KR20130106670A - Anti-reflective hardcoating film and manufacturing method of thereof - Google Patents

Abstract

PURPOSE: An anti-reflective hard coating film is provided to form an anti-reflective layer having a low refractive layer and a high refractive layer laminated in turn on at least one side of a transparent polymer film of which the outermost layer is a low refractive layer, and a hard coating layer having a photopolymer resin composition and inorganic particles, thereby improving permeability, durability, wet-proof property, and chemical resistance. CONSTITUTION: An anti-reflective hard coating film comprises an anti-reflective layer(10) and a hard coating layer(40). The anti-reflective layer has at least one of low refractive layers and one of high refractive layers laminated in turn on at least one side of a transparent polymer film, of which the outermost layer is a low refractive layer. The hard coating layer includes a photopolymer resin and inorganic particles(50) on at least one side of the transparent polymer film. The average diameter of the inorganic particles is 0.5-5 um, including 0.6-1.2 parts by weight for 100 parts by weight of the photopolymer resin composition.

Description

Anti-reflective hard coating film and manufacturing method thereof

The present invention relates to an antireflection hard coating film and a method of manufacturing the same. More specifically, a low refractive index layer and a high refractive index layer are alternately stacked on at least one surface of a transparent polymer film, and an outermost layer is an antireflection layer having a low refractive index layer. By forming a hard coating layer comprising a photocurable resin composition and inorganic particles, it is excellent in anti-glare performance and anti-reflection characteristics, antireflection hard coating film with improved transmittance, durability, moisture resistance, chemical resistance and a method of manufacturing the same It is about.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antireflection hard coating film, and more particularly, to an antireflection hard coating film to be applied to display materials of various display devices such as liquid crystal display devices, CRT display devices, plasma display devices, and EL display devices.

Conventionally, on the display screen of a liquid crystal display or a plasma display device, a transparent hard coating film having surface irregularities applied to a transparent polymer film is applied to protect the surface and prevent glare caused by external light. Has been. However, the conventional hard coating film by the surface roughness treatment is difficult to produce a film that can satisfy the anti-glare performance and surface hardness at the same time.

For example, in the case of the transparent hard coating layer containing the particles to be the matting agent, when the content of the particles is increased, the haze rises and the transparency is lowered. When the content is decreased, the gloss is increased and the antiglare performance is lowered. This happens.

In addition, when the particle size of the particles is reduced, the haze value is suppressed to improve transparency, but at the same time, if the thickness of the hard coating layer is not reduced, the formation of irregularities by the surface particles becomes difficult and the anti-glare performance is deteriorated. In addition, when the thickness of the hard coating layer is reduced, a problem arises in that the surface hardness is reduced. In addition, when the thickness of the hard coating layer is increased, the surface hardness is effective. However, since the particles are buried inside the hard coating layer, surface irregularities are difficult to be formed, thereby reducing the anti-glare performance.

Therefore, there is an urgent need for a hard coating film that solves the problems described above and has excellent optical properties and surface hardness that provide excellent anti-glare performance and transparency.

In addition, as the viewing angle of the display is diversified, a problem of deterioration in image quality is caused by glare caused by reflected light and reflection of the front surface of the display. An anti-reflection coating is introduced to solve this problem. However, this also has insufficient anti-reflective effect, the interference free phenomenon occurs due to the difference in refractive index with the transparent base material, the mechanical strength of the coating is weakened, the problem of deteriorating chemical properties such as weather resistance or water resistance Therefore, the situation needs to be improved.

Korean Patent Laid-Open No. 2009-0077767 (Patent Document 1) discloses a hard coating film having a coating layer having a concave-convex structure on a surface and an interface between a polyester film and a hard coating layer on at least one surface of a polyester film, a method of manufacturing the same, and antireflection The film is manufactured, and in Korean Patent Laid-Open Publication No. 2009-0020106 (Patent Document 2), it is possible to secure an ultraviolet transmittance to protect an internal material from ultraviolet light and to easily adjust the ultraviolet absorption function, and a composition for a hard coating layer using the same. Provided are an antireflection film comprising a coating film and the hard coating film.

The conventional anti-reflective hard coating film as described above does not realize a sufficient anti-glare effect and anti-reflection effect and durability at the same time, a problem such as transmittance is reduced.

Republic of Korea Patent Publication No. 2009-0077767 Republic of Korea Patent Publication No. 2009-0020106

The present invention is to solve the conventional problems, the low refractive index layer and the high refractive index layer is alternately laminated on at least one side of the transparent polymer film, and the outermost layer is formed of the antireflection layer, the photocurable resin composition and An object of the present invention is to provide an anti-reflection hard coating film having excellent anti-glare performance and anti-reflection characteristics and having improved transmittance, durability, moisture resistance, and chemical resistance by forming a hard coating layer including inorganic particles.

In addition, an object of the present invention is to provide a method of manufacturing the antireflective hard coat film.

According to the present invention for achieving the above object, at least one low refractive index layer and at least one high refractive index layer is alternately laminated on at least one side of the transparent polymer film, the outermost layer is an antireflection layer And it provides an anti-reflection hard coating film comprising a hard coating layer comprising a photocurable resin composition and inorganic particles on at least one side of the transparent polymer film.

It provides an antireflective hard coating film that satisfies the following formula 1 to formula 3.

[Formula 1]

[Formula 2]

(In Formula 1, D _H is the thickness of the high refractive layer, D _L is the thickness of the low refractive layer, n _H is the refractive index of the high refractive layer, and n _L is the refractive index of the low refractive layer.)

[Equation 3]

(In Formula 3, D _C is the thickness of the hard coat layer, and D _H + D _L is the total thickness of the antireflective layer.)

The inorganic particles have an average particle diameter of 0.5 to 5㎛, 0.6 to 1.2 parts by weight based on 100 parts by weight of the photocurable resin composition, the low refractive layer is tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane , Tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyl tree Ethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyl tree Ethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, ratio Nyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryl It includes one or two or more selected from oxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, vinyl siloxane oligomer, and the high refractive layer is photocurable An antireflective hard coating film comprising an acrylate resin, a diluent, a photopolymerization initiator, and titanium oxide (TiO ₂ ) is provided.

The inorganic particle is one selected from polyether modified polymethylsiloxane, polyether modified polydimethylsiloxane, polyether modified hydroxypolydimethylsiloxane, polyacrylate copolymer, silicone polyether copolymer, fluorosilicone or It is formed by coating with a mixture of two or more kinds, the anti-reflective hard coating film provides an anti-reflection hard coating film for a polarizing plate.

In addition, at least one low refractive layer and at least one high refractive layer are alternately stacked on at least one side of the transparent polymer film to form an antireflection layer having an outermost layer having a low refractive layer, and at least one of the transparent polymer film. Forming a hard coating layer comprising a photocurable resin composition and inorganic particles on the surface, provides a method for producing an antireflective hard coating film satisfying the following formulas (1) to (3).

[Formula 1]

[Formula 2]

(In Formula 1, D _H is the thickness of the high refractive layer, D _L is the thickness of the low refractive layer, n _H is the refractive index of the high refractive layer, and n _L is the refractive index of the low refractive layer.)

[Equation 3]

(In Formula 3, D _C is the thickness of the hard coat layer, and D _H + D _L is the total thickness of the antireflective layer.)

According to the anti-reflection hard coating film of the present invention and a method for manufacturing the same, a low refractive index layer and a high refractive index layer are alternately laminated on at least one surface of the transparent polymer film, and the outermost layer forms an antireflection layer having a low refractive index layer, and is photocurable. By forming a hard coating layer containing the resin composition and inorganic particles, it is excellent in anti-glare performance and anti-reflection characteristics, and has the advantage of improving the transmittance, durability, moisture resistance, chemical resistance.

In addition, it can be applied to various displays, LCD, PDP outermost protective sheet, it is possible to replace the conventional anti-reflection sheet and anti-glare sheet with one, there is an advantage that can be applied to a wider field.

1 is a cross-sectional view of the antireflective hard coating film of Example 1 of the present invention.

Hereinafter, preferred embodiments of the anti-reflective hard coating film of the present invention and a manufacturing method thereof will be described in detail. The invention can be better understood by the following examples, which are intended for purposes of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

In the antireflective hard coating film of the present invention, a low refractive index layer and a high refractive index layer are alternately laminated on at least one surface of the transparent polymer film, and an outermost layer forms an antireflection layer having a low refractive index layer, and an inorganic layer is formed on the back of the curable resin composition. It is characterized in that the hard coating layer comprising particles.

The transparent polymer film is not limited as long as the film is not impaired transparency, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, polystyrene, triacetyl cellulose, acrylic, polyvinyl chloride And the like, and it is preferable to use a polyethylene terephthalate or a triacetyl cellulose film.

The use of such a substrate can be applied to camera lenses, polarizing plates of liquid crystal display devices, and plasma displays, which require not only an anti-reflection effect but also excellent wear resistance and optical properties. Plastic materials are obtained by ultrasonic cleaning and various surface treatments with organic solvents of alcohols.

In addition, in order to improve the adhesiveness with the hard coat layer, the transparent polymer film is suitably formed by corona discharge treatment on the surface or by forming a primer layer. The thickness of the transparent polymer film may be appropriately selected depending on the material of the film, but generally 25 to 500 μm is appropriate, and more preferably 50 to 300 μm is more effective.

 The hard coating layer of the present invention is characterized in that it is formed by including the inorganic particles in the photocurable resin composition, which is to form an inorganic particle irregularities on the surface of the hard coating layer to improve the anti-glare effect.

It is preferable that the photocurable resin composition used here contains 5 to 500 weight part of organic solvents, and 0.01 to 5 weight part of photoinitiators with respect to 100 weight part of polyfunctional acrylate oligomers or acrylate monomers.

 The polyfunctional acrylate oligomer may be a urethane acrylate oligomer, epoxy acrylate oligomer, polyether acrylate, polyester acrylate or a mixture thereof, and the acrylate monomer may be dipentacritritol hexaacrylate or dipenta. Critritol pentaacrylate, pentaacrylthiotol tetraacrylate, dipentaerythritol pentaacrylate, pentaalkyltritol triacrylate, pentaerythritol triacrylate, trimethylolpropane trimethacrylate and trimethylolpropane triacrylic Ethylene Glycol Diacrylate, Ethylene Glycol Dimethacrylate, Diethylene Glycol Dimethacrylate, Triphenyl Glycol Diacrylate, Butanediol Diacrylate and Triethylene Glycol Diacrylate, Hydroxyl Ethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethoxyethyl (meth) acrylate, allyl methacrylate, caprolactone acrylate and triethylolpropane methacrylate and mixtures thereof can be used. .

As is commonly used in the art to which the present invention pertains, “oligomer” in the present invention means a polymer having a number average molecular weight of 10,000 or less, preferably 5,000 or less.

 In selecting an organic solvent, compatibility, workability, and coating property of the photocurable resin should be considered as a top priority, and the appearance of the film and the adhesion to the substrate may depend on the selection of an appropriate organic solvent. Considering this point, methanol, ethanol, propanol, isopropanol, butanol, pentanol, methylcellulsolve, ethylcellulsolve, butylcellulsolve; More preferably, methyl ethyl ketone, methyl isobutyl ketone, acetone, dimethylformamide, diacetone alcohol, normal methylpyrrolidone, xylene, toluene or mixtures thereof are used.

In the present invention, any photoinitiator may be used as the initiator used for the curing of photocurable resins in general, and those skilled in the art may easily select and use. Among them, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-1- [4- (2-hydroxyethoxy ) Phenyl] -2-methyl-1-propanone, methylbenzoylformate, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2 -Methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone, diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide, phosphine jade Seed phenyl bis (2,4,6-trimethyl benzoyl), bis (eta 5-2,4-cyclopentadien-1-yl) bis [2,6-difluoro-3- (monohydrogen-ferrol-1- I) phenyl] titanium, aodonium (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate, and a combination thereof is preferable.

In addition, the photocurable resin composition of this invention can be used, including additives, such as a leveling agent and a slip agent within 1.0 weight part based on 100 weight part of whole coating compositions as needed.

The inorganic particles included in the hard coating layer used 0.6 to 1.2 parts by weight of 100 parts by weight of the photocurable resin composition having an average particle diameter of 0.5 to 5 μm. As the inorganic particles, one or two or more kinds of silica, alumina, calcium carbonate, magnesium carbonate, aluminum hydroxide, titanium dioxide, zirconium oxide, silicone resin particles, and acrylic particles can be used. Of these, it is preferable to use silica, in particular porous silica. When an average particle diameter is 0.5 micrometer or less, the anti-glare performance falls, and when a 5 micrometer or more is used, a film surface will be rough and it will become difficult to commercialize. In addition, when the content of the inorganic particles is less than 0.6 parts by weight, the anti-glare performance appears, and when the content is more than 1.2 parts by weight, the particles are buried by the binder coating film, a rainbow occurs due to scattering of light, causing a problem in that the transmittance is lowered.

The inorganic particle is one selected from polyether modified polymethylsiloxane, polyether modified polydimethylsiloxane, polyether modified hydroxypolydimethylsiloxane, polyacrylate copolymer, silicone polyether copolymer, fluorosilicone or It is effective to coat and add two or more kinds of mixtures, and the content of the coating agent is preferably 50 to 200 parts by weight based on 100 parts by weight of the inorganic particles. This is to form a coating layer on the surface of the inorganic particles in an optimum content, to prevent blocking between the inorganic particles to be uniformly dispersed, to improve the transmittance and to improve the effect of preventing glare.

The coating layer of the hard coating layer containing the inorganic particles is photocured on the transparent polymer film by a general film coating method such as roll coating, Mayer bar coating, blade coating, gravure coating, micro gravure coating, slot die coating, slide coating, curtain coating, and the like. After coating the resin composition and dried for 30 seconds to 5 minutes, preferably 1 to 3 minutes in a temperature range of 50 to 150 ℃, preferably 70 to 90 ℃, completely remove the solvent in the resin composition 200 to 1000 mJ UV light of about / cm 2, preferably 400 to 600mJ / cm 2 light quantity is irradiated to obtain a completely cured film.

In addition, the thickness of the hard coat layer of the present invention is preferably 3 to 10 ㎛. If the thickness of the hard coat layer is less than 3 μm, the wear resistance and the adhesion of inorganic particles appear. If the thickness of the hard coat layer is higher than 10 μm, the inorganic particles are buried in the photocurable resin and the anti-glare performance is deteriorated. Over adhesion can be reduced and scratch resistance is weakened.

The antireflection layer of the present invention is characterized in that the outermost layer is a low refractive index layer, while at least one low refractive index layer and at least one high refractive index layer are alternately stacked, which is to improve the antireflection characteristics more efficiently. .

The material for applying the high refractive index layer that can be used in the present invention may be made of titanium oxide (TiO ₂ ) as the main raw material, and the low refractive layer material may use silicon oxide (SiO ₂ ) as the main raw material. In general, if the low refractive index layer is coated after the high refractive index layer is coated on the substrate in a two layer manner, an optically required antireflective reflectance may be obtained. If more reflectivity is required, the number of layers can be coated in multiple layers.

The high refractive layer comprises 0.1 to 20% by weight of an ultraviolet curable acrylate oligomer, 60 to 99% by weight of a diluent, 0.01 to 10% by weight of a photopolymerization initiator, and 1.0 to 10% by weight of titanium oxide (TiO ₂ ) inorganic materials. The low refractive layer is formed by including 10 to 50% by weight of the polysiloxane oligomer and 50 to 90% by weight of the diluent. The high refractive layer thus formed has a refractive index of 1.6 ~ 2.35.

After forming the high refractive layer, even if a thin film is subsequently coated on the characteristics of the coating surface, a serious problem may occur in which appearance properties of the coating surface are markedly uneven or water droplet-like. In order to solve this problem, it is desirable to further perform the step of finely adjusting the thickness for the highest refractive index coating layer, which can be achieved in the future as well as industrially sufficient manufacturing method on the laboratory scale.

In general, the oligomer is a compound having a molecular weight of 500 ~ 5,000 may be diluted with each monomer depending on the viscosity and physical properties. The terminal of the oligomer consists of acrylate or methacrylate, and according to the structure of the main chain, urethane acrylate, epoxy acrylate, polyester acrylate, acrylic acrylate, silicone acrylate or amino arc, aliphatic urethane depending on the kind of isocyanate It is divided into acrylates and aromatic urethane acrylates, and the main characteristics of the final product depend on the structure of the oligomers used. In detail, the urethane acrylates include urethane bonds as repeating units and are generally flexible. Have physical properties And a wide variety of types, divided into acrylates. Aliphatic urethane acrylates are yellow-free and have 2 to 6 functional groups; Aromatic urethane acrylates are of yellowing type and have fast reactivity; Epoxy acrylates contain epoxy bonds in the main chain and cause yellowing, but have excellent hardness, solvent resistance and curability; Polyester acrylates have low viscosity and good weather resistance; Acrylic acrylates have good weather resistance and water resistance, in particular good adhesion to all materials; Amino acrylates are used as curing accelerators to improve surface hardening and have yellowing disadvantages; Silicone acrylates are used as wetting agents, slip agents or release agents.

Among the oligomers forming the high refractive layer of the present invention, it is preferable to use a polyfunctional urethane acrylate capable of maximizing surface hardness by improving crosslinking density within a range that does not have yellowing and does not adversely affect flexibility, and the content thereof is all It is preferable to include 0.1 to 20% by weight based on the composition, if the content is less than 0.1% by weight, the binder role is not sufficient and if the content exceeds 20% by weight may cause a problem of reduced refractive index and reduced coating adhesion There is this.

Photoinitiators used in forming the high refractive layer in the present invention, α- hydroxycyclohexylphenylmethanone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- On, hydroxydimethylacetophenone, 2-methyl-1 [4-methylthiophenyl] -2-morpholinopropane-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphineoxide, 2 Preference is given to using those comprising, 2-dimethoxy-1,2-diphenylethan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphineoxide or benzophenone. Any low yellow type initiator may be used without limitation, but it is preferable to use an α-hydroxyalkylphenone-based material, more preferably 1-hydroxycyclohexylphenyl ketone or α, α-dimethoxy-α-hydroxy Acetophenone is used individually or in mixture with each other.

The content of the photopolymerization initiator is preferably 0.01 to 10% by weight based on the total composition. When the content is less than 0.01% by weight, the reactivity is slow. When the content is more than 10% by weight, the reactivity is increased, but yellowing and shortening of the coating solvent stability occur. .

Such photoinitiators only initiate the reaction by absorbing ultraviolet rays to generate free radicals, most of which do not participate in the reaction. Initiators vary the wavelength range absorbed according to the type, there are yellowing type and low yellowing type. In general, it absorbs a wavelength of 300 ~ 360nm, when used in combination of two or more to absorb a variety of wavelengths to promote reactivity. In addition, when the coating thickness is thin, the higher the content of the initiator, the better the reactivity, and when the coating thickness is thick, the total curing rate increases as the content decreases.

In addition, the polysiloxane oligomer forming the low refractive layer of the present invention is a refractive index of 1.40 to 1.47 by polymerizing at least one compound selected from silane coupling agents at 30 to 50 ℃ for 30 minutes to 4 hours by a sol-gel polymerization method, Polysiloxane oligomers having an average molecular weight of 1,000 to 3,000 can be obtained. By including a diluent in the siloxane oligomer obtained in this way, the low refractive layer which has a refractive index of 1.35-1.5 can be formed.

The silane coupling agent for forming polysiloxane oligomer in this invention is a hydrolyzable alkoxysilane, For example, Tetraalkoxysilane, such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane; Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyl Limethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyl Trimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane , γ-methacryloxypro Trialkoxysilanes such as philtriethoxysilane; Diaalkoxysilanes, such as dimethyldimethoxysilane and dimethyl diethoxysilane, include, but are not limited to, tetramethylsilane and tetraethoxysilane, in consideration of the refractive index and the characteristics of the coating film.

The polysiloxane oligomer obtained by the sol-gel reaction of the silane coupling agent may be concentrated or diluted if necessary. In this case, the concentration of silicon oxide (SiO ₂ ) is calculated as a solid content in the polysiloxane solution. Is preferred. When the concentration of silicon oxide (SiO ₂ ) is less than 0.5% by weight, it is difficult to obtain a desired thickness by a single coating process, and when it exceeds 15% by weight, it may be difficult to secure stability and storage of the solution.

In the case of triacetyl cellulose (TAC) and polyethylene terraphthalate (PET) films, the curing conditions should be carried out below the temperature at which the film is not damaged. In order to perform curing at such a low temperature, the siloxane oligomer polymerization degree is It can control with addition amount of decomposable alkoxysilane and water, and a kind of acid.

In addition, in the present invention, the thickness of the high refractive index layer and the low refractive index coating layer is not particularly limited, but the thickness of the high refractive layer is higher than that of the low refractive layer, and it is effective to satisfy the following formula 1 more effectively.

[Formula 1]

(In Formula 1, D _H is the thickness of the high refractive layer, and D _L is the thickness of the low refractive layer.)

The low refractive index layer and the high refractive index layer is formed in a few tens of nm to hundreds of nm thickness has a thin film characteristics, and maintains the optimal reflectivity design and outermost coating properties, and is preferable in terms of the optimal reflectance design, the outer layer is low Forming the refractive layer is effective for improving the antireflection efficiency.

In addition, it is effective that the difference in refractive index between the low refractive layer and the high refractive layer satisfies the following expression (2).

[Formula 2]

(In Formula 2, n _H is the refractive index of the high refractive layer, n _L is the refractive index of the low refractive layer.)

When the inter-layer refractive index ratio is less than 1.05 in Equation 2, the difference in refractive index between the layers may be insignificant, which may cause a problem in that the anti-reflection efficiency is reduced. Inhibits the synergistic effect of, but may cause a problem that the efficiency of light at the interface between the layers is reduced.

Therefore, in order to exhibit the anti-reflection effect more effectively, it is effective to satisfy the ranges of Equations 1 and 2 simultaneously.

In addition, the antireflection hard coating film is preferably formed to satisfy the following equation (3).

[Equation 3]

(In Formula 3, D _C is the thickness of the hard coat layer, and D _H + D _L is the total thickness of the antireflective layer.)

If the thickness ratio of the hard coating layer and the anti-reflection layer is less than 1 in Equation 3, a relatively hard coating layer is formed to be thin, which may not exhibit sufficient scratch resistance and anti-glare effect. It may be formed thin to minimize the improvement of the antireflection effect, and the hard coating layer may be thick, which may cause a problem of reducing optical properties such as transmittance.

The method of coating the coating layers of the present invention may be used a variety of known coating methods, and the above may be mentioned Mayer coating method, specifically, the coating method of the high refractive coating liquid of the present invention is a UV curable high refractive index composition plastic After applying to the hot air is irradiated by heating and drying, and then obtained by irradiating with ultraviolet light coating, the low refractive coating solution is coated on the nasal refractive layer with a Mayer bar, and then irradiated with hot air to harden.

In addition, the type of ultraviolet lamp used for ultraviolet irradiation is also not particularly limited as long as it is commonly used, and therefore, high-pressure mercury lamp, ultra-high pressure mercury lamp, electrodeless lamp, metal halide lamp and the like can be used. As a specific example, a cured coating film may be formed by irradiating ultraviolet light having a light quantity of 600 to 1,000 mJ / cm 2 while moving a lamp having an output of 60 to 240 W / cm in a belt conveyor.

Physical properties of the coating film prepared in Examples and Comparative Examples of the anti-reflection hard coating film of the present invention will be described in detail, and the measurement results are shown in Table 2 and Table 3 below.

Property measurement

(1) Hayes

The average value was calculated by measuring the permeability measured using HM-150 MURAKAMI HAZEMETER.

(2) transmittance

The average value was calculated by measuring the permeability measured using HM-150 MURAKAMI HAZEMETER.

(3) surface hardness

Pencil hardness was measured according to ASTM D3502.

(4) appearance

The degree of smoothness and roughness of the cured film were visually observed.

(5) adhesion

Cross-cut Cellotape Peeling Test for Cured Films Into the film, 11 sheets of film cutting lines reaching the substrate at intervals of 1 mm are inserted each 11 horizontally and vertically to make 100 1mm2 eyes and attach a cellophane tape on it. The work was repeated three times. The results are classified and displayed as follows.

Very good: no delamination of the cured film

Good: When the number of eyes of the peeled film is 1 to 5

Poor: When the number of eyes of peeled film is 5-50

Poor: When the number of eyes of the peeled film is 50 to 100

[Table 1]

Example 1

Hard coating layer  formation

After mixing 1.5 g of silica particles (Sylysia 420, Fuji Silysia Chemical) to 100 g of the hard coating agent composition of Table 1, it was coated with a # 10 bar coater on a triacetyl cellulose (TAC) film, and dried at 80 ° C. for 2 minutes. After removing the solvent in the composition, the film for hard coating was formed by irradiating 500 mJ / cm 2 ultraviolet-ray and photopolymerizing, and the coating film thickness was 7 micrometers.

Antireflection layer  formation

The high refractive index layer composition was coated with a # 14 bar coater on the back surface of the film on which the hard coating layer was formed, and dried at 80 ° C. for 2 minutes to remove the solvent in the composition, and then photopolymerized by irradiating UV with 500mJ / cm 2. The low-refractive layer composition was coated with a # 3 bar coater on top of the coating to cure at 120 ° C. for 2 minutes to remove the solvent in the composition, to form a coating, and the total thickness of the anti-reflection layer measured was 1.8 μm. In addition, the refractive index of the high refractive layer was 1.85, and the refractive index of the low refractive layer was 1.43.

[Example 2]

Except that 2.0g of silica particles were used in forming the hard coat layer, the same process as in Example 1 was performed. The thickness of the hard coating layer was 7.6㎛, the antireflection layer was the same as in Example 1.

[Example 3]

Except for using 2.5g of silica particles in the hard coat layer was formed in the same manner as in Example 1. The thickness of the hard coat layer was 8.4㎛, the antireflection layer was the same as in Example 1.

Comparative Example 1

It was formed in the same manner as in Example 1 except that the antireflection layer was not formed.

[Table 2]

Example 4

After mixing 1.5 g of silica particles (Sylysia 420, Fuji Silysia Chemical) to 100 g of the hard coating agent composition of Table 1, it was coated with a polyethylene terephthalate film with a # 10 bar coater and dried at 80 ° C. for 2 minutes to form a solvent in the composition. After the removal, the film for hard coating was formed by photopolymerization by irradiating 500 mJ / cm 2 ultraviolet ray, and the coating film thickness was 6.8 μm, and the antireflection layer was formed in the same manner as in Example 1.

[Example 5]

Except that 2.0g of silica particles were used in forming the hard coat layer, the same process as in Example 4 was performed. The thickness of the hard coat layer was 7.7㎛, the antireflection layer was the same as in Example 1.

[Example 6]

Except for using 2.5g of silica particles in the hard coat layer was formed in the same manner as in Example 4. The thickness of the hard coat layer was 8.7㎛, the antireflection layer was the same as in Example 1.

[Example 7]

A hard coat layer was formed in the same manner as in Example 4, except that 1.5 g of silica particles coated with a polyether modified polydimethylsiloxane (BYK-333, BYK Co., Ltd.) in a 1: 1 ratio were used. The hard coat layer had a thickness of 7.1 μm, and the antireflection layer was the same as in Example 1.

Comparative Example 2

It was formed in the same manner as in Example 4 except that the antireflection layer was not formed.

[Table 3]

In the antireflective hard coating film of the present invention, the thickness ratio (D _H / D _L ) of the high refractive index layer and the low refractive index layer of the antireflection layer in Examples 1 to 7 satisfied the range of Equation 1 as 4.186, the antireflection layer The refractive index ratio (n _H / n _L ) of 1.294 was also satisfied with the range of Formula 2. In addition, the thickness ratio (D _C / (D _H + D _L )) of the hard coat layer and the antireflection layer of Examples 1 to 7 was 3.8 to 4.83, which satisfies the range of Equation 3.

In addition, when the inorganic particles added to the hard coating layer is coated and used as shown in Example 7, it can be seen that the surface slip characteristics are improved to improve the transmittance and surface hardness.

Therefore, while satisfying the conditions of Formulas 1 to 3, as shown in Tables 2 and 3, the present invention formed an antireflective hard coat film having improved optical properties of transmittance and improved mechanical properties of surface hardness.

While the present invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention. Accordingly, the above description should not be construed as limiting the scope of the present invention defined by the limits of the following claims.

10: low refractive index antireflection layer
20: high refractive index antireflection layer
30: transparent polymer film layer
40: hard coat layer
50: inorganic particles

Claims (10)

At least one low refractive index layer and at least one high refractive layer laminated alternately on at least one side of the transparent polymer film, and an antireflection layer having an outermost layer as a low refractive layer; and photocurable on at least one side of the transparent polymer film Anti-reflection hard coating film comprising a hard coating layer comprising a resin composition and inorganic particles.
The method of claim 1,
The anti-reflection layer is an anti-reflection hard coating film that satisfies the following formula 1 and formula 2.
[Formula 1]

[Formula 2]

(In Formula 1, D _H is the thickness of the high refractive layer, D _L is the thickness of the low refractive layer, n _H is the refractive index of the high refractive layer, and n _L is the refractive index of the low refractive layer.)
The method of claim 1,
The anti-reflection hard coating film is an anti-reflection hard coating film that satisfies the following equation 3.
[Formula 3]

(In Formula 3, D _C is the thickness of the hard coat layer, and D _H + D _L is the total thickness of the antireflective layer.)
The method of claim 1,
The inorganic particles have an average particle diameter of 0.5 to 5㎛, antireflection hard coating film containing 0.6 to 1.2 parts by weight based on 100 parts by weight of the photocurable resin composition.
The method of claim 1,
The low refractive layer is tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyl Trimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimeth Methoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane , Phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltri Methoxysilane, 1 selected from γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and vinyl siloxane oligomer It comprises a species or two or more, wherein the high refractive layer is an antireflection hard coating film comprising a photocurable acrylate resin, a diluent, a photopolymerization initiator and titanium oxide (TiO ₂ ).
The method of claim 1,
The inorganic particles may be selected from polyether modified polymethylsiloxane, polyether modified polydimethylsiloxane, polyether modified hydroxypolydimethylsiloxane, polyacrylate copolymer, silicone polyether copolymer, and phlosilicon. Anti-reflective hard coating film formed by coating with two or more mixtures.
7. The method according to any one of claims 1 to 6,
The antireflective hard coat film has a transmittance of 92 to 98% and a surface hardness of 2H to 8H.
The antireflective hard coat film of any one of claims 1 to 6 is for a polarizing plate.
At least one low refractive index layer and at least one high refractive layer are alternately laminated on at least one side of the transparent polymer film, and an outermost layer forms an antireflection layer having a low refractive index layer, and on at least one side of the transparent polymer film Forming a hard coating layer comprising a photocurable resin composition and inorganic particles, the method of producing an antireflective hard coating film satisfying the following formula (3).
[Formula 3]

(In Formula 3, D _C is the thickness of the hard coat layer, and D _H + D _L is the total thickness of the antireflective layer.) The method of claim 8,
The manufacturing method is a method of manufacturing an antireflective hard coating film formed to satisfy the following formula 1 and formula 2.
[Formula 1]

[Formula 2]

(In Formula 1, D _H is the thickness of the high refractive layer, D _L is the thickness of the low refractive layer, n _H is the refractive index of the high refractive layer, and n _L is the refractive index of the low refractive layer.)

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