KR102118904B1 - Anti-relrection composition and optical film using thereof - Google Patents

Abstract

The present invention relates to an antireflection coating composition and an optical film using the same.

Description

Anti-reflective coating composition and optical film using the same{ANTI-RELRECTION COMPOSITION AND OPTICAL FILM USING THEREOF}

The present invention relates to an antireflection coating composition and an optical film using the same.

Various display devices such as liquid crystal displays (LCDs), plasma displays (PDPs), CRTs, and electroluminescent displays (ELs) are implemented to solve the problem of deterioration in image quality due to glare due to reflected light and reflection on the front of the display ( Anti-Glare) films are commonly used. However, the general anti-glare film has a disadvantage that the resolution is poor.

Accordingly, in recent years, a demand for a low-reflectance film having a good resolution and excellent anti-reflection function is increasing.

Conventionally, a fluorine-containing copolymer such as a fluorine-containing acrylic copolymer, a fluorine-containing olefin copolymer, or a fluorine-containing epoxy ring-opening copolymer, and a simple fluorine-containing fluorine-type fluorine compound have been used as a low-refractive composition for forming the low-refractive layer. . In general, the fluorine-based compound is excellent in low refractive index, water resistance, and anti-fouling properties, but has disadvantages such as hardness, slip resistance, scratch resistance, and abrasion resistance. Therefore, research has been continued to compensate for the disadvantages of the fluorine-based compound, excellent transparency, hardness when forming a thin film, scratch-resistant and abrasion-resistant photo-curing coating composition and anti-reflection film containing the same in Korea Patent Publication 10-2009-0041854 (2009.04.29). However, the present invention describes that the refractive index of a thin film containing a fluorine-based compound and a siloxane compound having a UV functional group has a value of 1.45 or less in order to lower the refractive index. The present invention uses a siloxane compound having a three-dimensional structure containing a fluorine-based compound and an acryl group, as well as an effect of improving a sufficient refractive index, as well as improving reflectance control properties and improving transmittance, and can achieve excellent scratch resistance and pencil hardness compared to the above invention. .

Korea Patent Publication No. 10-2009-0041854 (2009.04.29)

The present invention is to provide an antireflection coating composition capable of forming a coating layer having excellent transparency by maintaining a range in which the refractive index of the entire coating solution is 1.39 to 1.43 using a compound that does not cause a decrease in the refractive index of the entire coating solution. In addition, it is intended to provide an anti-reflection coating composition having excellent scratch resistance and an improved pencil hardness of 3H or more.

In addition, the present invention is to provide an optical film having a low-refractive coating layer coated with an anti-reflective coating composition.

In addition, the present invention is to provide a polarizing plate comprising the optical film and a display device including the polarizing plate.

The present invention relates to an antireflective coating composition comprising a silsesquioxane compound of Formula 1 below.

[Formula 1]

(In the above formula,

,

에서 선택되고, R ₁ , R ₂ , R ₃ and R ₄ are each independently

,

Is selected from,

R ₅ and R ₆ are each independently selected from hydrogen or (C1-C5)alkyl,

Wherein n is an integer selected from 1 to 10, m is an integer selected from 2 to 12, k is an integer selected from 1 to 10, j is an integer selected from 1 to 10.)

The compound of Formula 1 may have a refractive index of 1.3 to 1.42, and a refractive index of the entire composition may be 1.39 to 1.43.

In addition, the present invention has at least one surface of the base film, an optical having a low refractive index coating layer coated with an antireflective coating composition comprising a silsesquioxane compound of Formula 1, an ultraviolet curable compound, inorganic particles, a photoinitiator, a surfactant, and a solvent It's about the film.

The anti-reflective coating composition according to the present invention has an effect of improving mechanical properties such as scratch resistance, adhesion, and pencil hardness by using silsesquioxane.

In addition, the optical film having a low-refractive coating layer coated with the anti-reflection coating composition is excellent in total light transmittance of 95% or more, haze is lower than 0.3, pencil hardness is higher than 3H, and adhesion to the base film is high. It is excellent, and has excellent scratch resistance.

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

The inventors of the present invention have researched to develop an anti-reflective coating composition having excellent surface scratch resistance and excellent adhesion to a base film, and achieve the desired physical properties by using a silsesquioxane compound of Formula 1 below. The present invention was completed by discovering that it was possible.

In addition, the present invention was completed by discovering that the pencil hardness was increased by mixing and using a fluorine-based (meth)acrylate monomer and hollow silica fine particles as a UV curable compound together with the compound of Formula 1 below.

An aspect of the present invention relates to an antireflection coating composition comprising a silsesquioxane compound of Formula 1 below.

[Formula 1]

(In the above formula,

,

에서 선택되고, R ₁ , R ₂ , R ₃ and R ₄ are each independently

,

Is selected from,

R ₅ and R ₆ are each independently selected from hydrogen or (C1-C5)alkyl,

Wherein n is an integer selected from 1 to 10, m is an integer selected from 2 to 12, k is an integer selected from 1 to 10, j is an integer selected from 1 to 10.)

In one aspect of the present invention, the antireflection coating composition may include a silsesquioxane compound, an ultraviolet curable compound, inorganic particles, a photoinitiator, a surfactant, and a solvent.

Specifically, the anti-reflection coating composition is silsesquioxane compound 0.1 ~ 10% by weight, ultraviolet curing compound 0.5 ~ 10% by weight, inorganic particles 0.1 ~ 5% by weight, photoinitiator 0.01 ~ 2% by weight, surfactant 0.01 ~ 0.1% by weight And a residual amount of solvent.

The anti-reflective coating composition according to the present invention may be used to form a low-refractive coating layer of an optical film.

In addition, an aspect of the present invention is a low refractive index coating composition for preventing reflection, including a silsesquioxane compound of Formula 1, an ultraviolet curable compound, an inorganic particle, a photoinitiator, a surfactant, and a solvent on at least one surface of a base film. It relates to an optical film having a coating layer.

In addition, an aspect of the present invention relates to a polarizing plate comprising the optical film.

In addition, an aspect of the present invention relates to a display device including the polarizing plate.

The following specifically describes the components that can be used in the antireflection coating composition of the present invention.

[Silsesquioxane compound]

The silsesquioxane compound of the present invention is selected from Formula 1 below.

[Formula 1]

(In the above formula,

,

에서 선택되고, R ₁ , R ₂ , R ₃ and R ₄ are each independently

,

Is selected from,

R ₅ and R ₆ are each independently selected from hydrogen or (C1-C5)alkyl,

Wherein n is an integer selected from 1 to 10, m is an integer selected from 2 to 12, k is an integer selected from 1 to 10, j is an integer selected from 1 to 10.)

In one aspect of the invention, alkyl includes both straight chain or ground forms.

Specifically, in the compound of Formula 1,

이고, j는 1 ~ 10에서 선택되는 정수인 것일 수 있다.R ₁ , R ₂ , R ₃ and R ₄ are

, J may be an integer selected from 1 to 10.

In addition, in the compound of Formula 1,

과

이 5 ~ 9 : 1 ~ 5 몰비로 치환되며, R₅는 (C1-C5)알킬에서 선택되고, m은 2 ~ 12에서 선택되는 정수이고, j는 1 ~ 10에서 선택되는 정수인 것일 수 있다.R ₁ , R ₂ , R ₃ and R ₄ are

and

It is substituted with a molar ratio of 5 to 9: 1 to 5, R ₅ is selected from (C1-C5) alkyl, m is an integer selected from 2 to 12, and j may be an integer selected from 1 to 10.

In addition, in the compound of Formula 1,

과

이 5 ~ 9 : 1 ~ 5 몰비로 치환되며, R₆는 (C1-C5)알킬에서 선택되고, k는 1 ~ 10에서 선택되는 정수이고, j는 1 ~ 10에서 선택되는 정수인 것일 수 있다.R ₁ , R ₂ , R ₃ and R ₄ are

and

It is substituted with a molar ratio of 5 to 9: 1 to 5, R ₆ is selected from (C1-C5) alkyl, k is an integer selected from 1 to 10, j may be an integer selected from 1 to 10.

In one aspect of the present invention, the silsesquioxane compound is used to control the refractive index of the composition, and the refractive index is in the range of 1.3 to 1.42, and the fluorine and acrylic groups are substituted to form a composition having a low refractive index of the entire antireflection coating composition. It can be manufactured, and the photocuring with other curable compounds during UV curing has the effect of further improving the pencil hardness.

In one aspect of the present invention, the silsesquioxane compound is preferred because it has excellent compatibility with CTA to use a weight average molecular weight of 3,000 to 30,000. In one aspect of the present invention, the silsesquioxane compound is preferably used in a composition of 0.1 to 10% by weight, more preferably 1 to 5% by weight. If the solid content is less than 0.1% by weight, the effect is minimal, and when it exceeds 10% by weight, photocuring may proceed slowly. By using in the above content range, it is possible to prepare an antireflection coating composition having a refractive index of 1.39 to 1.43 of the entire coating composition.

[Ultraviolet curing type compound]

In one embodiment of the present invention, the ultraviolet curable compound may be one or more selected from (meth)acrylic resins and fluorine (meth)acrylates. Preferably, it is preferable to use a fluorine-based (meth)acrylate because it can realize low refraction of the final composition and has excellent compatibility with the silsesquioxane compound.

The content of solid content of the ultraviolet curable compound in the composition may be 0.5 to 10% by weight, more specifically 0.6 to 8% by weight. When the content of the UV curable compound is less than 0.5% by weight, the scratch resistance and abrasion resistance of the coating film may be lowered, and the viscosity of the coating solution may be too low to be transferred to the coating machine and the substrate, and when used in excess of 10% by weight The viscosity may increase, which may cause problems such as deterioration of the flatness and coating properties of the coating film.

The (meth)acrylic resin may include (meth)acrylate monomer, urethane acrylate oligomer, epoxy acrylate oligomer, ester acrylate oligomer, dipentaerythritol hexaacrylate, pentaerythritol triacrylate, pentaerythritol tetra Acrylate, trimethylenepropane triacrylate, ethylene glycol diacrylate, 9,9-bis(4-(2-acryloxyethoxyphenyl)fluorene, bis(4-methacryloxythiophenyl)sulfide, bis( 4-vinylthiophenyl) sulfide or the like can be used by mixing one or two or more.

Specific examples of the (meth)acrylic monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, ethylhexyl (meth)acrylate, lauryl (meth) )Acrylate, stylic (meth)acrylate, dodecyl (meth)acrylate, benzyl (meth)acrylate, 2-phenoxy ethyl (meth)acrylate, naphtholethyl (meth)acrylate, 2-phenylphenol Ethyl (meth)acrylate, 2-thiophenolethyl (meth)acrylate, fluorine-modified (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, isobornol (meth)acrylate, norbornene (meth) )Acrylate, tetrahydrofuranol (meth)acrylate, cyclopentene (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl ( Meta)acrylate, caprolactone modified hydroxy (meth)acrylate, (meth)acrylomorpholine, and the like, but are not limited thereto.

The fluorine-based (meth)acrylate may be used for improving a low refractive index, improving the uniformity of a film, and the like, and any one or more selected from Formulas 2 to 4 below.

[Formula 2]

(In the above formula, a is an integer selected from 1 to 10.)

[Formula 3]

[Formula 4]

(In the above formula, R ₇ is hydrogen or (C1-C6) alkyl, b is an integer selected from 0 to 4, and c is an integer selected from 1 to 3.)

[Weapons]

In one aspect of the present invention, the inorganic particles are used to increase the anti-reflection property by lowering the refractive index and increase scratch resistance.

The content is preferably 0.1 to 5% by weight, more preferably 0.5 to 3% by weight. By using in the above range, it is possible to control the refractive index of the coating composition, and the antireflection property can be exhibited satisfactorily.

The inorganic particles are preferably in the range of 30 to 150% with respect to the thickness of the low-refractive coating layer to be formed. In order to obtain a transparent film without scattering and diffusing visible light, and to form fine irregularities on the surface by the inorganic particles, to have excellent slip properties, the average particle diameter is 1 to 1000 nm, more specifically 2 to 100 nm, further It is preferable to use those having 10 to 80 nm. When the average particle diameter is less than 10 nm, the air content in the particles is small, so the effect of improving the refractive index is negligible, and when it exceeds 1000 nm, surface irregularities are formed and scattering of incident light may occur.

An example of the inorganic particles may be hollow or porous silica particles.

More preferably, the hollow silica particles may be used, and the hollow silica particles may have a lower refractive index to increase anti-reflection properties and further improve scratch resistance.

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

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

When trying to achieve the low refractive index of the hollow silica particles and its high porosity, the thickness of the outer shell is reduced and the strength of the particles is weakened. Therefore, from the viewpoint of scratch resistance, when the refractive index of the hollow silica particles is less than 1.17, scratch resistance may deteriorate. In addition, when the refractive index of the hollow silica particles exceeds 1.40, the refractive index may be high and the anti-reflection characteristics may deteriorate. The refractive index of the hollow silica particles is measured using an Abbe refractive index meter (manufactured by ATAGO).

The hollow silica particles may be crystalline particles or amorphous particles, and monodisperse particles are preferred. When considering the shape, spherical particles are most preferred, but amorphous particles can be used without problems. The average particle diameter of the hollow silica fine particles is also measured by using electron micrographs.

The hollow silica particles may be surface treated with a silane coupling agent. In this case, dispersibility with a solvent is improved, and the curing layer is participated in curing during the curing process, thereby improving the durability of the coating layer through network formation with a binder.

The silane coupling agent is specifically methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethane 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)acrylooxymethyltrimethoxysilane, γ-(meth)acryloxymethyltriethoxysilane, γ-(meth)acrylo Oxyethyltrimethoxysilane, γ-(meth)acrylooxyethyltriethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, γ -(Meth)acrylooxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyl Liethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluoro Looctylethyl triisopropoxysilane, trifluoropropyl trimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltri At least one member selected from the group consisting of methoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, and methyltrichlorosilane can be used.

In order to further improve the dispersibility of the inorganic particles, the inorganic particles may be used in a dispersion state in which (meth)acrylic monomers, oligomers, and the like are dispersed. At this time, the solid content of the inorganic particles is preferably 10 to 30% by weight.

[Photoinitiator]

In one embodiment of the present invention, it is preferable to use a compound capable of decomposing to ultraviolet light, for example, α-amino acetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine Propanone-1, diphenylketone benzyldimethylketal, 2-hydroxy-2-methyl-1-phenyl-1-one, 4-hydroxycyclophenylketone, dimethoxy-2-phenylatetophenone, anthraquinone, Fluorene, triphenylamine, carbazole, 3-methylacetophenone, 4-knoacetophenone, 4,4-dimethoxyacetophenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexylphenylketone and Any one or two or more mixtures selected from benzophenone can be used. However, the present invention is not limited thereto, and what is used in the art may be used without limitation.

The content is preferably 0.01 to 2% by weight, more specifically 0.05 to 1% by weight. When used in less than 0.01% by weight, uncured may occur, and when used in excess of 2 parts by weight, scratch resistance and abrasion resistance of the coating film may be deteriorated.

[Surfactants]

In one aspect of the present invention, the surfactant is used to further improve the bonding between the inorganic particles and the silsesquioxane compound and the ultraviolet curable compound. Leveling agent or wetting agent may be used as the surfactant, and it is preferable to use a fluorine-based compound or a polysiloxane-based compound.

The content is preferably 0.01 to 0.1% by weight, more preferably 0.02 to 0.05% by weight. If the content is less than 0.01% by weight, the effect is negligible, and when used in excess of 0.1% by weight, adhesion to the base film may be reduced, and scratch resistance and abrasion resistance of the coating film may be reduced.

[menstruum]

In one aspect of the present invention, the solvent is dissolved in each component uniformly, it is preferable to use in consideration of not reacting with these components.

Specifically, methanol, ethanol, isopropanol, butanol, methyl cellulose, ethyl solusorb, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, cyclohexanone, hexane, heptane, octane , Any one or a mixture of two or more selected from benzene, toluene, and xylene may be used.

The content of the solvent can be adjusted to control the solid content of the entire coating composition in a range of 2 to 10% by weight.

In addition to the above components, an anti-reflective coating composition of the present invention may be used together with antioxidants, UV absorbers, light stabilizers, thermal polymerization inhibitors, leveling agents, surfactants, lubricants, and the like, as necessary.

The present invention provides an optical film comprising a low-refractive layer formed using the anti-reflection coating composition.

An aspect of the present invention, at least one surface of the base film, the silsesquioxane compound of Formula 1, a UV curable compound, an inorganic particle, a photoinitiator, a low-refractive coating layer coated with an anti-reflective coating composition comprising a surfactant and a solvent. It has an optical film.

In one aspect of the present invention, the base film is cellulose acylate, polynorbornene, polyimide, polycarbonate, polyester, polystyrene, polyolefin, polysulfone, polyethersulfone, polyarylate, polyetherimide, polymethylmetha It may be composed of acrylate and polyether ketone, polyvinyl alcohol and polyvinyl chloride alone or a mixture thereof.

Preferably, it may be a cellulose acylate film among the above-described base film, and the antireflective coating composition of the present invention has excellent miscibility with the cellulose acylate resin, thereby providing a film having better adhesion with the base film. Can be.

The cellulose acylate resin is an ester of cellulose and acetic acid, and all or part of the hydrogen atoms of the hydroxyl groups present in the 2nd, 3rd and 6th positions of the glucose units constituting cellulose are acetyl, propyronyl, and butyryl groups. It may be substituted with any one or two or more selected from. More preferably, those in which all or part of the hydrogen atoms of the hydroxyl groups present in the second, third and sixth positions of the glucose unit constituting cellulose are substituted with acetyl groups can be used. Specifically, for example, diacetyl cellulose, triacetyl cellulose, and the like are included.

The degree of substitution of the cellulose acylate resin is not limited, but is preferably 2.7 or more, and more preferably 2.7 to 3.0. The substitution degree can be measured according to ASTM D-817-91.

The molecular weight range of the cellulose acylate resin is not limited, but the weight average molecular weight is preferably in the range of 200,000 to 350,000. In addition, the molecular weight distribution of the cellulose acylate resin is also preferably Mw/Mn (Mw is the weight average molecular weight, Mn is the number average molecular weight) of 1.4 to 1.8, and more preferably 1.5 to 1.7.

In one aspect of the present invention, the method for applying the antireflection coating composition may be used without limitation as long as it is a known method, and specifically, for example, a die coater, air knife, reverse roll, spray, blade, casting, gravure, The coating process is possible by a suitable method such as micro gravure or spin coating. It is preferable to cure by irradiating UV after the coating.

In one aspect of the invention, the low-refractive coating layer is preferably a dry coating thickness of 10 ~ 200nm, it is possible to obtain an excellent anti-reflection effect at the thickness.

In one aspect of the present invention, the low-refractive-coating layer may have a refractive index of 1.39 to 1.43.

In one aspect of the present invention, the optical film may further include a hard coating layer between the base film and the low-refractive coating layer.

The hard coating layer is for realizing the surface hardness, it is preferred that the refractive index is 1.49 ~ 1.53. The refractive index can obtain an excellent anti-reflection effect in the above range.

The composition for forming a hard coating layer for forming the hard coating layer is not limited, as long as it is commonly used in the art.

The optical film according to the present invention may be an antireflection film, and the present invention provides a polarizing plate including the antireflection film. Specifically, the polarizing plate according to the present invention includes a polarizing film, an antireflection film according to the present invention, provided on at least one surface of the polarizing film. A protective film may be provided between the polarizing film and the anti-reflection film. Further, as the protective film, a substrate for forming a single coating layer may be used as it is when manufacturing the antireflection film. The substrate provided with the polarizing film and the anti-reflection layer may be laminated by an adhesive. As the polarizing film, one known in the art may be used.

The present invention provides a display device including the anti-reflection film or polarizing plate. The display device may be a liquid crystal display device or a plasma display device. The display device according to the present invention may have a structure known in the art, except that the anti-reflection film according to the present invention is provided. For example, in the display device according to the present invention, the anti-reflection film may be provided on the outermost surface of the viewer side or the backlight side of the display panel. In addition, the display device according to the present invention may include a display panel, a polarizing film provided on at least one surface of the panel, and an anti-reflection film provided on an opposite side of the polarizing film in contact with the panel.

The following will be described as an example for a detailed description of the present invention, the present invention is not limited to the following examples.

Hereinafter, the physical properties of the film were measured by the following measuring method.

1) scratch resistance

Using a steel wool of #0000, the coating film was reciprocated 20 times under a load of 500 g and scratched. 1 to 5 depending on the degree of scratch.

1: When the coating film is completely peeled off

2: 20 or more scratches

3: 10 to 20 scratches

4: 1 to 10 scratches

5: No scratch

2) Pencil hardness

A 500 g weight was raised using a pencil hardness tester (produced by Chungbuk Tech) and tested using a Mitsubishi pencil.

3) Total light transmittance

The total light transmittance was measured by a transmittance meter (Haze Meter HM-150, manufactured by Murakami Color Research Laboratory) by applying ASTM D1003 Haze and Luminous Transmittance of Transparent Plastics standards.

4) Haze

The film sample 40 mm×40 mm was measured at a haze meter (Murakami Color Research Laboratory, HM-150) at 25° C. and 60% relative humidity.

5) Reflectance (%)

The adapter MPC2200 was mounted on a spectrophotometer UV2450 (Shima Corporation) to measure specular reflectance for an angle of incidence of 5° at an angle of incidence of 5° in a wavelength region of 380 to 780 nm, and an average reflectance of 450 to 650 nm was calculated.

6) Adhesion

Peeling was performed using cellophane tape after scratching 100 checkerboards (1 mm × 1 mm) with a knife. The pattern that was not peeled at all was indicated by ○, and 1 to 10 peelings were indicated by △, and 10 or more patterns peeled were indicated by ×.

[Example 1]

1) Preparation of low-refractive coating solution (1)

Silsesquioxane compound 1 (Dongjin Semichem, 300S, refractive index 1.4, weight average molecular weight 3000) 1 g and fluorine-based acrylate 1 (Kyoeisha, Linc-162A) 2 g and pentaerythritol triacrylate (NK Chemical, PETA) 2.5 g Was mixed with 224 g of methyl isobutyl ketone (MIBK) to dissolve completely.

Subsequently, 6 g of hollow silica (illumination catalyst, 20% by weight solid dispersion, silica average particle size of 40 nm) was mixed, 0.3 g of α-amino acetophenone (BASF, Irgacure 907) as a photoinitiator, and 0.05 g of BYK-3570 as a surfactant. It was added to prepare a low-refractive coating solution (1).

[Silsesquioxane compound 1]

이고, j는 6이다.)(In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are

And j is 6.)

[Fluorine acrylate 1]

(In the above formula, a is 8.)

2) Preparation of optical film

On the surface of the transparent substrate cellulose triacetate film having a thickness of 80 μm, a hard coating solution (Kyoeisha, HX-610UV) was applied to a dry coating thickness of 5 μm using a wire bar, and then dried and cured. Drying was performed at 90° C. for 1 minute, and curing was UV-cured under a nitrogen atmosphere for 10 seconds using a high-pressure mercury lamp of 120 W/cm.

The low-refractive coating solution (1) was applied to the top of the hard coating layer so that the dry coating thickness was 100 nm using a wire bar, followed by drying and curing. Drying was performed at 90° C. for 1 minute, and curing was UV-cured under a nitrogen atmosphere for 10 seconds using a high-pressure mercury lamp of 120 W/cm.

The physical properties of the prepared film were measured and are shown in Table 1 below.

[Example 2]

1) Preparation of low-refractive coating solution (2)

2 g of silsesquioxane compound 1 (Dongjin Semichem, 300S, refractive index 1.4, weight average molecular weight 3000), 1 g of fluorine-based acrylate (Kyoeisha, Linc-162A) and 2.5 g of pentaerythritol triacrylate (NK Chemical, PETA) The mixture was dissolved in 224 g of methyl isobutyl ketone (MIBK) to dissolve completely.

Subsequently, 6 g of hollow silica (illumination catalyst, 20% by weight solid dispersion, silica average particle size of 40 nm) were mixed, 0.3 g of α-amino acetophenone (BASF, Irgacure 907) as a photoinitiator, and 0.05 g of BYK-3570 as a surfactant. It was added to prepare a low-refractive coating solution (2).

2) Preparation of optical film

On the surface of the transparent substrate cellulose triacetate film having a thickness of 80 μm, a hard coating solution (Kyoeisha, HX-610UV) was applied to a dry coating thickness of 5 μm using a wire bar, and then dried and cured. Drying was performed at 90° C. for 1 minute, and curing was UV-cured under a nitrogen atmosphere for 10 seconds using a high-pressure mercury lamp of 120 W/cm.

The low-refractive coating solution (2) was applied to the top of the hard coating layer so that the dry coating thickness was 100 nm using a wire bar, followed by drying and curing. Drying was performed at 90° C. for 1 minute, and curing was UV-cured under a nitrogen atmosphere for 10 seconds using a high-pressure mercury lamp of 120 W/cm.

The physical properties of the prepared film were measured and are shown in Table 1 below.

[Example 3]

1) Preparation of low-refractive coating solution (3)

Silsesquioxane compound 1 (Dongjin Semichem, 300S, refractive index 1.4, weight average molecular weight 3000) 2 g and fluorine acrylate 2 (Kyoeisha, Linc-5A) 1 g and pentaerythritol triacrylate (NK Chemical, PETA) 2.5 g Was mixed with 224 g of methyl isobutyl ketone (MIBK) to dissolve completely.

Subsequently, 6 g of hollow silica (illumination catalyst, 20% by weight solid dispersion, silica average particle size of 40 nm) was mixed, 0.3 g of α-amino acetophenone (BASF, Irgacure 907) as a photoinitiator, and 0.05 g of BYK-3570 as a surfactant. A low-refractive coating solution (3) was prepared by addition.

[Fluorine-based acrylate 2]

2) Preparation of optical film

On the surface of the transparent substrate cellulose triacetate film having a thickness of 80 μm, a hard coating solution (Kyoeisha, HX-610UV) was applied to a dry coating thickness of 5 μm using a wire bar, and then dried and cured. Drying was performed at 90° C. for 1 minute, and curing was UV-cured under a nitrogen atmosphere for 10 seconds using a high-pressure mercury lamp of 120 W/cm.

The low-refractive coating solution (3) was applied to the top of the hard coating layer so that the dry coating thickness was 100 nm using a wire bar, followed by drying and curing. Drying was performed at 90° C. for 1 minute, and curing was UV-cured under a nitrogen atmosphere for 10 seconds using a high-pressure mercury lamp of 120 W/cm.

The physical properties of the prepared film were measured and are shown in Table 1 below.

[Example 4]

1) Preparation of low-refractive coating solution (4)

Silsesquioxane compound 2 (Dongjin Semichem, 300S-7, refractive index 1.45, weight average molecular weight 10,000) 2 g and fluorine-based acrylate 2 (Kyoeisha, Linc-5A) 1 g and pentaerythritol triacrylate (NK Chemical, PETA) 2.5 g of methyl isobutyl ketone (MIBK) was mixed with 224 g to dissolve completely.

Subsequently, 6 g of hollow silica (illumination catalyst, 20% by weight solid dispersion, silica average particle size of 40 nm) was mixed, 0.3 g of α-amino acetophenone (BASF, Irgacure 907) as a photoinitiator, and 0.05 g of BYK-3570 as a surfactant. The low-refractive coating solution (4) was prepared by addition.

[Silsesquioxane compound 2]

이고, j는 6이다.)
(In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are

And j is 6.)

2) Preparation of optical film

On the surface of the transparent substrate cellulose triacetate film having a thickness of 80 μm, a hard coating solution (Kyoeisha, HX-610UV) was applied to a dry coating thickness of 5 μm using a wire bar, and then dried and cured. Drying was performed at 90° C. for 1 minute, and curing was UV-cured under a nitrogen atmosphere for 10 seconds using a high-pressure mercury lamp of 120 W/cm.

The low-refractive coating solution (4) was applied to the top of the hard coating layer so that the dry coating thickness was 100 nm using a wire bar, followed by drying and curing. Drying was performed at 90° C. for 1 minute, and curing was UV-cured under a nitrogen atmosphere for 10 seconds using a high-pressure mercury lamp of 120 W/cm.

The physical properties of the prepared film were measured and are shown in Table 1 below.

[Example 5]

1) Preparation of low-refractive coating solution (5)

Silsesquioxane compound 3 (Dongjin Semichem, 300S-P, refractive index 1.32, weight average molecular weight 4,000) 2 g and fluorine-based acrylate 2 (Kyoeisha, Linc-5A) 1 g and pentaerythritol triacrylate (NK Chemical, PETA) 2.5 g was mixed with 224 g of methyl isobutyl ketone (MIBK) to dissolve completely.

Subsequently, 6 g of hollow silica (monocatalyst, 20% by weight solid dispersion, silica average particle diameter of 40 nm) were mixed, 0.3 g of α-amino acetophenone (BASF, Irgacure 907) as a photoinitiator, and 0.05 g of BYK-3570 as a surfactant. It was added to prepare a low-refractive coating solution (5).

[Silsesquioxane compound 3]

과

이 7 : 3 몰비로 치환되며, 상기 R₅는 CH₃이고 m은 6이다.)
(In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are

and

It is substituted with a 7:3 molar ratio, and R ₅ is CH ₃ and m is 6.)

2) Preparation of optical film

On the surface of the transparent substrate cellulose triacetate film having a thickness of 80 μm, a hard coating solution (Kyoeisha, HX-610UV) was applied to a dry coating thickness of 5 μm using a wire bar, and then dried and cured. Drying was performed at 90° C. for 1 minute, and curing was UV-cured under a nitrogen atmosphere for 10 seconds using a high-pressure mercury lamp of 120 W/cm.

The low-refractive coating solution 5 was applied to the top of the hard coating layer using a wire bar so that the dry coating thickness was 100 nm, followed by drying and curing. Drying was performed at 90° C. for 1 minute, and curing was UV-cured under a nitrogen atmosphere for 10 seconds using a high-pressure mercury lamp of 120 W/cm.

The physical properties of the prepared film were measured and are shown in Table 1 below.

[Example 6]

1) Preparation of low-refractive coating solution (6)

Silsesquioxane compound 4 (Dongjin Semichem, 300S-FM55, refractive index 1.35, weight average molecular weight 5,000) 2 g and fluorine-based acrylate 2 (Kyoeisha, Linc-5A) 1 g and pentaerythritol triacrylate (NK Chemical, PETA) 2.5 g was mixed with 224 g of methyl isobutyl ketone (MIBK) to dissolve completely.

Subsequently, 6 g of hollow silica (monocatalyst, 20% by weight solid dispersion, silica average particle diameter of 40 nm) were mixed, 0.3 g of α-amino acetophenone (BASF, Irgacure 907) as a photoinitiator, and 0.05 g of BYK-3570 as a surfactant. By addition, a low-refractive coating solution (6) was prepared.

[Silsesquioxane compound 4]

과

(In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are

and

This 5:5 molar ratio is substituted, and R ₆ is CH ₃ and k is 2.)

2) Preparation of optical film

On the surface of the transparent substrate cellulose triacetate film having a thickness of 80 μm, a hard coating solution (Kyoeisha, HX-610UV) was applied to a dry coating thickness of 5 μm using a wire bar, and then dried and cured. Drying was performed at 90° C. for 1 minute, and curing was UV-cured under a nitrogen atmosphere for 10 seconds using a high-pressure mercury lamp of 120 W/cm.

The low-refractive coating solution 6 was applied to the top of the hard coating layer so that the dry coating thickness was 100 nm using a wire bar, followed by drying and curing. Drying was performed at 90° C. for 1 minute, and curing was UV-cured under a nitrogen atmosphere for 10 seconds using a high-pressure mercury lamp of 120 W/cm.

The physical properties of the prepared film were measured and are shown in Table 1 below.

[Comparative Example 1]

1) Preparation of low-refractive coating solution (7)

3 g of fluorine-based acrylate 1 (Kyoeisha, Linc-162A) and 2.5 g of pentaerythritol triacrylate (NK Chemical, PETA) were mixed in 224 g of methyl isobutyl ketone (MIBK) to dissolve completely.

Subsequently, 6 g of hollow silica (monocatalyst, 20% by weight solid dispersion, silica average particle diameter of 40 nm) were mixed, 0.3 g of α-amino acetophenone (BASF, Irgacure 907) as a photoinitiator, and 0.05 g of BYK-3570 as a surfactant. A low refractive index coating solution (7) was prepared by addition.

2) Preparation of optical film

On the surface of the transparent substrate cellulose triacetate film having a thickness of 80 μm, a hard coating solution (Kyoeisha, HX-610UV) was applied to a dry coating thickness of 5 μm using a wire bar, and then dried and cured. Drying was performed at 90° C. for 1 minute, and curing was UV-cured under a nitrogen atmosphere for 10 seconds using a high-pressure mercury lamp of 120 W/cm.

The low-refractive coating solution (7) was applied to the top of the hard coating layer so that the dry coating thickness was 100 nm using a wire bar, followed by drying and curing. Drying was performed at 90° C. for 1 minute, and curing was UV-cured under a nitrogen atmosphere for 10 seconds using a high-pressure mercury lamp of 120 W/cm.

The physical properties of the prepared film were measured and are shown in Table 1 below.

[Comparative Example 2]

1) Preparation of low-refractive coating solution (8)

3 g of fluorine-based acrylate 2 (Kyoeisha, Linc-5A) and 2.5 g of pentaerythritol triacrylate (NK Chemical, PETA) were mixed in 224 g of methyl isobutyl ketone (MIBK) to dissolve completely.

Subsequently, 6 g of hollow silica (monocatalyst, 20% by weight solid dispersion, silica average particle diameter of 40 nm) were mixed, 0.3 g of α-amino acetophenone (BASF, Irgacure 907) as a photoinitiator, and 0.05 g of BYK-3570 as a surfactant. A low-refractive coating solution (8) was prepared by addition.

2) Preparation of optical film

On the surface of the transparent substrate cellulose triacetate film having a thickness of 80 μm, a hard coating solution (Kyoeisha, HX-610UV) was applied to a dry coating thickness of 5 μm using a wire bar, and then dried and cured. Drying was performed at 90° C. for 1 minute, and curing was UV-cured under a nitrogen atmosphere for 10 seconds using a high-pressure mercury lamp of 120 W/cm.

The low-refractive coating solution 8 was applied to the top of the hard coating layer so that the dry coating thickness was 100 nm using a wire bar, followed by drying and curing. Drying was performed at 90° C. for 1 minute, and curing was UV-cured under a nitrogen atmosphere for 10 seconds using a high-pressure mercury lamp of 120 W/cm.

The physical properties of the prepared film were measured and are shown in Table 1 below.

[Table 1]

As shown in Table 1, it can be seen that the embodiment of the present invention has excellent total light transmittance of 95% or more, low haze, and excellent scratch resistance and adhesion. In addition, when comparing Comparative Examples 1 and 2 and Examples 1 to 6, it was found that when the silsesquioxane compound of the present invention was added, the pencil hardness and scratch resistance were further improved compared to the comparative example.

Claims (18)

An antireflection coating composition comprising a silsesquioxane compound of Formula 1 and a fluorine-based (meth)acrylate.
[Formula 1]

(In the above formula,
R ₁ , R ₂ , R ₃ and R ₄ are each independently

,

Is selected from,
R ₅ and R ₆ are each independently selected from hydrogen or (C1-C5)alkyl,
Wherein n is an integer selected from 1 to 10, m is an integer selected from 2 to 12, k is an integer selected from 1 to 10, j is an integer selected from 1 to 10.) According to claim 1,
The anti-reflective coating composition having a refractive index of the silsesquioxane compound of 1.3 to 1.42 and a refractive index of the entire coating composition of 1.39 to 1.43. According to claim 1,
The anti-reflection coating composition is an anti-reflective coating composition comprising a silsesquioxane compound, a fluorine-based (meth)acrylate, inorganic particles, a photoinitiator, a surfactant, and a solvent. According to claim 3,
The antireflection coating composition further comprises a (meth)acrylic resin. According to claim 1,
The fluorine-based (meth) acrylate is a coating composition for anti-reflection at least one selected from the following formulas 2 to 3.
[Formula 2]

(In the above formula, a is an integer selected from 1 to 10.)
[Formula 3]

According to claim 3,
The inorganic particles are anti-reflective coating compositions of hollow or porous silica particles having an average particle diameter of 1 to 1000 nm. The method of claim 6,
The inorganic particles are hollow silica coatings having an average particle diameter of 10 to 80 nm for antireflection coating composition. According to claim 3,
The photoinitiator is α-amino acetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morphopropanone-1, diphenylketone benzyldimethylketal, 2-hydroxy-2-methyl- 1-phenyl-1-one, 4-hydroxycyclophenylketone, dimethoxy-2-phenylacetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3-methylacetophenone, 4-knoloaceto Antireflective coating composition which is a mixture of any one or two or more selected from phenone, 4,4-dimethoxyacetophenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexylphenylketone and benzophenone. According to claim 3,
The surfactant is a fluorine-based compound or a polysiloxane-based antireflection coating composition. According to claim 3,
The solvent is methanol, ethanol, isopropanol, butanol, methyl cellulose, ethyl solusorb, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, cyclohexanone, hexane, heptane, octane , Benzene, toluene, xylene, antireflection coating composition which is a mixture of any one or two or more. According to claim 3,
The anti-reflection coating composition is the silsesquioxane compound 0.1 ~ 10 wt%, fluorine-based (meth) acrylate 0.5 ~ 10 wt%, inorganic particles 0.1 ~ 5 wt%, photoinitiator 0.01 ~ 2 wt%, surfactant 0.01 ~ 0.1 An antireflection coating composition comprising weight percent and residual solvent. The method according to any one of claims 1 to 11,
The anti-reflection coating composition is an anti-reflective coating composition that is used to form a low-refractive coating layer of an optical film. A pencil hardness having an antireflection coating composition comprising at least one surface of the base film, a silsesquioxane compound represented by the following Chemical Formula 1, a fluorine-based (meth)acrylate, inorganic particles, a photoinitiator, a surfactant, and a solvent is 3 H or more. Optical film having a refractive coating layer.
[Formula 1]

(In the above formula,
R ₁ , R ₂ , R ₃ and R ₄ are each independently

,

Is selected from,
R ₅ and R ₆ are each independently selected from hydrogen or (C1-C5)alkyl,
Wherein n is an integer selected from 1 to 10, m is an integer selected from 2 to 12, k is an integer selected from 1 to 10, j is an integer selected from 1 to 10.) The method of claim 13,
The base film is cellulose acylate, polynorbornene, polyimide, polycarbonate, polyester, polystyrene, polyolefin, polysulfone, polyether sulfone, polyarylate, polyetherimide, polymethyl methacrylate and polyether ketone, An optical film consisting of polyvinyl alcohol and polyvinyl chloride alone or a mixture thereof. The method of claim 13,
The low-refractive coating layer is an optical film having a dry coating thickness of 10 to 200 nm and a refractive index of 1.39 to 1.43. The method of claim 13,
An optical film further comprising a hard coating layer between the base film and the low-refractive coating layer. A polarizing plate comprising the optical film of any one of claims 13 to 16. A display device comprising the polarizing plate of claim 17.