TWI532798B - Coating composition for low refractive layer, anti-reflection film using the same, polarizing plate and image displaying device including the film - Google Patents

Description

Low refractive index layer forming composition and antireflection thin film using the same Film, polarizing plate and display device

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

Recently, displays such as CRTs, LCDs, and PDPs have been developed, and various display devices using these displays have been used in various aspects. When these display devices are used in places where light is bright outside the house, the reflection of the display caused by external light such as sunlight or fluorescent lamps becomes a problem, thereby preventing external light from being reflected on the surface of the display. In, the requirements for anti-reflection are getting higher and higher.

Therefore, an antireflection film for making the outer appearance of the display device not well reflected is widely developed. As the antireflection film, an antireflection film having a multilayer structure (PCT/JP2003/008535) is known. The antireflection film of the above multilayer structure is known to have a two-layer structure composed of a high refractive index layer and a low refractive index layer; a three-layer structure composed of a medium refractive index layer, a high refractive index layer, and a low refractive index layer; A four-layer structure composed of a high refractive index layer, a low refractive index layer, a high refractive index layer, and a low refractive index layer.

In recent years, the antireflection film has been required to have not only an antireflection function but also an additional function such as scratch resistance, abrasion resistance, and contamination resistance. For this purpose, an antireflection film which uses a substance having contamination prevention property on the low refractive index layer is used. However, substances which can be used for the above antireflection film are limited, and Since the price of the material used in the prior art is high, not only the manufacturing cost is increased, but also the optical characteristics such as reflection characteristics, transmittance, haze, and the like are lowered due to the addition of such an additional function.

The present invention has been made to solve the above problems as described above, and an object of the invention is to provide a composition for forming a low refractive index layer, which is used when the composition for forming a low refractive index layer is applied to an antireflection film. It is excellent not only in antifouling properties and fingerprint resistance, but also excellent in antireflection properties such as reflectance.

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

Another object of the present invention is to provide a polarizing plate which is excellent in quality including the above-described antireflection film.

Another object of the present invention is to provide a display device having excellent quality as the above-described antireflection film.

In order to achieve the above object, the present invention provides a composition for forming a low refractive index layer, comprising: hollow cerium oxide particles (A); and a fluorinated (meth) acrylate compound (B) which allows a molecule a compound having three or more isocyanate groups, a fluoroalcohol represented by the following formula 1, and 2- Hydroxyethyl (meth) acrylate is obtained by reaction; (meth) acrylate monomer (C); photoinitiator (D) and solvent (E).

(In Formula 1, Y represents H or F independently, and n and m are integers of 0 to 200, respectively.)

Preferably, the fluorinated (meth) acrylate compound (B) contains at least one selected from the group consisting of compounds represented by the following formulas 2 to 9.

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

(In Expression 10, Y independently represents H or F, and n and m are integers of 0 to 200, respectively.)

Preferably, the hollow ceria particles have a refractive index of 1.17 to 1.40.

The low refractive index layer-forming composition may contain 0.1 to 20 parts by weight of the hollow cerium oxide particles (A) and the fluorinated (meth) acrylate compound (B) 0.1 to 100 parts by weight of the total. 30 parts by weight, 0.1 to 30 parts by weight of the (meth) acrylate 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 other object of the present invention, the present invention provides an antireflection film comprising: a transparent substrate; and a low refractive index layer which is used in the composition for forming a low refractive index layer according to the present invention. Formed on the upper surface of the transparent substrate.

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

Preferably, the refractive index of the low refractive index layer is 1.2 to 1.49 at 25 °C.

In order to achieve other objects of the present invention, the present invention provides a polarizing plate comprising the above-described antireflection film of the present invention.

In order to achieve other objects of the present invention, the present invention provides a display device comprising the above-described antireflection film of the present invention.

Since the composition for forming a low refractive index layer of the present invention contains hollow cerium oxide particles and a fluorinated (meth) acrylate compound having a predetermined structure, it is excellent in antifouling resistance and fingerprint resistance, and is reflective. Excellent anti-reflection properties such as rate. Thus, the antireflection film produced by using the composition for forming a low refractive index layer described above has excellent antifouling resistance, anti-fingerprint resistance, and antireflection property, and can be effectively 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 index layer of the present invention contains: hollow cerium oxide particles (A), a fluorinated (meth) acrylate compound (B), a (meth) acrylate monomer (C), and a photoinitiator. (D) and solvent (E).

Hollow ceria particles (A)

The above hollow cerium oxide particles are used in order to lower the refractive index, improve antireflection properties, and improve scratch resistance.

The refractive index of the hollow cerium oxide particles is preferably from 1.17 to 1.40, more preferably from 1.17 to 1.35, most preferably from 1.17 to 1.30. Here, the refractive index means the refractive index of the entire particle, and does not mean the refractive index of the cerium oxide, that is, the refractive index which forms the outer contour of the hollow particle.

At this time, the void ratio in the hollow ceria 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 it is desired to achieve a low refractive index of the hollow ceria particles and a high void ratio thereof, the thickness of the outer contour becomes thin and the strength of the particles becomes weak. Therefore, from the viewpoint of scratch resistance, any particles having a refractive index of hollow cerium oxide particles of less than 1.17 are not preferable because scratch resistance is lowered. Further, when the refractive index of the hollow ceria particles exceeds 1.40, the antireflection property is lowered due to the high refractive index, which is not preferable. The refractive index of the above hollow cerium oxide particles was measured using an Abbe refractive index measuring instrument (manufactured by ATAGO Co., Ltd.).

The above hollow cerium oxide particles can be easily produced by a known production method. For example, hollow cerium oxide particles produced by the method described in JP-A-2001-233611 and JP-A-2002-79616 can be used.

The average particle diameter of the hollow ceria particles is preferably from 30 to 150%, more preferably from 35 to 80%, particularly preferably from 40 to 60, of the low refractive index layer. %. That is, when the thickness of the low refractive index layer is 100 nm, the average particle diameter of the hollow ceria particles is preferably from 30 nm to 150 nm, more preferably from 35 nm to 80 nm, and particularly preferably from 40 nm to 60 nm. When the hollow ceria particles are within the above-described range, the ratio of the void portion is increased to achieve a low refractive index. Further, fine irregularities are formed on the surface of the low refractive index layer without causing a problem that the reflectance is lowered. The hollow ceria particles may be crystalline particles or non-crystalline particles, preferably monodisperse particles. From the viewpoint of morphology, spherical particles are most preferable, but irregularly shaped particles are also used. Further, the average particle diameter of the hollow cerium oxide fine particles was measured using an electron micrograph.

The hollow cerium oxide particles (A) may be particles which have been surface-treated with a silane coupling agent. In this case, the dispersibility with the solvent is improved, and the curing is carried out during the curing process, thereby The binder forms a network to increase the durability of the coating.

As the above decane coupling agent, specifically, a methyl tertiary methoxy decane, dimethyl dimethoxy decane, phenyl trimethoxy decane, diphenyl dimethoxy decane, methyl group can be used. Triethoxy decane, dimethyl diethoxy decane, phenyl triethoxy decane, diphenyl diethoxy decane, isobutyl trimethoxy decane, vinyl trimethoxy decane, vinyl three Ethoxy decane, vinyl tris(β-methoxyethoxy)decane, 3,3,3-trifluoropropyltrimethoxydecane, methyl-3,3,3-trifluoropropyldimethoxy Baseline, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxymethyltrimethoxymethyldecane, γ-glycidoxymethyltriethoxy Pyridin, γ-glycidoxyethyltrimethoxydecane, γ-glycidoxyethyltriethoxydecane, γ-glycidoxy Propyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, γ-(β-glycidoxymethoxy)propyltrimethoxydecane, γ-(methyl) Propylene methoxymethyltrimethoxydecane, γ-(meth)acryloxymethyltriethoxydecane, γ-(meth)acryloxyethyltrimethoxydecane, γ-(A) Acryloxyethyltriethoxydecane, γ-(meth)acryloxypropyltrimethoxydecane, γ-(meth)acryloxypropyltrimethoxydecane (repeated) , γ-(meth) propylene methoxy propyl triethoxy decane, butyl trimethoxy decane, isobutyl triethoxy decane, hexyl triethoxy decyl octyl triethoxy decane ( Hexyl triethoxy sila octyl triethoxy silane), mercaptotriethoxy decane, butyl triethoxy decane, isobutyl triethoxy decane, hexyl triethoxy decane, octyl triethoxy decane, 3- Urea isopropyl propyl triethoxy decane, perfluorooctyl ethyl trimethoxy decane, perfluorooctyl ethyl triethoxy decane, perfluorooctyl ethyl triisopropoxy decane, three Fluoropropyltrimethoxydecane N-β-(aminoethyl)γ-aminopropylmethyldimethoxydecane, N-β-(aminoethyl)γ-aminopropyltrimethoxydecane, N-phenyl-γ-(ammonia At least one of propyl)trimethoxynonane, γ-mercaptopropyltrimethoxynonane, trimethylnonanol, and methyltrichlorosilane.

The content of the hollow cerium oxide is not necessarily limited, but is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the total composition for forming a low refractive index layer. When the content of the hollow enamel is less than 0.1 part by weight based on the above-mentioned basis, a sufficient refractive index reducing effect cannot be obtained, and when it exceeds 20 parts by weight, there is a problem that scratch resistance is lowered.

Fluorinated (meth) acrylate compound (B)

The above fluorinated (meth) acrylate compound is for ensuring excellent contamination As the substance to be added for prevention and fingerprint resistance, a compound having three or more isocyanate groups in the molecule, and a fluoroalcohol represented by the following formula 1 and 2-hydroxyethyl group can be used according to the present invention. A compound obtained by reacting a methyl acrylate.

(In Formula 1, Y is an integer indicating that H or F is independent, and n and m are each an integer of 0 to 200.)

As the compound having three or more isocyanate groups in the above molecule, an isocyanuric acid type trifunctional isocyanate derived from 1,4-diisocyanobutane butane; and 1,6-diisocyanide can be used. a hexane-derived isocyanuric acid type trifunctional isocyanate; an isocyanuric acid type trifunctional isocyanate derived from 1,8-diisocyanatooctane; a derivative derived from 1,12-diisocyanodecane decane Cyanuric acid type trifunctional isocyanate; isocyanuric acid type trifunctional isocyanate derived from 1,5-diisocyanoguanidin-2-methylpentane; from trimethyl-1,6-diisocyanoguanidinylhexane Derivatized isocyanuric acid trifunctional isocyanate; isocyanuric acid trifunctional isocyanate derived from 1,3-bis(isocyanatomethyl)cyclohexane; from trans-1,4-cyclohexenyl Isocyanate-derived isocyanuric acid trifunctional isocyanate; isocyanuric acid trifunctional isocyanate derived from 4,4'-methylenebis(cyclohexyl isocyanate); isocyanuric acid type III derived from isophorone diisocyanate Functional isocyanate; isocyanuric acid trifunctional isocyanate derived from toluene-2,4-diisocyanate; Isocyanurate-type trifunctional isocyanates 2,6-diisocyanate-derived; isobutyl-1,4-xylene by the Cyanate ester-derived isocyanuric acid trifunctional isocyanate; isocyanuric acid trifunctional isocyanate derived from tetramethylxylene-1,3-diisocyanate; derived from 1-chloromethyl-2,4-diisocyanate Isocyanuric acid trifunctional isocyanate; isocyanuric acid trifunctional isocyanate derived from 4,4'-methylenebis(2,6-dimethylphenylisocyanate); 4,4'-oxidized double ( Phenyl isocyanate)-derived isocyanuric acid trifunctional isocyanate; trifunctional isocyanate derived from hexamethylene diisocyanate; toluene diisocyanate of trimethane propanol adduct; and 1,6-diisocyanide A compound in a trifunctional biuret type compound or the like of an alkane.

Preferably, the compound having three or more isocyanate groups in the above molecule may be selected from the group consisting of trifunctional isocyanate derived from hexamethylene diisocyanate, toluene diisocyanate of trimethane propanol adduct, and isophor. A compound of a keto diisocyanate-derived isocyanuric acid trifunctional isocyanate and a hexamethylene diisocyanate biuret type isocyanate.

As the fluoroalcohol represented by the above formula 1, specifically, it can be selected from the group consisting of 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-nonafluoro- 1-pentanol, 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecanofluoro-1-octanol (2,2,3,3, a compound in 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8 - Pentadecafluoro-1-octanol).

Preferably, the compound having three or more isocyanate groups in the above molecule and the fluoroalcohol and 2-hydroxyethyl (meth) acrylate represented by the above formula 1 are reacted in the presence of a solvent. Carry out the reaction.

The solvent is not particularly limited, and ethers, ketones and the like are preferably used in view of compatibility. More preferably, a fluorine-based solvent may be used as a solvent, and specifically, hydrofluorocarbon and hydrofluoroether may be used. Commercially available products may be used, and Vertrel XF (manufactured by Du Pont) may be used. CF ₃ CHFCHFCF ₂ CF ₃ ), Zeorora H (heptafluorocyclopentane) manufactured by Zeon Corporation of Japan, HFE-7100 (C ₄ F ₉ OCH ₃ ) manufactured by 3M Company, 7200 (C ₄ F ₉ OC ₂ H ₅ ), etc. At least one of them.

Preferably, the fluorinated (meth) acrylate compound (B) may contain at least one selected from the group consisting of compounds represented by the following formulas 2 to 9.

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

(In Expression 10, Y is an integer that independently represents H or F, and n and m are 0 to 200, respectively.)

It is preferable to use 0.1 to 30 parts by weight of the above fluorinated (meth) acrylate compound (B) based on 100 parts by weight of the total composition for forming a low refractive index layer. When the content of the fluorine compound (B) is less than 0.1 part by weight based on the above-mentioned basis, it is difficult to achieve the effects of antifouling and fingerprint erasability, and when it exceeds 30 parts by weight, the workability is deteriorated due to poor compatibility.

(meth) acrylate monomer (C)

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

The above (meth) acrylate monomer is not particularly limited, and those generally used in the field can be used. Specifically, the above (meth) acrylate monomer It can be selected from: dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di-trimethylolpropane Tetrakis (meth) acrylate, (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acrylate, tris (2-hydroxyethyl) isocyanuric acid tri ( Methyl) acrylate, ethylene glycol di(meth) acrylate, propylene glycol (meth) acrylate, 1,3-butylene glycol di(meth) acrylate, 1,4-butanediol di(a) Acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di( Methyl) acrylate, dipropylene glycol di(meth) acrylate, bis(2-hydroxyethyl)isocyanurate di(meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (a) Acrylate, hydroxybutyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofuranyl (A) Acrylate, At least one of phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, and the like.

The content of the (meth) acrylate monomer is not particularly limited, but is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the total composition for forming a low refractive index layer. When the content of the above (meth) acrylate monomer is less than 0.1 part by weight based on the above-mentioned basis, there is a problem in surface curing of the low refractive index layer, and when it exceeds 30 parts by weight, the refractive index of the low refractive index layer rises and antireflection The effect is reduced.

Photoinitiator (D)

The above photoinitiator can use the substance used in the field without limitation.

As the photoinitiator, specifically, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinil-1-one, diphenyl ketone phenyl may be used. Mercaptodimethylketal, 2-hydroxy-2-methyl-1-phenyl-1-one, 4-hydroxycyclophenyl ketone, dimethoxy-2-phenylacetophenone, anthracene, Anthracene, triphenylamine, carbazole, 3-methylacetophenone, 4-chloroacetophenone, 4,4-dimethoxyacetophenone, 4,4-diaminobenzophenone, 1- At least one of hydroxycyclohexyl phenyl ketone and benzophenone.

The content of the photoinitiator is preferably 0.05 to 5 parts by weight based on 100 parts by weight of the total composition for forming a low refractive index layer. When the content of the photoinitiator is less than 0.05 parts by weight based on the above-mentioned basis, the curing rate of the composition for forming a refractive index layer becomes slow, and when it exceeds 5 parts by weight, it sometimes occurs in the low refractive index layer due to excessive curing. crack.

Solvent (E)

The solvent is not particularly limited as long as it is known as a solvent for the composition for forming a low refractive index layer in the technical field.

For example, the above solvent is preferably an alcohol (methanol, ethanol, isopropanol, butanol, ethylene glycol ethyl ether, ethylene glycol ether, etc.), a ketone (methyl ethyl ketone, methyl methyl ketone, methyl group). Isobutylketone, diethyl ketone, dipropyl ketone, cyclohexanone, etc.), hexanes (hexane, heptane, octane, etc.), benzenes (benzene, toluene, xylene, etc.). The solvents listed above may be used alone or in combination of two or more.

The content of the solvent may be 50 to 98 parts by weight based on 100 parts by weight of the total composition for forming the low refractive index layer. When the solvent is less than 50 parts by weight based on the above-mentioned basis, the viscosity is increased to cause the film to be coated. It is difficult, and when it exceeds 98 parts by weight, it takes a long time in the hardening process, so that there is a problem of economical reduction.

The composition for forming a low refractive index layer of the present invention may further comprise, in addition to the above components, a light stimulating agent, an antioxidant, a UV absorber, a light stabilizer, a thermal polymerization inhibitor, a leveling agent, a surfactant, and a lubricant. Agents, etc.

In the present invention, an antireflection film comprising a low refractive index layer produced by using the above composition for forming a low refractive index layer is provided.

More specifically, the antireflection film includes a transparent substrate and a low refractive index layer formed by using the low refractive index layer of the present invention on one surface or both surfaces of the transparent substrate.

In this case, in the antireflection film of the present invention, a hard coat layer may be contained between the transparent substrate and the low refractive index layer in order to increase the physical strength of the film. That is, a preferred example of the antireflection film of the present invention is that a hard coat layer is formed on the upper surface of the transparent substrate, and a low refractive index layer formed by curing the composition for forming the low refractive index layer is formed on the upper surface thereof.

As the transparent substrate, any film may be used as long as it is a transparent plastic film, and for example, a cycloolefin-containing monomer having a monomer such as norbornene or a polycyclic norbornene monomer may be used. Unit of a cyclic olefin derivative selected from the group consisting of diethyl phthalocyanine, triethyl hydrazine cellulose, Acetyl cellulose butyrate, isobutyl ester cellulose, propylene cellulose, butadiene fiber Cellulose, ethylene-vinyl acetate copolymer, polyester, polystyrene, polyamine, polyetherimide, polyacrylic, polyimine, Polyether oxime, polyfluorene, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether Ketone, polyetheretherketone, polyether oxime, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate A substance such as polyurethane, epoxy or the like, and an unstretched film, a uniaxial or biaxially stretched film can be used.

Among them, a uniaxial or biaxially stretched polyester film which is excellent in transparency and heat resistance, and a cycloolefin derivative film which is excellent in transparency and heat resistance and can cope with an increase in size of a film, is transparent and has no optical From the viewpoint of the opposite sex, a triacetyl cellulose film can be suitably used.

The transparent base film has a thickness of 8 to 1000 μm, preferably 40 to 100 μm.

The hard coat layer formed on the transparent substrate preferably has a refractive index at a temperature of 25 ° C of 1.48 to 2.00, more preferably 1.50 to 1.90, from the viewpoint of obtaining an optical design of a good antireflection film. It is preferably 1.50 to 1.80. Since the antireflection film according to the present invention contains at least one low refractive index layer on the hard coat layer, when the refractive index is less than the above range, the antireflection property is lowered, and when the refractive index is larger than the above range, the reflected light is present. The disadvantage of thickening the color.

The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of a photocurable compound. These compounds are not particularly limited, and for example, can be formed by coating a composition for forming a hard coat layer containing a polyfunctional monomer or a polyfunctional oligomer on a transparent support, and then The above polyfunctional monomer or polyfunctional oligomer is subjected to a crosslinking reaction or a polymerization reaction.

The functional group of the polyfunctional monomer or the polyfunctional oligomer is preferably a photopolymerizable, electron beam polymerizable or radiation polymerizable group. Among them, a photopolymerizable functional group is preferred.

Examples of the photopolymerizable functional group include an unsaturated polymerizable functional group such as a (meth)acryl fluorenyl group, a vinyl group, a styryl group, or an allyl group. Among them, (meth) propylene is preferable.醯基.

Specific examples of the photopolymerizable polyfunctional monomer having the photopolymerizable functional group include neopentyl glycol acrylate, 1,6-hexanediol (meth)acrylate, and propylene glycol di(meth)acrylate. (meth)acrylic acid diesters of diols; triethylene glycol di(meth) acrylate, dipropylene glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate, polypropylene glycol a polyoxy diol (meth) acrylate such as di(meth) acrylate; a (meth) acrylate diester of a polyhydric alcohol such as pentaerythritol di(meth) acrylate; 2,2-double {4- Ethylene oxide (Acryloxy.diethoxy)phenyl}propane, 2,2-bis{4-(Acryloxy.polypropoxy)phenyl}propane or the like A (meth)acrylic acid diester of a propylene oxide adduct. Further, 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, polyhydric alcohols and esters of (meth)acrylic acid are more preferably used.

More preferably, the photopolymerizable polyfunctional monomer is a polyfunctional monomer having three or more (meth) acrylonitrile groups in one molecule. Specific examples of the polyfunctional monomer having three or more (meth) acrylonitrile groups in one molecule include trimethylolpropane tri(meth)acrylic acid. Ester, trimethylolethane tri(meth)acrylate, 1,2,4-cyclohexanetetra(meth)acrylate, pentaglycerol triacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol III (Meth) acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra(meth) acrylate, dipentaerythritol hexa(meth) acrylate, tripentaerythritol triacrylate, tripentaerythritol hexatriacrylate Ester and the like.

The above photopolymerizable polyfunctional monomers may be used singly or in combination of two or more kinds.

Preferably, a photoinitiator is used for the polymerization reaction of the photopolymerizable polyfunctional monomer. The photoinitiator is preferably a photoradical initiator and a photocationic initiator, and particularly preferably a photoradical initiator.

As the above photoradical initiator, those known in the art can be used, for example, selected from the group consisting of acetophenones, benzophenones, Methyl benzamidine benzoate, α-amyl phthalate, and monosulfide A photoradical initiator in methyl thiuram, thioxanthone or the like.

In the antireflection film according to the present invention, the hard coat layer and the low refractive index layer which are sequentially formed on the transparent substrate may be subjected to extrusion coating, pneumatic blade coating, reverse roll, spray, scraper, casting, The composition for forming a hard coat layer and the composition for forming a low refractive index layer according to the present invention are formed by a suitable method such as gravure, micro gravure, and spin coating.

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 the composition for forming a hard coat layer is applied, it is dried at a temperature of 30 to 150 ° C for 10 seconds to 1 hour, preferably for 30 seconds to 10 minutes. After the completion of the drying, the hard coat layer is formed by photocuring by irradiating UV light to form a hard coat layer. The irradiation amount of the above UV light is about 0.01 to 10 J/cm ² , preferably 0.1 to ² J/cm ² .

The coating composition for forming the low refractive index layer has a coating thickness of 0.01 to 2 μm, preferably 0.05 to 0.3 μm. After coating the composition for forming a low refractive index layer, it is dried at a temperature of 30 to 150 ° C for 10 seconds to 1 hour, preferably 30 seconds to 10 minutes. After drying, the composition for forming a low refractive index layer is photocured by irradiation with UV light to form a low refractive index layer. The irradiation amount of the above UV light is about 0.01 to 10 J/cm ² , preferably 0.1 to ² J/cm ² .

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

The low refractive index layer has a relatively low refractive index as compared with the above hard coat layer. In order to obtain an optical design of the antireflection film, the low refractive index layer preferably has a refractive index at 25 ° C in the range of 1.20 to 1.49. When the refractive index of the low refractive index layer is less than the above range, the antireflection property is lowered, and when it is higher than the above range, there is a disadvantage that the color of the reflected light becomes rich.

The antireflection film produced by the above method has excellent scratch resistance, antireflection properties, and excellent adhesion.

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

Although the above polarizing plate is not particularly limited, various types can be used. The polarizing plate is, for example, a polyvinyl alcohol film, and a dichroic substance such as iodine or a dichroic dye is adsorbed onto a hydrophilic polymer film such as an ethylene-vinyl acetate copolymer-based saponified film. Uniaxially stretched film; or dehydrated material of polyvinyl alcohol or deacetylated acid of polyvinyl chloride A polyene-based oriented film such as a physical property. Among these films, a polarizing plate composed of a polyvinyl alcohol film and a dichroic material such as iodine is preferable. Although the thickness of these polarizing plates is not particularly limited, it is generally about 5 to 80 μm.

The present invention also provides a display device using the above antireflection film.

For example, by incorporating the antireflection film polarizing plate of the present invention into a display device, it is possible to manufacture a variety of display devices having excellent visibility. Further, the antireflection film of the present invention can also be mounted on a window of a display device. The antireflection film of the present invention can be applied to LCDs of various driving methods such as a reflective type, a transmissive type, a transflective type LCD, a TN type, an STN type, an OCB type, a HAN type, a VA type, and an IPS type. Further, the antireflection film of the present invention can be preferably applied to various display devices such as a plasma display, a field emission display, an organic EL display, an inorganic EL display, and an electronic paper.

The invention is further exemplified by the following examples, but the following examples are merely illustrative of the invention and are not intended to limit or limit the scope of the invention.

[Synthesis Example 1] Fluorinated (meth) acrylate compound

Add 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-octanol (manufactured by TCI) 20 parts by weight, by different 24 parts by weight of a sulphuric acid diisocyanate-derived isocyanuric acid trifunctional isocyanate (manufactured by Degussa Co., Ltd.), 6 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (manufactured by Aldrich Co., Ltd.), heptafluorocyclopentane 30 parts by weight of an alkane (manufactured by Aldrich Co., Ltd.) and 0.1 part by weight of dibutyltin dilaurate, and the temperature of the reaction vessel was raised to 50 ° C, followed by stirring for 2 hours. When the characteristic peak 2260 cm ^-1 of the isocyanate of the infrared spectroscopic spectrum completely disappeared, the reaction was terminated, whereby a compound having a solid content of 50 w% was obtained.

[Synthesis Example 2] Fluorinated (meth) acrylate compound

Add 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-octanol (manufactured by TCI) 10 parts by weight, by different 22 parts by weight of a sulphuric acid diisocyanate-derived isocyanuric acid trifunctional isocyanate (manufactured by Degussa Co., Ltd.), 18 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (manufactured by Aldrich Co., Ltd.), heptafluorocyclopentane 30 parts by weight of an alkane (manufactured by Aldrich Co., Ltd.) and 0.1 part by weight of dibutyltin dilaurate, and the temperature of the reaction vessel was raised to 50 ° C, followed by stirring for 2 hours. When the characteristic peak 2260 cm ^-1 of the isocyanate of the infrared spectroscopic spectrum completely disappeared, the reaction was terminated, whereby a compound having a solid content of 50 w% was obtained.

[Synthesis Example 3] Fluorinated (meth) acrylate compound

Add 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-octanol (manufactured by TCI) 20 parts by weight, from six 24 parts by weight of a trifunctional isocyanate (manufactured by BASF Corporation), 6 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (manufactured by Aldrich Co., Ltd.), and heptafluorocyclopentane (Aldrich Co., Ltd.) 30 parts by weight of 0.1 parts by weight of dibutyltin dilaurate were produced, and the temperature of the reaction vessel was raised to 50 ° C, followed by stirring for 2 hours. When the characteristic peak 2260 cm ^-1 of the isocyanate of the infrared spectroscopic spectrum completely disappeared, the reaction was terminated, whereby a compound having a solid content of 50 w% was obtained.

[Synthesis Example 4] Fluorinated (meth) acrylate compound

Add 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-octanol (manufactured by TCI) 13 parts by weight, from six 22 parts by weight of a trifunctional isocyanate (manufactured by BASF Corporation), 15 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (manufactured by Aldrich Co., Ltd.), and 30 parts by weight of heptafluorocyclopentane 0.1 parts by weight of dibutyltin dilaurate, and the temperature of the reaction vessel was raised to 50 ° C, followed by stirring for 2 hours. When the characteristic peak 2260 cm ^-1 of the isocyanate of the infrared spectroscopic spectrum completely disappeared, the reaction was terminated, whereby a compound having a solid content of 50 w% was obtained.

[Synthesis Example 5] Fluorinated (meth) acrylate compound

Add 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-octanol (manufactured by TCI) 20 parts by weight, trimethane 18 parts by weight of toluene diisocyanate (manufactured by Ai Jing Chemical Co., Ltd.), 6 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (manufactured by Aldrich Co., Ltd.), 30 parts by weight of heptafluorocyclopentane 0.1 parts by weight of dibutyltin dilaurate, and the temperature of the reaction vessel was raised to 50 ° C, followed by stirring for 2 hours. When the characteristic peak 2260 cm ^-1 of the isocyanate of the infrared spectroscopic spectrum completely disappeared, the reaction was terminated, whereby a compound having a solid content of 50 w% was obtained.

[Synthesis Example 6] Fluorinated (meth) acrylate compound

Add 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecylfluoro-1-octanol (manufactured by TCI) 15 parts by weight, trimethane 20 parts by weight of toluene diisocyanate (manufactured by Ai Jing Chemical Co., Ltd.), 15 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (manufactured by Aldrich Co., Ltd.), 30 parts by weight of heptafluorocyclopentane 0.1 parts by weight of dibutyltin dilaurate, and the temperature of the reaction vessel was raised to 50 ° C, followed by stirring for 2 hours. When the characteristic peak 2260 cm ^-1 of the isocyanate of the infrared spectroscopic spectrum completely disappeared, the reaction was terminated, whereby a compound having a solid content of 50 w% was obtained.

[Synthesis Example 7] Fluorinated (meth) acrylate compound

Add 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-octanol (manufactured by TCI) 20 parts by weight, Liuya 23 parts by weight of methyl diisocyanate biuret type isocyanate (manufactured by BASF Corporation), 7 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (manufactured by Aldrich Co., Ltd.), 30 parts by weight of heptafluorocyclopentane, 0.1 part by weight of dibutyltin dilaurate, and the temperature of the reaction vessel was raised to 50 ° C, and stirred for 2 hours. When the characteristic peak 2260 cm ^-1 of the isocyanate of the infrared spectroscopic spectrum completely disappeared, the reaction was terminated, whereby a compound having a solid content of 50 w% was obtained.

[Synthesis Example 8] Fluorinated (meth) acrylate compound

Add 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-octanol (manufactured by TCI) 12 parts by weight, Liuya 23 parts by weight of methyl diisocyanate biuret type isocyanate (manufactured by BASF Corporation), 15 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of propylene glycol monoethyl ether (manufactured by Aldrich Co., Ltd.), 30 parts by weight of heptafluorocyclopentane, 0.1 part by weight of dibutyltin dilaurate, and the temperature of the reaction vessel was raised to 50 ° C, and stirred for 2 hours. When the characteristic peak 2260 cm ^-1 of the isocyanate of the infrared spectroscopic spectrum completely disappeared, the reaction was terminated, whereby a compound having a solid content of 50 w% was obtained.

[Production Example] Composition for forming a hard coat layer

70 parts by weight of urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., U-15HA), 30 parts by weight of pentaerythritol triacrylate (manufactured by Kyoei Co., Ltd., PE-3A), and 3 parts by weight of photoinitiator (BASF Corporation ( A composition having a refractive index of 1.51 was prepared by mixing with an old CIBA company, D-1173), 150 parts by weight of methyl ethyl ketone, and 100 parts by weight of toluene.

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

The components were mixed at a ratio shown in the following Table 1 and Table 2 to prepare a composition for forming a low refractive index layer.

The respective components used in the above Tables 1 and 2 are as follows.

Fluoropolymer: CC-04 (refractive index 1.41, solid content in butyl acetate 50w T%, manufactured by Central Glass)

Hollow ceria particles: refractive index 1.30, average particle size 40nm, manufactured by Catalyst Chemicals Co., Ltd.

Acrylate monomer (a): dipentaerythritol penta/hexaacrylate (refractive index 1.476, manufactured by Nippon Synthetic Co., DPHA), acrylate monomer (b): pentaerythritol tri/tetraacrylate (refractive index 1.47, (Miwon Corporation) Company manufacturing, M340)

MIBK: methyl isobutyl ketone (manufactured by Oiji Chemical Co., Ltd.)

MEK: methyl ethyl ketone (manufactured by Oiji Chemical Co., Ltd.)

I-184: 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Corporation)

BYK-378: Modified eucalyptus oil (manufactured by BYK)

[Experimental example]

The composition for a hard coat layer prepared in the above Preparation Example was applied to one surface of a transparent substrate composed of a triacetonitrile cellulose film having a thickness of 80 μm, and dried by heating, and then hardened to a thickness of 5 μm by ultraviolet curing. coating. The composition for forming a low refractive index layer prepared in the above Examples and Comparative Examples was applied onto the hard coat layer, and dried by heating, and then a low refractive index layer having a thickness of 0.1 μm was formed by ultraviolet curing.

The physical properties described below were measured for the antireflection film produced in the above manner, and the results are shown in Table 3 below.

(1) Scratch resistance

The abrasion resistance was tested by a steel wool tester (WT-LCM100, manufactured by Protec, Korea) at 10 kg/(2 cm 2 Cm) for 10 round trips. Steel wool used # 0000.

A: Scratch is 0

A': Scratch is 1~10

B: Scratch is 11~20

C: Scratch is 21~30

D: More than 31 scratches

(2) Adhesiveness

On the coated surface of the film, 11 straight lines were drawn at intervals of 1 mm, and 100 regular squares were produced, and the tape was used (CT-24, Japan). The nichiban company made three peel tests. The experiment was carried out by the above-described regular quadrilateral having three three quadrangles and the average value was recorded.

The adhesion was recorded as shown below.

Adhesion = n/100

n: the number of quadrilaterals that are not stripped out of all quadrilaterals

100: the number of all quads

Therefore, when one is not peeled off, it is recorded as 100/100.

(3) Surface reflectance

A spectrophotometer UV2450 (manufactured by Shimadzu Corporation) was mounted with an adapter MPC2200, and in the wavelength region of 380 to 780 nm, the specular reflectance at an exit angle of 5° at an incident angle of 5° was measured, thereby calculating Average reflectance from 450 to 650 nm.

(4) Haze

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

(5) Water contact angle

After dropping water droplets onto the surface of the film at normal temperature (25 ° C), the contact angle with respect to water droplets was measured 1 minute later using a contact angle measuring device (CAM100 manufactured by KSV Corporation). The contact angle used was the average value calculated by measuring the left and right contact angles of the water droplets five times by the same sample.

【table 3】

As shown in the above Table 3, in the case of Examples 1 to 14 containing the fluorinated (meth) acrylate compound and hollow cerium oxide particles according to the present invention, it is possible to In comparison with Comparative Examples 1 to 3, the water contact angle, which is a scale indicating stain resistance, showed a high value, and not only excellent stain resistance but also excellent scratch resistance. Moreover, it is also possible to determine the phenomenon that the reflectance characteristics are excellent and the excellent antireflection effect is exhibited.

Claims (8)

A composition for forming a low refractive index layer, comprising: hollow cerium oxide particles (A); and a fluorinated (meth) acrylate compound (B) having three or more isocyanate groups in a molecule a compound, which is obtained by reacting a fluoroalcohol represented by the following formula 1 and 2-hydroxyethyl (meth) acrylate; a (meth) acrylate monomer (C); a photoinitiator (D) and a solvent ( E), In Formula 1, Y each independently represents H or F, and n and m are each an integer of 0 to 200, wherein the fluorinated (meth) acrylate compound (B) comprises, selected from the following formulas 2 to 9. At least one of the compounds, [Chemical Formula 3] [Chemical Formula 7] In the formulae 2 to 9, X is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and Rf is represented by the following formula 10. In Formula 10, Y independently represents H or F, and n and m are each an integer of 0 to 200. The composition for forming a low refractive index layer according to Item 1, wherein the composition for forming a low refractive index layer is characterized in that The hollow ceria particles have a refractive index of 1.17 to 1.40. The composition for forming a low refractive index layer according to the first aspect of the invention, wherein the composition for forming a low refractive index layer contains the hollow cerium oxide particles (A) with respect to 100 parts by weight of the whole. 0.1 to 20 parts by weight, 0.1 to 30 parts by weight of the fluorine compound (B), 0.1 to 30 parts by weight of the (meth) acrylate monomer (C), and 0.05 to 5 parts of the photoinitiator (D) The parts by weight and the solvent (E) are 50 to 98 parts by weight. An antireflection film comprising: a transparent substrate; and a low refractive index layer formed by using the composition for forming a low refractive index layer according to any one of claims 1 to 3 On the upper surface of the transparent substrate. The antireflection film of claim 4, further comprising a hard coat layer formed between the transparent substrate and the low refractive index layer. The antireflection film according to claim 4, wherein the low refractive index layer has a refractive index of 1.2 to 1.49 at 25 °C. A polarizing plate comprising the antireflection film according to item 4 of the patent application. A display device comprising the antireflection film according to item 4 of the patent application.