KR102171280B1 - Manufacturing method of optical member comprising multi layered low-reflection coating layer and optical member menufactured by the same - Google Patents

Abstract

The present specification provides a method of manufacturing an optical member including a multilayer type low-reflection coating layer and an optical member manufactured using the same.

Description

TECHNICAL FIELD The manufacturing method of an optical member including a multi-layered low-reflection coating layer, and an optical member manufactured using the same BACKGROUND OF THE INVENTION 1.

The present specification relates to a method of manufacturing an optical member including a multi-layered low-reflection coating layer and an optical member manufactured using the same.

In recent years, the display market is growing rapidly, not only for TVs, monitors, and laptop panels, which are traditional consumers, but also for mobile devices represented by smartphones and dashboards for automobiles. Among the ever-evolving display technologies, the reflectivity of the surface is a specification that has a great influence on customer satisfaction. In the case of a film introduced at the outermost part of a display, it has a reflectance of about 4% due to Fresnel reflection in general, and such a high reflectance adversely affects the visibility of the display in an environment exposed to daylight and illumination light. In order to solve this problem, coatings such as AG (anti-glare) or AR (anti-reflection) have been introduced, but since the AG coating disperses not only the reflected light but also the light emitted from the display, there is a problem of poor visibility. Since it is manufactured by a vapor deposition process, it is difficult to increase in size and has a high cost.

Accordingly, it is necessary to develop a coating layer that has a low reflectivity and can be produced at a low price.

Korean publication: KR 10-2011-0112222 A

The present specification provides a method of manufacturing an optical member including a multilayer type low reflection multilayer type low reflection coating layer, and an optical member manufactured using the same.

However, the problem to be solved by the present invention is not limited to the above-mentioned problems, and other problems that are not mentioned will be clearly understood by those skilled in the art from the following description.

An exemplary embodiment of the present invention, by adding an acidic catalyst to a dispersion containing a first solvent and an alkoxy silane, forming a sol-gel solution for a low refractive index layer; Forming a sol-gel solution for a high refractive layer by adding an acidic catalyst to a dispersion containing a second solvent and a metal alkoxide; Forming a multi-layered sol-gel layer by alternately applying and drying the sol-gel solution for the low refractive layer and the sol-gel solution for the high refractive layer on a substrate; And contacting the multi-layered sol-gel layer with a base catalyst to form a multi-layered low-reflective coating layer in which low and high refractive layers are alternately provided.

All of the above processes are performed in an atmosphere of 120° C. or less to provide a method of manufacturing an optical member including a multilayered low-reflective coating layer.

An exemplary embodiment of the present invention provides an optical member including a multilayered low-reflective coating layer manufactured by the above manufacturing method.

The manufacturing method according to an exemplary embodiment of the present invention is a simple and inexpensive method to manufacture an optical member including a multilayered low-reflection coating layer having excellent performance.

The manufacturing method according to an exemplary embodiment of the present invention has an advantage that a high temperature heat treatment process is not required by using only a simple chemical treatment.

Since the manufacturing method according to an exemplary embodiment of the present invention is performed at a low temperature, there is an advantage in that an optical member having a multilayered low-reflection coating layer formed directly on a polymer substrate can be manufactured.

Since the manufacturing method according to an exemplary embodiment of the present invention is performed through a coating process, there is an advantage that mass production is possible using a continuous roll-to-roll process. In addition, since the manufacturing method according to an exemplary embodiment of the present invention does not use a high-temperature firing process and all processes are performed in an atmosphere of 120° C. or less, it can be performed in a continuous roll-to-roll process by applying a flexible polymer substrate.

Throughout the present specification, when a member is said to be positioned “on” another member, this includes not only the case where a member is in contact with the other member, but also the case where another member exists between the two members.

Throughout the specification of the present application, when a certain part "includes" a certain component, it means that other components may be further included rather than excluding other components unless specifically stated to the contrary.

Throughout this specification, the description of “A and/or B” means “A or B, or A and B”.

As used throughout the specification of the present application, the term "step (to)" or "step of" does not mean "step for".

In the present specification, the unit "parts by weight" may mean a ratio of weight between each component.

In the case of a low-reflective layer in which a conventional low-refractive-index layer and a high-refractive layer are alternately provided, a low-refractive material such as MgF ₂ , Na ₃ AlF ₆ is deposited using a deposition process to form a low-refractive-index layer, and ZrO ₂ , TiO ₂ A high refractive layer was formed by depositing a high refractive material, such as, to form a multilayer low refractive coating layer. However, when the deposition process is used as described above, it is difficult to mass-produce and increase the area, and there is a problem that very high process costs are involved. In addition, when the liquid composition is used to form the low reflection layer, there is a problem in that the low reflection layer cannot be directly formed on a polymer film having a low glass transition temperature by firing at a high temperature of 300°C or higher, and a high manufacturing cost is involved.

Recognizing such a problem, the present inventors have developed a method of manufacturing an optical member including the following multi-layered low-reflection coating layer, which does not undergo a high-temperature firing process and can be produced in large area and mass at low process cost.

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

An exemplary embodiment of the present invention, by adding an acidic catalyst to a dispersion containing a first solvent and an alkoxy silane, forming a sol-gel solution for a low refractive index layer; Forming a sol-gel solution for a high refractive layer by adding an acidic catalyst to a dispersion containing a second solvent and a metal alkoxide; Forming a multi-layered sol-gel layer by alternately applying and drying the sol-gel solution for the low refractive layer and the sol-gel solution for the high refractive layer on a substrate; And contacting the multi-layered sol-gel layer with a base catalyst to form a multi-layered low-reflective coating layer in which low and high refractive layers are alternately provided.

All of the above processes are performed in an atmosphere of 120° C. or less to provide a method of manufacturing an optical member including a multilayered low-reflective coating layer.

For low refractive layer Forming a sol-gel solution

According to an exemplary embodiment of the present invention, the method of manufacturing an optical member including the multi-layered low-reflection coating layer is a sol-gel solution for a low refractive layer by adding an acidic catalyst to a silica precursor dispersion containing a first solvent and an alkoxy silane. And forming.

According to an exemplary embodiment of the present invention, the alkoxy group of the alkoxy silane may be an alkoxy group having 1 to 10 carbon atoms or less. Specifically, according to an exemplary embodiment of the present invention, the alkoxy silane is tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), methoxytriethoxysilane (MTEOS), methyltrimethoxysilane (MTMS). , Methyltriethoxysilane (MTES), trimethoxyphenylsilane (TMPS), triethoxyphenylsilane (TEPS), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxy Propyltrimethoxysilane, vinyltrimethoxysilane, 3-(acryloyloxy)propyltrimethoxysilane, 1,2-bis(triethoxysilane)ethane, and 3-methacryloxypropyltrimethoxysilane It may include at least one of. More specifically, according to an exemplary embodiment of the present invention, the alkoxy silane may be tetraethoxysilane (TEOS).

According to an exemplary embodiment of the present invention, the first solvent may include an organic solvent. Specifically, according to an exemplary embodiment of the present invention, the organic solvent may include an organic solvent having a boiling point of 50 ℃ to 150 ℃. Specifically, according to an exemplary embodiment of the present invention, the first solvent may include water and an organic solvent.

According to an exemplary embodiment of the present invention, the first solvent is an alcohol-based solvent; Ketone solvents; And it may include an organic solvent including at least one of the acetate-based solvent.

According to an exemplary embodiment of the present invention, the alcohol-based solvent may include at least one of ethyl alcohol, n-propyl alcohol, i-propyl alcohol, i-butyl alcohol, n-butyl alcohol and t-butyl alcohol.

According to an exemplary embodiment of the present invention, the ketone-based solvent may include at least one of acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl ketone, methyl isopropyl ketone, and acetylacetone.

According to an exemplary embodiment of the present invention, the acetate-based solvent may include at least one of methyl acetate, ethyl acetate, propyl acetate, and butyl acetate.

The organic solvent may improve the stability of the silica precursor sol. Further, the content of the first solvent may be included in the silica precursor dispersion in a mole number of 2 to 8 times the mole number of the alkoxysilane.

According to an exemplary embodiment of the present invention, the first solvent may be a mixed solvent of water and an organic solvent. Specifically, the solvent may be a mixed solvent of water and an alcohol-based solvent.

According to an exemplary embodiment of the present invention, the first solvent may be a mixed solvent of water and an alcohol-based solvent.

According to an exemplary embodiment of the present invention, the silica precursor dispersion may further include nanoparticles including at least one of silica, ceria, titania, and zirconia as necessary.

According to an exemplary embodiment of the present invention, the silica precursor dispersion may further include a fluorine-based slip agent and/or a silicon-based slip agent, if necessary.

According to an exemplary embodiment of the present invention, the silica precursor dispersion may further include a drying retarder if necessary.

According to an exemplary embodiment of the present invention, an acidic catalyst may be added to the silica precursor dispersion to form a sol-gel solution for a low refractive index layer.

Specifically, the acidic catalyst may sol-gelize the silica precursor dispersion by adjusting the pH of the silica precursor dispersion to 0 to 5.

According to an exemplary embodiment of the present invention, the acidic catalyst may include at least one of hydrochloric acid, sulfuric acid, fluorosulfuric acid, nitric acid, phosphoric acid, acetic acid, hexafluorophosphoric acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.

Specifically, the acidic catalyst may sol-gelize silica precursors including alkoxy silanes contained in the silica precursor dispersion by adjusting the pH of the silica precursor dispersion.

According to an exemplary embodiment of the present invention, the acidic catalyst may hydrolyze the silica precursor to form a silica precursor sol represented by the following general formula 1.

[General Formula 1]

In the general formula 1, n is a plurality of integers, and the value of n may change depending on the time, temperature, humidity, etc. after the silica precursor sol is made, so the value of n may change. For example, the n value of General Formula 1 may be an integer of 2 to 10 million or less.

According to an exemplary embodiment of the present invention, the step of forming the sol-gel solution for the low refractive index layer may be performed at a temperature of 80 °C or less. Specifically, the step of forming the sol-gel solution for the low refractive layer may be performed at a temperature of room temperature (25°C) to 80°C or less.

According to an exemplary embodiment of the present invention, the sol-gel content of the sol-gel solution for the low refractive layer may be 5 wt% or more and 40 wt% or less. Specifically, the sol-gel content of the sol-gel solution for the low refractive layer may be 8 wt% or more and 20 wt% or less, or 10 wt% or more and 15 wt% or less.

In the present specification, the content of the sol-gel in the sol-gel solution for the low refractive layer is the residual after drying the sol-gel solution for the low refractive layer at 80° C. for 1 hour and then performing a dehydration reaction at 200° C. for 24 hours. The content of the sol-gel in the sol-gel solution for the low refractive layer can be measured through the solid content, and the silica precursor contained in the sol-gel solution for the low refractive layer is 100% reacted to calculate the sol-gelation amount. The content of the sol-gel in the solution can be calculated.

When the sol-gel content in the sol-gel solution for the low refractive layer is within the above range, the viscosity of the sol-gel solution for the low refractive layer is appropriately adjusted to facilitate handling during coating. Furthermore, when the sol-gel content in the sol-gel solution for the low refractive layer is within the above range, the drying time after application of the sol-gel solution for the low refractive layer is shortened to prevent stains that may occur in the low refractive layer. In addition, the thickness of the low refractive layer may be uniformly implemented.

For high refractive layer Forming a sol-gel solution

According to an exemplary embodiment of the present invention, the method of manufacturing an optical member including the multi-layered low-reflection coating layer is a sol-gel solution for a high refractive layer by adding an acidic catalyst to a dispersion of a metal oxide precursor containing a second solvent and a metal alkoxide. And forming.

According to an exemplary embodiment of the present invention, the metal alkoxide is aluminum isopropoxide, aluminum sec-butoxide, cerium isopropoxide, hafnium tert-butoxide, magnesium aluminum isopropoxide, yttrium isopropoxide, It may include at least one of titanium isopropoxide, rubidium isopropoxide, zirconium n-propoxide, and zirconium isopropoxide. Specifically, the metal alkoxide may include zirconium isopropoxide and/or titanium isopropoxide.

According to an exemplary embodiment of the present invention, the second solvent may be the same as the example of the first solvent described above.

According to an exemplary embodiment of the present invention, the second solvent may be a mixed solvent including an alcohol-based solvent and a ketone-based solvent. Specifically, the second solvent may be a mixed solvent including ethanol and acetylacetone.

The content of the second solvent may be included in the metal oxide precursor dispersion in a mole number of 2 to 8 times the mole number of the metal alkoxide.

According to an exemplary embodiment of the present invention, the metal oxide precursor dispersion may further include nanoparticles including at least one of silica, ceria, titania, and zirconia as necessary.

According to an exemplary embodiment of the present invention, the metal oxide precursor dispersion may further include a drying retarder if necessary.

According to an exemplary embodiment of the present invention, an acidic catalyst may be added to the dispersion of the metal oxide precursor to form a sol-gel solution for a high refractive layer.

Specifically, the acidic catalyst may sol-gelize the metal oxide precursor dispersion by adjusting the pH of the metal oxide precursor dispersion to 0 to 5.

According to an exemplary embodiment of the present invention, the acidic catalyst may include at least one of hydrochloric acid, sulfuric acid, fluorosulfuric acid, nitric acid, phosphoric acid, acetic acid, hexafluorophosphoric acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.

Specifically, the acidic catalyst may sol-gelize metal oxide precursors including metal alkoxides contained in the metal oxide precursor dispersion by adjusting the pH of the metal oxide precursor dispersion.

According to an exemplary embodiment of the present invention, the step of forming the sol-gel solution for the high refractive layer may be performed at a temperature of 80 °C or less. Specifically, the step of forming the sol-gel solution for the high refractive layer may be performed at a temperature of room temperature (25°C) to 80°C or less.

According to an exemplary embodiment of the present invention, the sol-gel content of the sol-gel solution for the high refractive layer may be 5 wt% or more and 40 wt% or less. Specifically, the sol-gel content of the sol-gel solution for the high refractive layer may be 8 wt% or more and 20 wt% or less, or 10 wt% or more and 15 wt% or less.

In the present specification, the sol-gel content of the sol-gel solution for a high refractive layer is determined by drying the sol-gel solution for a high refractive layer at 80° C. for 1 hour and then performing a dehydration reaction at 200° C. for 24 hours. The content of the sol-gel in the sol-gel solution for the high refractive layer can be measured, and the amount of sol-gelation by 100% reaction of the metal oxide precursor contained in the sol-gel solution for the high refractive layer is calculated. -You can calculate the gel content.

When the sol-gel content in the sol-gel solution for the high refractive layer is within the above range, the viscosity of the sol-gel solution for the high refractive layer is appropriately adjusted to facilitate handling during coating. Further, when the sol-gel content in the sol-gel solution for the high refractive layer is within the above range, the drying time after application of the sol-gel solution for the high refractive layer is shortened to prevent stains that may occur in the high refractive layer, and the The thickness of the high refractive layer can be uniformly implemented.

Forming a multi-layered sol-gel layer

According to an exemplary embodiment of the present invention, the method of manufacturing an optical member including the multilayered low-reflection coating layer is by alternately applying and drying the sol-gel solution for the low refractive layer and the sol-gel solution for the high refractive layer on a substrate. And forming a multi-layered sol-gel layer.

According to an exemplary embodiment of the present invention, the step of forming the multilayer sol-gel layer includes applying the sol-gel solution for the low refractive layer on a substrate, drying, and then applying the sol-gel solution for the high refractive layer. It may be to perform the drying method repeatedly.

Through this, the substrate/high refractive sol-gel layer/low refractive sol-gel layer, the substrate/low refractive sol-gel layer/high refractive sol-gel layer/low refractive sol-gel layer, or the substrate/high refractive sol-gel layer/low It is possible to form a multi-layered sol-gel layer having the same structure as the refractive sol-gel layer/high refractive sol-gel layer/low refractive sol-gel layer.

The multi-layered sol-gel layer may include two or more and ten or less low-refractive sol-gel layers and high-refractive sol-gel layers.

According to an exemplary embodiment of the present invention, the outermost layer of the multi-layered low-reflection coating layer may be provided with a low refractive index layer. Through this, the multi-layered low-reflection coating layer can implement a lower reflectance.

According to an exemplary embodiment of the present invention, the sol-gel solution for the low refractive layer and the sol-gel solution for the high refractive layer may be applied without limitation by coating methods generally known in the art such as bar coating and spin coating.

According to an exemplary embodiment of the present invention, the substrate may be an optical film provided with the multilayered low-reflective coating layer. Specifically, the substrate may be a polarizing film, a brightness enhancing film, or a retardation film. In addition, the substrate may be a display panel or a touch panel.

According to an exemplary embodiment of the present invention, the substrate may be an optical film having at least one functional layer of a high refractive index layer, a hard coating layer, and an antireflection layer on one surface. Specifically, the low refractive silica coating layer may be formed on the functional layer of the substrate.

Since the method of manufacturing an optical member including a multi-layered low-reflection coating layer according to the present invention does not undergo a high-temperature firing process, the substrate may be an optical film rather than a liner separated from the coating layer after forming the coating layer. , It may be a display polymer substrate such as a polarizing plate.

Further, according to an exemplary embodiment of the present invention, the substrate may be a polymer substrate. Specifically, the polymer substrate may include films such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene ether ketone (PEEK), and polyimide (PI) in the form of a single layer or a multilayer. However, it is not limited thereto, and any film made of a polymer material may be applied without limitation.

According to an exemplary embodiment of the present invention, the coating thickness of the sol-gel solution for the low refractive layer and the sol-gel solution for the high refractive layer can be adjusted according to the use of the multilayered low reflection coating layer, for example, from 50 nm to It can be applied to a thickness of 1 μm.

According to an exemplary embodiment of the present invention, drying the sol-gel solution for the low refractive layer and the sol-gel solution for the high refractive layer is to remove the first solvent and the second solvent by drying at a temperature of 120° C. or less, respectively. I can.

According to an exemplary embodiment of the present invention, drying the sol-gel solution for the low refractive layer may be drying at a temperature of 120° C. or lower to remove the first solvent to form a low refractive sol-gel layer.

Through the process of drying the sol-gel solution for the low refractive layer, the low refractive sol-gel layer may be evenly distributed on the substrate or the high refractive sol-gel layer.

According to an exemplary embodiment of the present invention, drying the sol-gel solution for a high refractive layer may be drying at a temperature of 120° C. or lower to remove the second solvent to form a high refractive sol-gel layer.

Through the process of drying the sol-gel solution for the high refractive layer, the high refractive sol-gel layer may be evenly distributed on the substrate or the low refractive sol-gel layer.

That is, through the process of drying the sol-gel solution for the low refractive layer and the sol-gel solution for the high refractive layer, a multi-layered sol-gel layer in which low refractive sol-gel layers and high refractive sol-gel layers are alternately formed is formed. Can be.

In addition, since the first solvent and/or the second solvent may be evaporated at a low temperature, the first solvent and/or the second solvent may be dried at a temperature of 120° C. or less, 100° C. or less, or 80° C. or less. Can be removed.

According to an exemplary embodiment of the present invention, the drying may be performed at a temperature of 50°C or more and 120°C or less, 60°C or more and 100°C or less, or 60°C or more and 80°C or less.

According to an exemplary embodiment of the present invention, the drying may be performed for 30 seconds to 5 minutes at a temperature of 50° C. or more and 120° C. or less, 60° C. or more and 100° C. or less, or 60° C. or more and 80° C. or less. Specifically, the drying may be performed for 30 seconds to 2 minutes at a temperature of 60 ℃ to 80 ℃.

The drying may include removing all of the solvent in the low refractive sol-gel layer and/or the high refractive sol-gel layer, as well as removing some of the solvent.

According to an exemplary embodiment of the present invention, after drying the sol-gel solution for the low-refractive-index layer to form a low-refractive sol-gel layer, the step of surface modification using plasma treatment may be further included.

In addition, according to an exemplary embodiment of the present invention, after drying the sol-gel solution for the high refractive layer to form a high refractive sol-gel layer, a step of surface modification using plasma treatment may be further included.

The plasma treatment may be performed by a direct method or an indirect method using atmospheric pressure plasma.

The step of surface modification may improve the side-to-side adhesion of the low-refractive sol-gel layer and/or the high-refractive sol-gel layer, and at least one of an amine base catalyst and a phosphoric acid base catalyst in a subsequent process It is possible to form a multi-layered low-reflection coating layer having a higher strength by increasing the contact with the base catalyst containing.

Multi-layered Low reflection Step of forming a coating layer

According to an exemplary embodiment of the present invention, the multi-layered sol-gel layer is brought into contact with a base catalyst to form a multi-layered low-reflection coating layer having alternately low and high refractive layers.

According to an exemplary embodiment of the present invention, the base catalyst may serve to cure the sol-gel of the multilayer sol-gel layer on the substrate.

According to an exemplary embodiment of the present invention, the low refractive index layer may include a silica-based matrix. Specifically, the base catalyst including at least one of the amine base catalyst and the phosphoric acid base catalyst may cure the silica precursor sol represented by Formula 1 of the low refractive coating layer with a silica film. Through this, the low refractive index coating layer may be cured into a low refractive index layer made of a silica matrix.

According to an exemplary embodiment of the present invention, the high refractive layer may include a metal oxide-based matrix. Specifically, the base catalyst including at least one of the amine base catalyst and the phosphoric acid base catalyst may cure the metal alkoxide sol of the high refractive coating layer into a metal oxide-based matrix consisting of metal and oxygen.

According to an exemplary embodiment of the present invention, the light refractive index of the low refractive layer may be 1.40 to 1.47, 1.42 to 1.46, or 1.44 to 1.45 at a wavelength of 550 nm.

According to an exemplary embodiment of the present invention, the photorefractive index of the high refractive layer may be 2.0 to 2.8, 2.3 to 2.7, or 2.5 to 2.7 at a wavelength of 550 nm.

According to an exemplary embodiment of the present invention, the base catalyst may have a boiling point of 80° C. or more and 500° C. or less.

In addition, according to an exemplary embodiment of the present invention, the base catalyst may have a vapor pressure of 10,000 Pa or less, 5,000 Pa or less, or 1 Pa or less at room temperature (25° C.).

According to an exemplary embodiment of the present invention, the base catalyst may be an anhydride having a boiling point of 80° C. or higher. Specifically, since the base catalyst does not contain moisture, it is possible to form a dense crosslinked structure by effectively dehydrating the low refractive coating layer and the high refractive coating layer.

For example, in the case of a low refractive coating layer, a reaction in which the silica precursor sol represented by the general formula 1 is cured into silica by the base catalyst involves a reaction in which water is removed, and when water is present during curing, the reaction There is a problem that the speed is significantly reduced. In order to prevent this, in the step of forming a silica coating layer on the substrate, curing of the silica precursor sol may be rapidly performed using the base catalyst that does not contain moisture. Likewise, the high refractive coating layer may also have a dense crosslinked structure by the base catalyst. Specifically, the base catalyst may be a liquid anhydride having a boiling point of 80° C. or higher.

Furthermore, through the process of bringing the multi-layered sol-gel layer into contact with the base catalyst, a low refractive layer and a high refractive layer can be simultaneously formed.

According to an exemplary embodiment of the present invention, the base catalyst has a high boiling point and a high flash point, is thermally stable, and has a remarkably low risk of fire during processing. Furthermore, the base catalyst has the advantage of low vapor pressure, low odor and very low risk of explosion.

According to an exemplary embodiment of the present invention, the base catalyst may be liquid at a temperature of 120° C. or less.

According to an exemplary embodiment of the present invention, the base catalyst may include an organic solvent. When the base catalyst is solid at a temperature of 120° C. or less, it may be dissolved in an organic solvent and used. Through this, the base catalyst may be liquid at a temperature of 120° C. or less.

Organic solvents that may be included in the base catalyst are N,N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), 1,3-dimethyl-2- Imidazolidinone, N,N-diethylacetamide (DEAc), N,N-dimethylmethoxyacetamide, dimethylsulfoxide, pyridine, dimethylsulfone, hexamethylphosphoamide, tetramethylurea, N-methylcapro Lactam, tetrahydrofuran, m-dioxane, P-dioxane, 1,2-dimethoxyethane, bis(2-methoxyethyl) ether, 1,2-bis(2-methoxyethoxy)ethane, bis Among [2-(2-methoxyethoxy)] ether, poly(ethylene glycol) methacrylate (PEGMA), gamma-butyrolactone (GBL), and ekamide (Equamide M100, Idemitsu Kosan Co., Ltd) It may include at least one.

The step of forming the multi-layered low-reflection coating layer is to cure the multi-layered sol-gel layer using the base catalyst, and has the advantage that the process can be conveniently performed using a chemical method without going through a high-temperature sintering process. have. In addition, the base catalyst may prevent physical properties from deteriorating due to contact with water during curing of the multilayer sol-gel layer. Further, since the base catalyst has a high boiling point and a low vapor pressure, it can help to improve the working environment by greatly reducing the risk of fire due to exposure to toxic gases or volatility during work.

According to an exemplary embodiment of the present invention, the step of forming the multi-layered low-reflective coating layer may be using an immersion method, a coating method, or a spray method.

Specifically, according to an exemplary embodiment of the present invention, in contacting the multilayer sol-gel layer provided on the substrate with the base catalyst, a method of depositing a liquid material such as spin coating, dip coating, or spray coating may be used. have.

Specifically, according to an exemplary embodiment of the present invention, contacting the multi-layered sol-gel layer provided on the base material with the base catalyst includes the base material having the multi-layered sol-gel layer provided on one surface thereof. It may be immersed in a base catalyst.

When the multi-layered sol-gel layer and the base catalyst are contacted using the immersion method, the process can be performed very simply, and production equipment can be minimized.

According to an exemplary embodiment of the present invention, the base catalyst may include at least one of an amine base catalyst, a phosphoric acid base catalyst, and an imidazole base catalyst.

According to an exemplary embodiment of the present invention, the step of forming the multi-layered low-reflective coating layer may use an amine-based base catalyst. Specifically, according to an exemplary embodiment of the present invention, the step of forming the multi-layered low-reflective coating layer may use trioctylamine (TOA) as an amine-based base catalyst.

According to an exemplary embodiment of the present invention, the base catalyst may include at least one of the compounds represented by the following Chemical Formulas 1 to 10.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In Formulas 1 to 10,

R1 to R32 are each independently hydrogen; Or a C1-C40 linear or branched alkyl group; Or an aryl group having 6 to 50 carbon atoms; and,

n and x are any one integer from 1 to 3, o to q are any one of 1 to 4, m and r to w are any one of 1 to 5,

When n is 2 or more, R6 may be the same or different, when m is 2 or more, R7 may be the same or different, and when o is 2 or more, R16 may be the same or different, and when p is 2 or more, R17 is the same. Or they may be different, and when q is 2 or more, R18 may be the same or different, when r is 2 or more, R19 may be the same or different, and when s is 2 or more, R20 may be the same or different, and t is If 2 or more, R21 may be the same or different, if u is 2 or more, R22 may be the same or different, if v is 2 or more, R23 may be the same or different, and if w is 2 or more, R25 may be the same or different. May be, and when x is 2 or more, R32 may be the same or different.

In the present specification, the alkyl group may be substituted or unsubstituted, may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present specification, "substitution" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited as long as the position where the hydrogen atom is substituted, that is, the position where the substituent can be substituted, and two or more substitutions If so, two or more substituents may be the same or different from each other.

In the present specification, "substituted or unsubstituted" is deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amino group; Alkyl group; Cycloalkyl group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Alkenyl group; Silyl group; Boron group; Phosphine oxide group; Amine group; Arylamine group; Aryl group; And a heteroaryl group containing at least one of N, O, S, Se and Si atoms is substituted with one or two or more substituents selected from the group consisting of, or two or more of the substituents exemplified above are substituted with a connected substituent, or It means not having a substituent.

In the present specification, the aryl group may be substituted or unsubstituted, and when the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but it is preferably 6 to 50 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, or a quarterphenyl group, but is not limited thereto. When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferably 10 to 40 carbon atoms. Specifically, the polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

Specifically, according to an exemplary embodiment of the present invention, the base catalyst may include at least one of the compounds represented by the following Formulas 1-1 to 10-3.

[Formula 1-1]

[Formula 2-1]

[Formula 3-1]

[Formula 4-1]

[Chemical Formula 5-1]

[Formula 6-1]

[Chemical Formula 7-1]

[Chemical Formula 8-1]

[Chemical Formula 9-1]

[Formula 10-1]

[Formula 10-2]

[Formula 10-3]

According to an exemplary embodiment of the present invention, the step of forming the multi-layered low-reflection coating layer may be to contact the multi-layered sol-gel layer provided on the substrate with the base catalyst at a temperature of 60°C to 120°C. have. Specifically, the step of forming the multi-layered low-reflective coating layer may be performed at a temperature of 60°C to 100°C, or 70°C to 90°C. Specifically, in the step of forming the multi-layered low-reflection coating layer, the base material having a multi-layered sol-gel layer on one side is 60°C to 120°C, 60°C to 100°C, 70°C to 90°C, or 70°C. It may be to be immersed in the base catalyst adjusted to 80 ℃.

According to an exemplary embodiment of the present invention, the step of forming the multilayered low-reflection coating layer may be performed for 1 minute to 20 minutes, or 3 minutes to 10 minutes. Specifically, the step of forming the multi-layered low-reflection coating layer may be performed for 3 to 7 minutes at a temperature of 70 to 90°C.

According to an exemplary embodiment of the present invention, the thickness of the low refractive layer and the thickness of the high refractive layer may be 50 nm or more and 200 nm or less, respectively. Specifically, the thickness of the low refractive silica coating layer may be 50 nm or more and 120 nm or less.

Since the method of manufacturing an optical member including a multi-layered low-reflection coating layer according to an exemplary embodiment of the present invention is performed at a low temperature of 120° C. or less, there is an advantage in that a multi-layered low-reflection coating layer can be formed directly on a polymer substrate. . Specifically, in the method of manufacturing an optical member including a multilayered low-reflection coating layer according to an exemplary embodiment of the present invention, since the entire process is performed at a temperature of 120°C or less, 100°C or less, or 80°C or less, heat of the polymer substrate There is an advantage of preventing deformation, and using this, it is possible to form a multilayered low-reflection coating layer directly on the polymer substrate.

Furthermore, the multi-layered low-reflection coating layer manufactured by the method of manufacturing an optical member including the multi-layered low-reflection coating layer is equal to or higher than the low-reflection coating layer that undergoes a high-temperature sintering process of 500° C. Stiffness can be achieved.

According to an exemplary embodiment of the present invention, the optical member including the multi-layered low-reflection coating layer may be manufactured by a continuous roll-to-roll process.

Since the manufacturing method according to an exemplary embodiment of the present invention is performed by a solution process rather than a deposition process, there is an advantage that is very suitable for mass production through a continuous roll-to-roll process. Furthermore, since the manufacturing method according to an exemplary embodiment of the present invention does not require a high-temperature firing process, a flexible polymer substrate having low heat resistance can be applied. Therefore, the manufacturing method according to an exemplary embodiment of the present invention can directly form a multilayered low-reflection coating layer on a flexible polymer substrate by using a roll-to-roll continuous process.

An exemplary embodiment of the present invention provides an optical member including a multilayered low-reflective coating layer manufactured by the above manufacturing method. Specifically, an exemplary embodiment of the present invention provides an optical member provided with a multilayered low-reflective coating layer manufactured by the above manufacturing method on one surface of a substrate.

Specifically, since the multi-layered low-reflection coating layer has excellent surface strength and low light reflectance, it can be applied as a low-reflection coating layer of a display device.

According to an exemplary embodiment of the present invention, the substrate may be a polarizing film, a brightness enhancing film, or a retardation film. Specifically, the optical member may be a polarizing plate provided with the multi-layered low-reflective coating layer.

An exemplary embodiment of the present invention provides a display device including the optical member.

Hereinafter, examples will be described in detail to illustrate the present invention in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention is not construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely describe the present invention to those of ordinary skill in the art.

[ Example One]

For low refractive layer Preparation of sol-gel solution

TEOS was mixed with ethanol to prepare a silica precursor dispersion. The prepared silica precursor dispersion was stirred, and an aqueous hydrochloric acid solution was added dropwise to prepare a sol-gel solution for a low refractive layer. The molar ratio of TEOS, ethanol, water and hydrochloric acid at the time of preparing the sol-gel solution for the low refractive layer was 1:4:4:0.2. The solid content of the sol-gel solution for the low refractive layer is calculated to be about 11 wt%. That is, the content of the sol-gel in the sol-gel solution for the low refractive layer is about 11 wt%.

For high refractive layer Preparation of sol-gel solution

A metal oxide precursor dispersion was prepared by mixing zirconium n-propoxide in a mixed solvent of ethanol and acetylacetone. The prepared metal oxide precursor dispersion was stirred, and an aqueous acetic acid solution and an aqueous hydrochloric acid solution were added dropwise to prepare a sol-gel solution for a high refractive layer. The molar ratio of zirconium n-propoxide, water, ethanol, acetic acid, and hydrochloric acid in the preparation of the sol-gel solution for the high refractive layer was 1:4:12:1:0.47. The solid content of the sol-gel solution for the high refractive layer is calculated to be about 9 wt%. That is, the content of the sol-gel in the sol-gel solution for the high refractive layer is about 9 wt%.

The high refractive sol-gel solution for the high refractive layer was coated on a PET substrate (photorefractive index: 1.58 @550 ㎚) using bar coating, and dried in a convection oven at 80° C. for 1 minute, and a high refractive sol having a thickness of 70 nm- A gel layer was formed. Then, the sol-gel solution for the low refractive layer was coated on the high refractive sol-gel layer using bar coating, and dried in a convection oven at 80° C. for 1 minute to obtain a low refractive sol-gel having a thickness of 95 nm. A layer was formed.

Further, a laminate having a high-refractive sol-gel layer and a low-refractive sol-gel layer sequentially provided on the substrate was immersed in trioctyl amine (TOA) at 80° C. for 5 minutes, then taken out, and washed with distilled water at 40° C. . Thereafter, the water was removed and dried for 2 minutes in a convection oven at 80° C., and a high refractive layer (matrix composition: ZrO ₂ ) and a low refractive layer (matrix composition: SiO ₂ ) were sequentially provided on the substrate. The optical member was prepared.

[ Example 2]

An optical member was manufactured in the same manner as in Example 1, except that the thickness of the low refractive layer was adjusted to 70 nm.

[ Comparative example One]

The sol-gel solution for the low refractive layer of Example 1 was used, and the sol-gel solution for the low refractive layer was coated on a PET substrate (photorefractive index: 1.58 @550 nm) using bar coating, and a convection oven at 80° C. It was dried in a (convection oven) for 1 minute to form a 70 nm-thick low-refractive sol-gel layer. Further, the laminate having a low refractive sol-gel layer on the substrate was immersed in trioctyl amine (TOA) at 80° C. for 5 minutes, then taken out, and washed with distilled water at 40° C. Thereafter, water was removed and dried in a convection oven at 80° C. for 2 minutes to prepare an optical member having a low refractive index layer (matrix composition: SiO ₂ ) on the substrate.

[ Comparative example 2]

The sol-gel solution for the high refractive layer of Example 1 was used, and the sol-gel solution for the high refractive layer was coated on a PET substrate (photorefractive index: 1.58 @550 nm) using bar coating, and a convection oven at 80° C. oven) for 1 minute to form a 70 nm-thick high-refractive sol-gel layer. Further, the laminate having a high refractive sol-gel layer on the substrate was immersed in trioctyl amine (TOA) at 80° C. for 5 minutes, then taken out, and washed with distilled water at 40° C. Thereafter, water was removed and dried in a convection oven at 80° C. for 2 minutes to prepare an optical member having a high refractive index layer (matrix composition: ZrO ₂ ) on the substrate.

[ Comparative example 3]

The sol-gel solution for the high refractive layer of Example 1 was used, and the sol-gel solution for the high refractive layer was coated on a PET substrate (photorefractive index: 1.58 @550 nm) using bar coating, and a convection oven at 80° C. oven) for 1 minute to form a 140 nm-thick high refractive sol-gel layer. Further, the laminate having a high refractive sol-gel layer on the substrate was immersed in trioctyl amine (TOA) at 80° C. for 5 minutes, then taken out, and washed with distilled water at 40° C. Thereafter, water was removed and dried in a convection oven at 80° C. for 2 minutes to prepare an optical member having a high refractive index layer (matrix composition: ZrO ₂ ) on the substrate.

[ Comparative example 4]

The sol-gel solution for the low refractive layer and the sol-gel solution for the high refractive layer of Example 1 were used, and the sol-gel solution for the low refractive layer was coated on a PET substrate (photorefractive index: 1.58 @550 nm) using bar coating. Then, it was dried in a convection oven at 80° C. for 1 minute to form a low refractive sol-gel layer having a thickness of 95 nm. Then, the sol-gel solution for the high refractive layer was coated on the low refractive sol-gel layer using bar coating, dried for 1 minute in a convection oven at 80° C., and a high refractive sol-gel layer having a thickness of 70 nm Formed.

Furthermore, a laminate having a low-refractive sol-gel layer and a high-refractive sol-gel layer sequentially provided on the substrate was immersed in trioctyl amine (TOA) at 80° C. for 5 minutes, then taken out, and washed with distilled water at 40° C. . Thereafter, water was removed and dried for 2 minutes in a convection oven at 80° C., and a low refractive layer (matrix composition: SiO ₂ ) and a high refractive layer (matrix composition: ZrO ₂ ) were sequentially provided on the substrate. The optical member was prepared.

The optical reflectance and steel wool hardness of the optical members according to Examples 1 to 2 and Comparative Examples 1 to 4 are shown in Table 1 below.

Lower coating layer Top coating layer Light reflectance
(%, @50nm) Steel wool hardness
(g, @ 10 times) Matrix composition thickness
(Nm) Matrix composition thickness
(Nm) PET - - - - 5.05 <40 Example 1 ZrO ₂ 70 SiO ₂ 95 1.03 600 Example 2 ZrO ₂ 70 SiO ₂ 70 2.47 560 Comparative Example 1 SiO ₂ 70 - - 2.51 420 Comparative Example 2 ZrO ₂ 70 - - 24.1 480 Comparative Example 3 ZrO ₂ 140 - - 5.05 700 Comparative Example 4 SiO ₂ 95 ZrO ₂ 70 17.2 600

In the present specification, the optical refractive index and the thickness of the sample were taken as the average value of the optical refractive index and thickness measured at random 10 points of the sample using an ellipsometer (J.A. Woollam, M-2000UI).

In the present specification, the light reflectance is a value obtained by measuring light reflectance for each wavelength including regular reflected light at random 10 points of the sample using a spectrophotometer (Konica Minolta, CM-2600d) after attaching the sample to black PET. The average value of was taken.

In this specification, the hardness of the steel wool is determined by visually checking whether the surface is damaged by applying a load to the surface of the sample using an abrasion tester (KP-M4360) and repeating it 10 times at 25 cpm (cycle per minute). It was measured by the method.

According to Table 1, it can be seen that the optical members according to Examples 1 and 2 exhibit lower light reflectance compared to Comparative Examples 1 to 3 provided with a single-layer coating layer. In addition, it can be seen that the optical member according to Comparative Example 4 in which the high refractive coating layer is provided on the outermost side exhibits a considerably higher level of light reflectance than the optical members according to Examples 1 and 2. Furthermore, it can be seen that the surface hardness of the optical members according to Examples 1 and 2 does not significantly decrease even when a multi-layered coating layer is provided.

Claims (17)

Forming a sol-gel solution for a low refractive layer by adding an acidic catalyst to a silica precursor dispersion containing a first solvent and an alkoxy silane;
Forming a sol-gel solution for a high refractive layer by adding an acidic catalyst to a dispersion of a metal oxide precursor containing a second solvent and a metal alkoxide;
Forming a multi-layered sol-gel layer by alternately applying and drying the sol-gel solution for the low refractive layer and the sol-gel solution for the high refractive layer on a substrate; And
Including; by contacting the multi-layered sol-gel layer with a base catalyst, forming a multi-layered low-reflective coating layer having a low refractive layer and a high refractive layer alternately provided;
All of the above processes are performed in an atmosphere of 120° C. or less. A method of manufacturing an optical member including a multilayered low-reflection coating layer. The method according to claim 1,
The sol-gel solution for the low refractive layer and the sol-gel solution for the high refractive layer have a sol-gel content of 5 wt% or more and 40 wt% or less, respectively. The method according to claim 1,
The method of manufacturing an optical member including a multi-layered low-reflective coating layer wherein the low refractive layer includes a silica-based matrix. The method according to claim 1,
The method of manufacturing an optical member including a multi-layered low-reflection coating layer, wherein the high refractive layer includes a metal oxide-based matrix. The method according to claim 1,
The method of manufacturing an optical member including a multi-layered low-reflection coating layer, wherein the outermost layer of the multi-layered low-reflection coating layer is provided with a low refractive index layer. The method according to claim 1,
The alkoxy silane is tetraethoxysilane, tetramethoxysilane, methoxytriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, trimethoxyphenylsilane, triethoxyphenylsilane, 2-(3, 4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, 3-(acryloyloxy)propyltrimethoxysilane, 1,2-bis(tri Ethoxysilane) ethane, and 3-methacryloxypropyltrimethoxysilane A method of manufacturing an optical member comprising a multi-layered low-reflection coating layer comprising at least one of. The method according to claim 1,
The metal alkoxide is aluminum isopropoxide, aluminum sec-butoxide, cerium isopropoxide, hafnium tert-butoxide, magnesium aluminum isopropoxide, yttrium isopropoxide, titanium isopropoxide, rubidium isopro A method of manufacturing an optical member comprising a multilayered low-reflective coating layer comprising at least one of widthside, zirconium n-propoxide, and zirconium isopropoxide. The method according to claim 1,
The base catalyst is a method of manufacturing an optical member including a multi-layered low-reflective coating layer that has a boiling point of 80° C. or higher. The method according to claim 1,
The base catalyst comprises at least one of an amine base catalyst, a phosphoric acid base catalyst, and an imidazole base catalyst. A method for manufacturing an optical member including a multilayer type low reflection coating layer. The method according to claim 1,
The base catalyst is a method of manufacturing an optical member including a multi-layered low-reflection coating layer containing at least one of the compounds represented by the following formulas 1 to 10:
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In Formulas 1 to 10,
R1 to R32 are each independently hydrogen; Or a C1-C40 linear or branched alkyl group; Or an aryl group having 6 to 50 carbon atoms; and,
n and x are any one integer from 1 to 3, o to q are any one of 1 to 4, m and r to w are any one of 1 to 5,
When n is 2 or more, R6 may be the same or different, when m is 2 or more, R7 may be the same or different, and when o is 2 or more, R16 may be the same or different, and when p is 2 or more, R17 is the same. Or they may be different, and when q is 2 or more, R18 may be the same or different, when r is 2 or more, R19 may be the same or different, and when s is 2 or more, R20 may be the same or different, and t is If 2 or more, R21 may be the same or different, if u is 2 or more, R22 may be the same or different, if v is 2 or more, R23 may be the same or different, and if w is 2 or more, R25 may be the same or different. May be, and when x is 2 or more, R32 may be the same or different. The method according to claim 1,
Each of the first solvent and the second solvent is an alcohol-based solvent; Ketone solvents; And an organic solvent containing at least one of acetate-based solvents. A method of manufacturing an optical member comprising a multilayered low-reflection coating layer. The method according to claim 1,
The acidic catalyst includes at least one of hydrochloric acid, sulfuric acid, fluorosulfuric acid, nitric acid, phosphoric acid, acetic acid, hexafluorophosphoric acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.An optical member including a multilayered low-reflection coating layer Method of manufacturing. The method according to claim 1,
Drying the sol-gel solution for the low refractive layer and the sol-gel solution for the high refractive layer includes a multilayered low-reflection coating layer that is dried at a temperature of 120° C. or less to remove the first solvent and the second solvent. Method of manufacturing an optical member. The method according to claim 1,
The step of forming the multi-layered low-reflection coating layer includes contacting the base catalyst at a temperature of 60°C to 120°C with a multi-layered sol-gel layer provided on the substrate. Method of manufacturing the member. The method according to claim 1,
The optical member including the multi-layered low-reflective coating layer is manufactured by a continuous roll-to-roll process. An optical member comprising a multi-layered low-reflection coating layer manufactured by the manufacturing method according to claim 1. The method of claim 16,
The substrate is a polarizing film, a luminance enhancing film, or an optical member comprising a multi-layered low-reflection coating layer that is a retardation film.