KR20140032819A - Anti-reflective coating film for organic light emitting diode and polarizing plate comprising the same - Google Patents

Abstract

The present invention relates to an organic light emitting diode display panel comprising a surface-treated antireflective film and an organic light emitting diode display comprising the same. More specifically, the organic light emitting diode display panel forms a surface-treated coating film having an anti-reflective layer on a polarizing plate, thereby preventing reflection-color, improving visibility, and reducing fatigability.

Description

Anti-reflective coating film for organic light emitting diode and polarizing plate comprising the same}

The present invention relates to an OLED display having a surface treatment coating film for an organic light emitting diode (OLED) display having an antireflective coating and an antireflective layer, a polarizing plate including the same, and a panel having the polarizing plate.

Recently, interest in organic light emitting diodes (OLEDs) is increasing among flat panel displays, which can realize vivid colors, ultra thin designs, and can operate at ultra low power (2 ~ 1-V). This is because it has many advantages.

Looking at the structure of the OLED includes a glass substrate and a metal electrode, the metal electrode uses a quarter-wave film to suppress the reflection of the external light introduced into the panel by showing a mirror-like reflection effect. However, there is a problem that the display color is not natural and has a unique color.

In addition, when the OLED display screen is implemented, specific reflective colors such as red, blue, and green are displayed depending on the unique characteristics of the electrode / quad wave film and the viewing angle. Displaying such a specific color lowers the visibility of the display and increases the fatigue of the user, and thus, there is a need for a technology to offset the surface coating.

On the other hand, the purpose of the surface treatment on the surface of the display is to improve the wear resistance of the display and to reduce the reflection of the external light source to improve the image contrast. The reduction of the amount of reflection of external light includes a method of inducing diffuse reflection through surface irregularities and inducing vanishing interference with a multilayer coating design.

When applying the anti-glare coating having the surface irregularities, there is a problem that the resolution is reduced in the high resolution display and the sharpness of the image due to the diffuse reflection on the surface. Therefore, in recent years, the antireflection film containing the antireflection layer using a binder, an organic copolymer, inorganic particle, etc. is applied.

However, a method for improving the visibility of OLED and reducing the fatigue of the user has not been developed yet.

The present invention is to provide a surface treatment coating film for an organic light emitting diode (OLED) display which satisfies all the basic physical properties and improves visibility, excellent user fatigue and anti-reflection.

Another object of the present invention is to provide a polarizing plate including the coating film and an organic light emitting diode display having such a polarizing plate.

The present invention relates to a transparent substrate;

A hard coating layer formed on the transparent substrate and including a crosslinked polymer of a 3 to 6 functional polyfunctional acrylate monomer and having a refractive index of 1.20 to 1.55; And

It is formed on the hard coating layer, and includes a low reflection coating layer having a lower refractive index than the hard coating layer and the refractive index difference is Δn> 0.05,

The low reflection coating layer provides an antireflection film including a crosslinked polymer of a 3 to 6 functional multifunctional acrylate monomer, and hollow particles.

The low reflection coating layer may have an average reflectance of 2% or less and a thickness of 20 to 350 nm.

The low reflection coating layer may be formed using a composition including 1 to 100 parts by weight of the photopolymerization initiator and 10 to 360 parts by weight of the hollow particles based on 100 parts by weight of the multifunctional acrylate monomer. The hard coating layer may be formed using a hard coating solution composition containing 1 to 10 parts by weight of the photopolymerization initiator and 0.1 to 10 parts by weight of the surfactant based on 100 parts by weight of the multifunctional acrylate monomer.

Moreover, this invention provides the polarizing plate in which one or more layers of the above-mentioned antireflection film are formed in the surface.

In another aspect, the present invention provides an organic light emitting diode display comprising the polarizing plate.

The organic light emitting diode display includes a metal electrode formed on a glass substrate; A quarter wave film formed on the metal electrode; The panel containing the above-mentioned polarizing plate formed on the said quarter wave film can be provided.

In addition, a bi-wavelength film may be further formed between the quarter-wave film and the polarizing plate.

The organic light emitting diode display includes a polarizing plate including the antireflective film, whereby a minimum reflection wavelength of λ ₁ defined as a reflection wavelength in the polarizing plate by external light is 500 to 550 nm, and The maximum reflection wavelength of λ ₂ , defined as the reflection wavelength, may be 400 to 650 nm.

As described above, the present invention can adjust the visibility by lowering the reflectance by providing the anti-reflection film on the surface of the polarizing plate. Therefore, when the polarizing plate is applied to the panel for an organic light emitting diode display, it is possible to satisfy the basic physical properties such as durability and to improve the visibility of the display and to reduce the fatigue of the user, and to provide an excellent antireflection property. have.

1 is a simplified cross-sectional view of an organic light emitting diode display panel according to an embodiment of the present invention.
2 is a simplified cross-sectional view of an organic light emitting diode display panel according to another embodiment of the present invention.

Hereinafter, an anti-reflection film and a polarizing plate and a display device including the same according to specific embodiments of the present invention will be described in detail.

Anti-reflective coating film (anti-reflective coating film) of the surface treatment film is a film having a high transmittance and low reflection characteristics, in the field of the optical display has an anti-glare function with the protection function of the display surface, thereby improving the visibility It is a functional film.

Accordingly, the present invention provides a method of improving display visibility by lowering the reflectance as well as adjusting the visibility by including an antireflection film having a low reflection coating on the surface of the polarizing plate. The present invention is characterized by coating an antireflective film coating having a wavelength range in which offset interference occurs on the polarizing plate to counteract the problems caused by the use of a quarter wave film. In addition, the present invention is to correct the reflection color of the OLED display panel represented by the external light by adjusting the refractive index of the surface treatment (anti-reflection) film by using the destructive interference of light.

According to one embodiment of the invention, a transparent substrate; A hard coating layer formed on the transparent substrate and including a crosslinked polymer of a 3 to 6 functional polyfunctional acrylate monomer and having a refractive index of 1.20 to 1.55; And a low reflection coating layer formed on the hard coating layer and having a lower refractive index than the hard coating layer and having a refractive index difference of Δn> 0.05, wherein the low reflection coating layer is a crosslinked polymer of a 3 to 6 functional polyfunctional acrylate monomer, and There is provided an antireflective film comprising hollow particles.

The antireflection film of the present invention means a surface treatment coating film for OLED displays. The anti-reflection film may be provided in a structure in which a hard coating layer and a low reflection coating layer are sequentially formed on the light transmissive substrate.

The low reflection coating layer may be an antireflection layer, and may include an acrylate-based crosslinked polymer having a predetermined molecular weight and hollow particles through crosslinking of the acrylate monomer and the hollow particle. The crosslinked polymer included in the low reflection coating layer of the present invention may be a crosslinked copolymer of an acrylate compound having a weight average molecular weight of less than 600. In this case, the hollow particles may be included in the form of a layer, may be mixed with the crosslinked polymer and dispersed on the hard coating layer. When the hollow particles are included in the form of a layer, a plurality of hollow particles continuously connected in a direction parallel to the substrate may be densely distributed in the form of a layer. Therefore, the low reflection coating layer of the present invention may exhibit an excellent anti-reflection effect than conventional.

The low reflection coating layer has a lower refractive index than the hard coating layer, and the refractive index difference is preferably Δn> 0.05. Preferably, the hard coating layer has a refractive index of 1.20 to 1.55. In addition, the low reflection coating layer may have a refractive index of at least 1.15-1.5 or more. If the difference in refractive index is less than 0.05, there is a problem in that the reflectance is not increased to have low reflection characteristics.

In addition, the low reflection coating layer may have an average reflectance of 2% or less and a thickness of 20 to 350 nm. In addition, the hard coating layer may have a thickness of about 1 μm to about 8 μm.

The low reflection coating layer may be formed using a composition including 1 to 100 parts by weight of the photopolymerization initiator and 10 to 360 parts by weight of the hollow particles based on 100 parts by weight of the multifunctional acrylate monomer. Therefore, the low reflection coating layer may include a crosslinked copolymer of the acrylate monomer having the weight average molecular weight described above and hollow particles.

The 3- to 6-functional polyfunctional acrylate monomers include pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, trimethylene propane triacrylate, dipentaerythritol heptaacrylate, dipentaerythritol hydride Roxy pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylene propyl triacrylate, propoxylated glycerol triacrylate, 1,6-hexanedioldiacrylate, propoxylated glycerol tri Two or more types selected from the group of polyfunctional acrylate monomers consisting of acrylate, tripropylene glycol diacrylate, and ethylene glycol diacrylate can be used. For example, the polyfunctional acrylate monomer may be a mixture of pentaerythritol triacrylate and dipentaerythritol hepacrylate.

The hollow particles may be one having a number average particle diameter of 5 to 80 nm, for example, hollow silica particles. The particle diameter of the hollow particles may be determined in a range capable of maintaining the transparency of the film and yet exhibiting an antireflection effect. According to another example, the hollow particles may have a number average particle diameter of 10 to 75 nm, or about 20 to 70 nm.

In this case, the term "hollow particles" may refer to particles having an empty space on the surface and / or inside of the organic or inorganic particles. For example, the term “hollow silica particles” may refer to particles having a void space on the surface and / or inside of the silica particles as silica particles derived from a silicon compound or an organosilicon compound. Therefore, the low reflection coating layer of the present invention can achieve a low refractive index and antireflection effect by using hollow particles.

The hollow particles may be used in an amount of 10 to 360 parts by weight based on 100 parts by weight of the multifunctional acrylate monomer described above. The content of the hollow particles can be adjusted in the above-described range so that the minimum distribution by the hollow particles can be achieved, but in order to form a desirable distribution according to the phase separation.

In addition, the hollow particles may be included in a colloidal phase having a solid content of 5 to 40% by weight as a dispersion in a dispersion medium (water or an organic solvent). The organic solvent usable as the dispersion medium may include alcohols such as methanol, isopropyl alcohol (IPA), ethylene glycol, butanol, etc .; Ketones such as methyl ethyl ketone and methyl iso butyl ketone (MIBK); Aromatic carbon hydrogens such as toluene and xylene; Amides such as dimethyl formamide, dimethyl acetamide and N-methyl pyrrolidone; Esters such as ethyl acetate, butyl acetate and? -Butyrolactone; Ethers such as tetrahydrofuran and 1,4-dioxane; Or mixtures thereof.

In addition, when forming the low reflection coating layer in the present invention, the above-described antireflective coating composition may further include a copolymer of fluorine-based or fluorine-based and silicon-based as a leveling agent as a binder-forming compound. For example, the antireflective coating composition of the present invention may further include 1 to 30 parts by weight of a leveling agent based on 100 parts by weight of the multifunctional acrylate monomer. The present invention can lower the refractive index of the low refractive index layer by using the leveling agent, and can increase the compatibility with hollow particles and improve scratch resistance by including a polar functional group.

As the fluorine-based copolymer or copolymer mixed with fluorine-based and silicon-based, a commercial article satisfying the above conditions may be used. Examples of such commercial articles include F444, RS-907, RS-922, and RS-759 (manufacturer: DIC). Etc. can be mentioned.

On the other hand, the hard coating layer may be formed by using a hard coating solution composition containing 1 to 10 parts by weight of the photopolymerization initiator and 0.1 to 10 parts by weight of surfactant based on 100 parts by weight of the multifunctional acrylate monomer.

The polyfunctional acrylate monomer is a photocurable compound, it may be selected from the materials used in the above-described low reflection coating layer may be used one or more.

The type of the surfactant is not particularly limited, and any substance well known in the art may be used.

On the other hand, the composition for the hard coating layer and the low reflection coating layer according to the above-described embodiment may each further include a solvent. The solvent serves to adjust the viscosity of the composition to an appropriate range, and at the same time to control the smooth phase separation and distribution tendency of the hollow particles.

In order to fully express the above effects, the solvent may be one or more selected from the group consisting of alcohols, ketones, aromatic hydrocarbons, amides, esters and ethers. In addition, the present invention may use any solvent that meets the above properties. Examples of such a solvent may be preferably methanol, ethanol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, or acetone, but is not limited to the above examples. .

If the flowability of the composition is not good when the coating may cause defects such as streaks in the coating layer, in order to impart the minimum flowability required for the composition, the solvent may be included in a certain amount or more. For example, the solvent may be included in an amount of 300 to 2000 parts by weight based on 100 parts by weight of the polyfunctional acrylate monomer. In this case, when the solvent is added in an excessive amount, the solid content may be too low, so that defects may occur during drying and curing, and the distribution tendency of the hollow particles may deviate from a preferable range, and it is preferable to use within the above range.

Also in the present invention, the photopolymerization initiator used in the composition for the hard coating layer and the low reflection coating layer is 1-hydroxy cyclohexylphenyl ketone, benzyl dimethyl ketal, hydroxydimethyl acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether It may be at least one selected from the group consisting of, benzoin isopropyl ether, and benzoin butyl ether. The polymerization initiator is a compound that can be activated by energy rays such as ultraviolet rays to induce a polymerization reaction of the compound for forming a binder, and a compound conventional in the art can be used.

At this time, the content of the photopolymerization initiator is preferably used within each of the above-described ranges so that the polymerization reaction of the compound for forming a binder, which is a polyfunctional acrylate monomer, can be sufficiently made. When the photopolymerization initiator is added in an excessive amount in each composition, mechanical properties such as scratch resistance or abrasion resistance of each layer forming the antireflection film may be lowered, which is not appropriate. In addition, if the content is used in a small amount, the reaction does not occur smoothly, which causes uncuring and remains as an impurity, and the crosslinking density is lowered, which may lower the mechanical properties of the film. Can cause.

On the other hand, the antireflection film is not particularly limited in its production method, and is produced by a dry method or a wet method. Preferably, the antireflective film can be produced by a wet method. The dry method is a method of laminating a plurality of thin film layers by vapor deposition, sputtering, or the like. The wet method is a method of coating a composition including a binder, a solvent, and the like on a substrate, and drying and curing the wet method, which has a lower manufacturing cost than the dry method and is widely used commercially.

Therefore, the method for producing an antireflective film of the present invention may be prepared according to a wet coating method, and separately prepare a composition for hard coating and a coating composition for an antireflection layer (low reflection prevention layer).

Thereafter, the hard coating layer may be formed by coating, drying, and curing a separate layer by a coating method using a composition including a binder and inorganic fine particles on a transparent substrate. The low refractive index layer in which the hollow particles and the like are dispersed is formed by coating the composition for a low reflection coating layer described above on the hard coating layer, and drying and curing.

The transparent substrate may be one or more films selected from the group consisting of triacetyl cellulose (TAC) polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC) and norbornene-based polymer, but is not limited thereto. It is to be understood that all of the substrates well known in the art can be used.

In the above-described method for producing an antireflection film, the method of applying the composition on at least one side of the substrate may be performed using conventional coating apparatuses and methods well known in the art. For example, the present invention can be carried out using a wet coating method such as a roll coating method, a bar coating method, a spray coating method, a dip coating method, or a spin coating method.

In addition, the drying step is most preferred for 0.1 to 60 minutes at a temperature of 5 to 150 ℃, more preferably 0.1 to 20 minutes at a temperature of 20 to 120 ℃, in order to promote phase separation of the composition and erosion into the substrate It may be performed for 1 to 10 minutes at a temperature of 30 to 110 ℃.

In the curing step, energy may be added to the dried composition by irradiation with light or the like to initiate a polymerization reaction, through which the eroded and dried composition may be cured. This curing step is carried out for 1 to 600 seconds at an ultraviolet dose of 0.1 to 2 J / cm 2, more preferably for 2 to 200 seconds at an ultraviolet dose of 0.1 to 1.5 J / cm 2, most preferably at an ultraviolet dose of 0.2 to induce a sufficient curing reaction. To 1 J / cm 2 for 3 to 100 seconds.

On the other hand, according to another embodiment of the present invention, there is provided a polarizing plate in which at least one anti-reflection film is formed on the surface.

The polarizing plate of the present invention can be formed by laminating the aforementioned antireflection film on at least one surface of a polarizing plate including a general polarizer or the general polarizer. The anti-reflection film may be laminated in a form attached to the upper polarizer. The polarizing plate may be further provided with a conventional protective film as needed.

The general polarizer is a film uniaxially stretched by adsorbing a dichroic substance such as iodine or a dichroic dye to a hydrophilic polymer film such as a polyvinyl alcohol-based film, a dehydration product of polyvinyl alcohol, or a dehydrochlorination product of polyvinyl chloride. Polyene oriented films and the like can be used. The thickness of these polarizers is not particularly limited.

In addition, according to another embodiment of the present invention, an organic light emitting diode display including the polarizing plate is provided.

The polarizing plate may be included in a panel for an organic light emitting diode display. Therefore, the organic light emitting diode display of the present invention includes a metal electrode formed on the glass substrate; A quarter wave film formed on the metal electrode; The panel including the polarizing plate in which the antireflection film formed on the said quarter wave film is laminated | stacked 1 or more layers can be provided.

In addition, according to the present invention, a bi-wavelength film may be further formed between the quarter-wave film and the polarizing plate.

The quadrature film means a quarter wave retardation film (QWF, quarter phase plate, or lambda / 4 film), which represents a phase difference of π / 2 in two linearly polarized light beams having vibration planes perpendicular to each other. And converts linearly polarized light into circularly polarized light or vice versa.

The quarter wave film and the half wave film may be made of the same material or of different materials. For example, the quarter wave film and the half wave film can be made of nematic or smectic, preferably nematic liquid crystal material, polymerizable by in situ polymerization. As a preferred method of preparation, the polymerizable material can be coated on a substrate, oriented in a planar orientation and subsequently polymerized by exposure to heat or ultraviolet light. The quarter wave retardation film or the bi-wavelength film may also be provided in the form of a polymer film uniaxially stretched to exhibit anisotropic optical properties.

According to this configuration, the present invention has a minimum reflection wavelength of λ ₁ defined as a reflection wavelength in a polarizing plate by external light of 500 to 550 nm, and a maximum reflection of λ ₂ defined as a reflection wavelength in an antireflection film by external light. It is possible to provide an organic light emitting diode display having a wavelength of 400 to 650 nm.

In the present invention, the configuration of the panel for the OLED is not limited to the above structure, and may include a structure well known in the art except for providing the polarizing plate including the anti-reflection film of the present invention described above.

Hereinafter, with reference to the accompanying drawings, it will be described with respect to the OLED panel having a polarizing plate including an anti-reflection film according to an embodiment of the invention.

1 is a simplified cross-sectional view of an organic light emitting diode display panel according to an embodiment of the present invention. 2 is a simplified cross-sectional view of an organic light emitting diode display panel according to another embodiment of the present invention.

1 and 2, an OLED display panel comprising: a metal electrode formed on a glass substrate; A quarter wave film is adopted on the metal electrode, and an OLED display panel having a polarizing plate having an antireflection layer is provided in order to prevent reflection color caused by external light and improve visibility. In addition, the present invention includes a bi-wavelength film on the quarter-wave film.

For example, the present invention includes a metal electrode 1 formed on a glass substrate; A quarter wave film (2) formed on said metal electrode; The above-described antireflection film 4 formed on the quarter wave film provides a panel comprising a polarizing plate 3 formed on the surface (FIG. 1).

In addition, the present invention is a metal electrode (1) formed on a glass substrate; A quarter wave film (2) formed on said metal electrode; A bi-wavelength film (5) formed on said quarter wave film; The above-described antireflection film 4 formed on the bi-wavelength film 5 provides a panel comprising a polarizing plate 3 formed on the surface (FIG. 2).

According to this configuration, the present invention is provided with an anti-reflection film is formed on the surface of the polarizing plate, the anti-reflection film is formed, thereby eliminating the problems caused by the use of a quarter-wave film can provide an anti-glare function with the protection function of the display surface compared with the existing Visibility can be improved.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

≪ Example 1 >

(Hard Coating Liquid Composition Preparation)

A hard coating solution composition was prepared by mixing 60 g of pentaerythritol triacrylate, a polyfunctional acrylate monomer, 5 g of Irgacure 184 as a photoinitiator, 2 g of a surfactant, and 120 g of methyl ethyl ketone (MEK) with a solvent. The surfactant is commonly used in the industry, and DIC Co., Ltd. product (F477) was used.

(Antireflection layer (low reflection) coating liquid composition prepared)

15 g of pentaerythritol triacrylate, a polyfunctional acrylate monomer, 10 g of dipentaerythritol heptaacrylate, 5 g of Igacure 184 as a photopolymerization initiator, and methyl isobutyl ketone (MIBK) dispersion of hollow silica particles (catalytically manufactured company) A mixture consisting of 200 g and 5 g of a fluorinated copolymer (DIC, RS 907) as a leveling agent was diluted with a MIBK solvent to prepare a coating liquid having a solid content of 2.4 wt%.

(Reflective film (coating film) manufacture)

The hard coating composition was coated on a triacetyl cellulose film with # 10 mayer bar, dried at 90 ° C. for 2 minutes, and cured at 150 mJ / cm 2 UV energy and 8 m / min speed to prepare a hard coating film having a thickness of 5 μm. .

Subsequently, the low reflection coating composition was coated on the hard coating film with # 7 mayer bar, dried at 60 ° C. for 1 minute, and cured at 150 mJ / cm 2 UV energy and 5 m / min speed under nitrogen purging to obtain 100 nm. An antireflection film was prepared.

After forming a metal electrode on a transparent substrate by a conventional method, an OLED display panel was manufactured by laminating a quarter wave film and a polarizing plate. In addition, the above-described antireflection film was laminated on the polarizing plate to prepare a panel having the structure of FIG. 1.

<Example 2>

In the OLED panel, an antireflection film and an OLED panel were manufactured in the same manner as in Example 1 except that a bi-wavelength film was formed on the quadrant wavelength to have the structure of FIG. 2.

<Example 3>

20 g of UA-306I (Kyoeisha), a polyfunctional (meth) acrylate monomer, 40 g of pentaerythritol triacrylate, 5 g of Igacure 127 as a photoinitiator, 2 g of surfactant, and 120 g of methyl ethyl ketone (MEK) as a solvent Mixing to prepare a hard coating solution composition. The surfactant is commonly used in the industry, and DIC (F557) was used.

(Antireflection layer (low reflection) coating liquid composition prepared)

15 g of polyfunctional (meth) acrylate monomer PE3A-MS (Shin-Nakamura) and 20 g of UA-306T (Kyoeisha), 2.5 g of Igacure 184 as a photopolymerization initiator, methyl isobutyl ketone of hollow silica particles ( MIBK) A dispersion consisting of 200 g of a dispersion (catalytically manufactured company) and 5 g of a fluorinated copolymer (DIC, RS 759-4) as a leveling agent was diluted with a MIBK solvent to prepare a coating liquid having a solid concentration of 2.4 wt%.

(Reflective film (coating film) manufacture)

The hard coating composition was coated on a triacetyl cellulose film with # 10 mayer bar, dried at 90 ° C. for 2 minutes, and cured at 150 mJ / cm 2 UV energy and 8 m / min speed to prepare a hard coating film having a thickness of 5 μm. .

Subsequently, the low reflection coating composition was coated on the hard coating film with # 7 mayer bar, dried at 60 ° C. for 1 minute, and cured at 150 mJ / cm 2 UV energy and 5 m / min speed under nitrogen purging to obtain 100 nm. An antireflection film was prepared.

After forming a metal electrode on a transparent substrate by a conventional method, an OLED display panel was manufactured by laminating a quarter wave film and a polarizing plate. In addition, the above-described antireflection film was laminated on the polarizing plate to prepare a panel having the structure of FIG. 1.

<Example 4>

In the OLED panel, an antireflection film and an OLED panel were manufactured in the same manner as in Example 3, except that a bi-wavelength film was formed on the quarter wave to have the structure of FIG. 2.

&Lt; Comparative Example 1 &

(Hard Coating Liquid Composition Preparation)

A hard coating solution composition was prepared by mixing 60 g of pentaerythritol triacrylate, a polyfunctional acrylate monomer, 5 g of Irgacure 184 as a photoinitiator, 2 g of a surfactant, and 120 g of methyl ethyl ketone (MEK) with a solvent. The surfactant is commonly used in the industry, and DIC Co., Ltd. product (F477) was used.

(Antireflection layer (low reflection) coating liquid composition prepared)

15 g of tetramethylpropane triacrylate, a polyfunctional acrylate monomer, 5 g of Irgacure 184 as a photopolymerization initiator, 200 g of methyl isobutyl ketone (MIBK) dispersion (catalyzed chemical company) of hollow silica particles and a leveling agent A mixture consisting of 5 g of a fluorine copolymer (DIC, RS 907) was diluted with a MIBK solvent to prepare a coating solution having a solid concentration of 2.4 wt%.

(Reflective film (coating film) manufacture)

The hard coating composition was coated on a triacetyl cellulose film with # 10 mayer bar, dried at 90 ° C. for 2 minutes, and cured at 150 mJ / cm 2 UV energy and 8 m / min speed to prepare a hard coating film having a thickness of 5 μm. .

Thereafter, the low-reflective coating composition was coated with # 3 mayer bar on the hard coat film, dried at 60 ° C. for 1 minute, and then cured at 150 mJ / cm 2 UV energy and 5 m / min speed under nitrogen purging to obtain 100 nm. An antireflection film was prepared.

<Experimental Example>

The following items were evaluated for the antireflection films prepared through the Examples and Comparative Examples, and the results are shown in Table 1 below.

1) Reflectance measurement: After the back side of the antireflection film was blacked, the low reflection characteristic was evaluated at the minimum reflectance value. At this time, the measurement equipment is Shimadzu's Solid Spec. A 3700 spectrophotometer was used.

2) Transmittance and Haze Measurement: The transmittance and Haze were evaluated using HR-100 of Murakami, Japan.

3) Scratch resistance evaluation: After reciprocating 10 times of steel wool (loaded at 500 g / cm 2 to the antireflection film at a speed of 24 m / min), the number of wounds of 1 cm or more in length was examined on the surface. At this time, if there is no wound on the film surface, it is very good (◎), the number of wounds of 1 cm or more in length is 1 or more and less than 5 is excellent (○), 5 or more and less than 15 is normal (△), 15 or more It evaluated as bad (X).

4) Adhesion Evaluation: Adhesion to each film was evaluated through a cross cut test (ASTM D-3359) using a Nichiban tape.

Reflectance (%) Transmittance (%) Haze (%) Scratch resistance Adhesion Example 1 1.5 > 95 0.3 500g 5B Example 2 1.5 > 95 0.3 500g 5B Example 3 1.5 > 95 0.3 500g 5B Example 4 1.5 > 95 0.3 500g 5B Comparative Example 1 1.5 93 0.3 300g 5B

As can be seen through Table 1, the anti-reflection film according to Examples 1 to 4 was more excellent in scratch resistance and transmittance while satisfying the same physical properties as the conventional reflectivity and adhesion, compared to the film of Comparative Example 1. Therefore, when including the anti-reflection film of the present invention can improve the visibility and reduce the fatigue of the user.

1: substrate
2: quarter wave film (λ / 4 film)
3: polarizer
4: antireflection film
5: two-wavelength film (λ / 2 film)

Claims (15)

Transparent substrate;
A hard coating layer formed on the transparent substrate and including a crosslinked polymer of a 3 to 6 functional polyfunctional acrylate monomer and having a refractive index of 1.20 to 1.55; And
It is formed on the hard coating layer, and includes a low reflection coating layer having a lower refractive index than the hard coating layer and the refractive index difference is Δn> 0.05,
The low reflection coating layer is an antireflection film comprising a crosslinked polymer of a 3 to 6 functional multifunctional acrylate monomer, and hollow particles.
The method of claim 1,
The low reflection coating layer has an average reflectance of 2% or less and a thickness of 20 to 350 nm.
The method of claim 1, wherein the low reflection coating layer
The antireflection film formed using the composition containing 1-10 weight part of photoinitiators, and 10-360 weight part of hollow particles with respect to 100 weight part of polyfunctional acrylate monomers.
The method of claim 1, wherein the multifunctional acrylate monomer is pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, trimethylene propane triacrylate, dipentaerythritol heptaacrylate, dipentaerythritol Hydroxy pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylene propyl triacrylate, propoxylated glycerol triacrylate, 1,6-hexanedioldiacrylate, propoxylated glycerol At least one antireflection film selected from the group of polyfunctional acrylate monomers consisting of triacrylate, tripropylene glycol diacrylate, and ethylene glycol diacrylate.
The antireflection film according to claim 1, wherein the hollow particles are hollow silica particles having a number average particle diameter of 5 to 80 nm.
The method of claim 1, wherein the hard coating layer
An antireflection film formed by using a hard coating liquid composition containing 1 to 10 parts by weight of a photopolymerization initiator and 0.1 to 10 parts by weight of a surfactant based on 100 parts by weight of the polyfunctional acrylate monomer.
The method according to claim 3 or 6,
The photopolymerization initiator is a group consisting of 1-hydroxy cyclohexylphenyl ketone, benzyl dimethyl ketal, hydroxydimethyl acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin butyl ether At least one antireflection film selected from.
The method according to claim 3 or 6,
The composition is an anti-reflection film further comprises one or more solvents selected from the group consisting of alcohols, ketones, aromatic hydrocarbons, amides, esters and ethers.
The method of claim 3, wherein the composition
100 parts by weight of a polyfunctional acrylate monomer
An antireflection film further comprising 1 to 3 parts by weight of the leveling agent.
The method of claim 1, wherein the transparent substrate
Triacetyl cellulose (TAC) Antireflection film comprising at least one film selected from the group consisting of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC) and norbornene-based polymers.
The polarizing plate in which the antireflection film of Claim 1 is formed in one or more layers on the surface.
An organic light emitting diode display comprising the polarizing plate according to claim 11.
The method of claim 12,
A metal electrode formed on the glass substrate;
A quarter wave film formed on the metal electrode;
An organic light emitting diode display comprising a panel comprising the polarizing plate of claim 13 formed on said quarter wave film.
The organic light emitting diode display according to claim 13, wherein a bi-wavelength film is further formed between the quarter-wave film and the polarizing plate.
14. The method of claim 13,
The minimum reflection wavelength of λ ₁ defined as the reflection wavelength in the polarizing plate by external light is 500 to 550 nm, and the maximum reflection wavelength of λ ₂ defined as the reflection wavelength in the antireflection film by external light is 400 to 650 nm. Organic light emitting diode display.

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