-butyl acetate, a solution in which 0.03 parts by weight of 2,2'-azobisisobutyronitrile (AIBN) was completely dissolved was added dropwise. After an additional 5 hours of reaction while maintaining the jacket outside temperature at 50 ° C, n-butyl acetate was added to dilute to a solid concentration of 60% to prepare a final polymer. A hydroxyl group-containing polymer having a weight average molecular weight (polystyrene-like equivalent) of 7,000 was obtained by the GPC method.

Synthesis Example 3 Synthesis of Fluoropolymer

A 4-neck jacket reactor (1L) was equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping lot, and a nitrogen gas introduction tube, and 100 parts by weight of n-butyl acetate, 1H, 1H, and 7H-dodecafluoro 5 parts by weight (1 mol) of heptyl acrylate (central glass), 10 parts by weight (40 mol) of 3-trifluoromethoxypropene (central glass), 3-aryloxy-1,1,1,5,5, 10 parts by weight (8 mol) of 5-hexafluoropentan-3-ol (Central Glass) was added thereto, and the temperature of the reactor was raised to 50 ° C. To 10 parts by weight of n-butyl acetate was added dropwise a solution in which 0.03 parts by weight of 2,2'-azobisisobutyronitrile (AIBN) was completely dissolved. After an additional 5 hours of reaction while maintaining the jacket outside temperature at 50 ° C., n-butyl acetate was added to dilute the solid concentration to 60% to prepare a final polymer. The hydroxyl group containing polymer of 5,500 weight average molecular weights (polystyrene conversion) by GPC method was obtained.

Synthesis Example 4 Synthesis of Fluoropolymer

A 4-neck jacket reactor (1 L) was equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot, and a nitrogen gas introduction tube, and 100 parts by weight of n-butyl acetate, 1H, 1H, 5H-octafluoropentyl (Meth) acrylate (central glass company) 15 weight part (20 mol), 3-aryloxy-1,1,1,5,5,5-hexafluoropentan-3-ol (central glass company) 10 weight part (20 mol) was added and the reactor external temperature was raised to 50 ° C. To 10 parts by weight of n-butyl acetate, a solution in which 0.03 parts by weight of 2,2'-azobisisobutyronitrile (AIBN) was completely dissolved was added dropwise. After an additional 5 hours of reaction while maintaining the jacket outside temperature at 50 ° C, n-butyl acetate was added to dilute to a solid concentration of 60% to prepare a final polymer. The hydroxyl-group containing polymer of 8,500 weight average molecular weights (polystyrene conversion) by GPC method was obtained.

Synthesis Example 5 Synthesis of Fluoropolymer

A 4-neck jacketed reactor (1L) was equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot and a nitrogen gas introduction tube, and 100 parts by weight of n-butyl acetate, 3- (2,2,2-tree Fluoro-1-trifluoromethylethoxy) propene (central glass) 15 parts by weight (25 mol), 3-aryloxy-1,1,1,5,5,5-hexafluoropentan-3-ol ( 10 parts by weight (15 mol) of Central Glass, Inc. was added thereto, and the temperature of the reactor was increased to 50 ° C. To 10 parts by weight of n-butyl acetate, a solution in which 0.03 parts by weight of 2,2'-azobisisobutyronitrile (AIBN) was completely dissolved was added dropwise. After an additional 5 hours of reaction while maintaining the jacket outside temperature at 50 ° C, n-butyl acetate was added to dilute to a solid concentration of 60% to prepare a final polymer. The hydroxyl group containing polymer of 7,500 by weight average molecular weight (polystyrene conversion) by GPC method was obtained.

 [Example of Manufacturing Composition for Hard Coating Layer]

70 parts by weight of urethane acrylate (Shin-Nakamura Chemical Co., U-15HA), 30 parts by weight of pentaerythritol triacrylate (public company, 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. A composition having a refractive index of 1.51 was prepared.

[Examples 1 to 10 and Comparative Examples 1 to 3]

The hard coating layer composition prepared above was coated on one side of a 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 composition for forming a low refractive index layer having the composition shown in Table 1 was applied on the hard coating layer to form a low refractive layer having a thickness of 0.1 μm by heat curing after heat drying.

Composition Example Comparative example One 2 3 4 5 6 7 8 9 10 One 2 3 Fluoropolymerization Synthesis Example 1 10 20 40 Synthesis Example 2 10 5 0.1 Synthesis Example 3 10 30 Synthesis Example 4 10 51 Synthesis Example 5 10 Fluorine Compound 10 Hollow Silica Particles 8 8 8 8 8 13 5 5 25 5 50 10 8 Acrylate Monomer (a) 10 10 10 10 10 10 10 15 10 15 10 Acrylate Monomer (b) 10 10 menstruum MIBK 70 70 70 70 60 70 53 43 58 32 33 68 70 Photoinitiator I-184 1.5 1.5 1.5 1.5 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 0.4 0.5 0.5 0.5 0.5 Refractive Index of Low Refractive Layer 1.37 1.37 1.38 1.37 1.38 1.37 1.36 1.32 1.34 1.35 1.38 1.45 1.4

Fluorine compound: Silicone fluorine modified copolymer (DIC Corporation)

Hollow silica particles: 20% solids in MIBK (refractive index 1.30, average particle diameter 60nm, catalyzed sand)

Acrylate monomer (a): dipentaerythritol penta / hexaacrylate (refractive index 1.476, Japanese synthetic yarn, DPHA)

Acrylate monomer (b): pentaerythritol tri / tetraacrylate (refractive index 1.47, Miwon Corporation, M340)

MIBK: methyl isobutyl ketone

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

BYK-378: Silicone Modified Oil (BYK)

Experimental Example

The physical properties of the antireflection films prepared in Examples and Comparative Examples were measured as follows, and the results are shown in Table 2 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) 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.

(3) 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.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example 1 Comparative Example 2 Comparative Example 3 Scratch resistance A A A A A A A A A A C B B Water contact angle (°) 106 107 106 108 107 110 109 108 112 107 89 92 100 reflectivity(%) 0.96 0.97 1.03 0.93 1.04 1.01 0.96 0.97 0.98 0.99 0.96 1.33 1.22

As shown in Table 2, in the case of Examples 1 to 10 containing the hydroxyl group-containing fluoropolymer and hollow silica particles according to the present invention, the results show that the scratchability is very excellent compared to Comparative Examples 1 to 3 not containing the same. Can be. In addition, in the case of Examples 1 to 10 it can be confirmed that the excellent reflectance characteristics to implement an excellent anti-reflection effect. In addition, in Examples 1 to 10, the water contact angle, which is a measure of fouling resistance, was high, indicating that the fouling resistance was excellent.

Claims (10)

A hollow silica particle (A), a hydroxyl-containing fluoropolymer (B), a (meth) acrylate monomer (C), a photoinitiator (D), and a solvent (E), The composition for low refractive layer formation characterized by the above-mentioned. The hydroxyl-containing fluoropolymer (B) of claim 1, wherein the hydroxyl group-containing fluoropolymer (B) comprises a fluorine-containing vinyl monomer polymerization unit (B1); And a fluorine-containing vinyl monomer polymerization unit (B2) containing a hydroxyl group. The method of claim 2, wherein the fluorine-containing vinyl monomer polymerization unit (B1) comprises a polymerization unit represented by the following formula (1), the fluorine-containing vinyl monomer polymerization unit (B2) containing a hydroxyl group is a polymerization represented by the following formula (3) A composition for forming a low refractive index layer comprising the unit. [Formula 1]

(In Formula 1, X is a hydrogen atom or a methyl group, Rf is a linear or branched hydrocarbon compound having 1 to 50 carbon atoms, and the hydrogen atom in the molecule is substituted with 50% or more of fluorine, and n is a corresponding component in the hydroxyl group-containing fluoropolymer. Mole% of 1 ≦ n ≦ 50.) (3)

(In Formula 3, Rf is a linear or branched hydrocarbon compound having 1 to 50 carbon atoms, in which a hydrogen atom in a molecule is substituted with 50% or more of fluorine, and p is a mole% of the corresponding component in the hydroxyl group-containing fluoropolymer, where 1 ≦ p ≦ 50.) The composition of claim 3, wherein the fluorine-containing vinyl monomer polymerization unit (B1) further comprises a polymerization unit represented by the following Chemical Formula 2. [Formula 2]

(In Formula 2, Rf is a linear or branched hydrocarbon compound having 1 to 50 carbon atoms, in which a hydrogen atom in a molecule is substituted with fluorine by 50% or more. 50.) The composition for forming a low refractive index layer according to claim 1, wherein the hydroxyl group-containing fluoropolymer (B) is contained in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the total composition for forming a low refractive index layer. 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 5. The antireflection film according to claim 6, wherein at least one hard coating layer having a higher refractive index than the low refractive layer is formed between the transparent substrate and the low refractive layer. The antireflection film according to claim 6, wherein the low refractive index layer has a refractive index of 1.2 to 1.49 at 25 ° C. The antireflection film of Claim 6 was provided, The polarizing plate characterized by the above-mentioned. The antireflection film of claim 6 is provided.