KR101081746B1 - Anti-reflective coating composition, anti-reflective coating layer and substrate comprising the anti-reflective coating layer - Google Patents

Abstract

PURPOSE: An anti-reflective coating liquid, an anti-refractive coating layer, and an anti-reflective coating member including the same are provided to improve thermal stability, transmissivity, a self cleaning function, and hardness by offering anti-reflective coating liquid. CONSTITUTION: An anti-refractive coating layer(10) is formed in the surface of a material(20). The anti-refractive coating layer is formed with a normal coating method or a slit-die coating method. The anti-refractive coating layer has excellent film regularity when being formed by the slit-die coating method. Anti-refractive coating liquid includes the binder including silicate, a metal oxide particle, and vehicle.

Description

Anti-reflective coating solution, anti-reflective coating layer and anti-reflective coating substrate comprising same {ANTI-REFLECTIVE COATING COMPOSITION, ANTI-REFLECTIVE COATING LAYER AND SUBSTRATE COMPRISING THE ANTI-REFLECTIVE COATING LAYER}

The present invention relates to an antireflective coating solution, an antireflective coating layer, and an antireflective coating substrate including the same. More specifically, the present invention includes specific silicate and specific metal oxide particles, which have excellent thermal stability, transmittance, self-cleaning function and hardness, significantly reduce reflectance, have an infrared and ultraviolet blocking function, and have excellent film uniformity. An antireflective coating layer and an antireflective coating substrate comprising the same.

Glass or optical materials used in glasses, building materials, displays, etc. have a significant reflectance, so reflected light may cause the screen to be invisible or aesthetically deteriorated. Accordingly, antireflective coatings have been applied to the surface of the material to reduce reflected light from the transparent, translucent material. Such anti-reflective coating can be usefully used in optical devices, glasses, optical communication components, optoelectronic devices, solar devices and display parts.

Conventionally, a silicon-based binder was mixed with a metal oxide such as titania or silica as an antireflective coating material.

However, the conventional coating composition has a disadvantage in that the transmittance during post-processing performed at a temperature of 750 ° C. or higher is lowered in hardness.

Therefore, it is necessary to develop an anti-reflective coating solution that is excellent in thermal stability, transmittance and hardness, can significantly reduce reflectance, has a self-cleaning function and an infrared / ultraviolet reflecting function, and has excellent film uniformity.

One object of the present invention is to provide an antireflective coating liquid having excellent thermal stability, transmittance, self-cleaning function and hardness, significantly reducing reflectance, and infrared and ultraviolet reflecting functions.

Another object of the present invention is to provide an antireflective coating liquid that can be applied to various coating methods.

Still another object of the present invention is to provide an antireflective coating layer having excellent film uniformity using the antireflective coating solution.

Still another object of the present invention is to provide an antireflective coating substrate having excellent transmittance and reduced reflectance by applying the antireflective coating layer.

One aspect of the invention relates to an antireflective coating solution. The anti-reflective coating solution includes (A) a binder including a silicate represented by the following Formula 1; (B) metal oxide particles; And (C) vehicle. The anti-reflective coating liquid is characterized in that the viscosity of 1.5 to 10 cps:

[Formula 1]

(HSiO _1.5 ) x (MO _1.5 ) y

(Wherein M is Al, B, or a combination thereof, x is 0.99-0.60, y is 0.01-0.40, and x + y = 1).

The binder (A) further comprises at least one selected from water glass (sodium silicate), 3-methacryloxypropyltrimethoxy silane, tetraethyl orthosilicate (TEOS) and tetramethyl ortho silicate (TMOS) Anti-reflective coating solution.

In an embodiment, the silicate represented by Formula 1 may be aluminoborosilicate.

In embodiments, the metal oxide particles (B) may have an average particle diameter of 4 to 80 nm.

The metal oxide particles (B) may include one or more particles of SnO 2, W 2 O 3, SiO 2, TiO 2, Cu 2 O 3, and Fe 2 O 3.

The antireflective coating solution (A) 10 to 90% by weight of the binder; 1 to 15% by weight of the metal oxide particles (B) and 3 to 75% by weight of the vehicle (C).

The vehicle (C) may be an organic solvent, water or a combination thereof.

The antireflective coating solution may have a viscosity of 1.8 to 9 cps.

The antireflective coating solution may further include additives such as viscosity modifiers, adhesion enhancers, antioxidants, flame retardants, pigments, dyes, heat stabilizers, weather stabilizers, antistatic agents and UV blockers. These additives can be used individually or in mixture of 2 or more types.

Another aspect of the invention relates to an antireflective coating layer formed from the antireflective coating solution.

Another aspect of the invention relates to an antireflective coating substrate comprising the antireflective coating layer. In an embodiment the antireflective coating substrate is a substrate; And the anti-reflective coating layer formed on at least one surface of the glass.

In embodiments, the antireflective coating layer may be formed by spray coating, spin coating, dip coating, slit die coating, or a combination thereof.

The present invention is excellent in thermal stability, transmittance, self-cleaning function and hardness, significantly reduce the reflectance, infrared and ultraviolet ray blocking function, can provide an antireflective coating liquid that can be applied to various coating methods. In addition, it is possible to provide an antireflective coating layer having excellent film uniformity using the antireflective coating solution. The anti-reflective coating substrate to which the anti-reflective coating layer is applied has an excellent transmittance and an effect of reducing the reflectance.

1 is a cross-sectional view of an antireflective coating substrate according to one embodiment of the present invention.
2 is a graph comparing the transmittance before and after the strengthening process at 750 ℃ of the coating solution prepared according to Example 1.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later. In addition, the size of the components constituting the invention in the drawings are only exaggerated for clarity of the specification, it is not limited thereto.

Anti-reflective coating solution

The antireflective coating solution of the present invention comprises (A) a binder; (B) metal oxide particles; And (C) vehicle.

 (A) binder

The binder (A) is characterized in that it comprises a silicate represented by the formula (1):

[Formula 1]

_{(HSiO 1 .5) x (MO} 1 .5) y

(Wherein M is Al, B, or a combination thereof, x is 0.99-0.60, y is 0.01-0.40, and x + y = 1).

In an embodiment, the binder (A) may be an aluminosilicate represented by the following Chemical Formula 1-1, a borosilicate represented by the Chemical Formula 1-2, an aluminoborosilicate represented by the Chemical Formula 1-3, or a combination thereof:

[Formula 1-1]

_{(HSiO 1 .5) x (AlO} 1 .5) y

(X is 0.99-0.60, y is 0.01-0.40 (where x + y = 1))

[Formula 1-2]

_{(HSiO 1 .5) x (BO} 1 .5) z

(X is 0.99-0.60, z is 0.01-0.40 (where x + z = 1))

[Formula 1-3]

_{(HSiO 1 .5) x (AlO} 1 .5) y (BO 1 .5) z

(X is 0.98-0.20, y is 0.01-0.40, z is 0.01-0.40 (where x + y + z = 1))

The aluminosilicate may be prepared from the reaction of a silane precursor with an aluminum precursor. The borosilicate may be prepared from the reaction of a silane precursor and a boron precursor. In addition, the aluminoborosilicate may be prepared from the reaction of the silane precursor, the aluminum precursor, and the boron precursor.

Among the aluminosilicates, borosilicates, and aluminoborosilicates, the aluminoborosilicates can express more excellent transmittance and antireflection effect and can be most preferably applied.

As the silane precursor, trialkoxysilane, trichlorosilane and tribromosilane may be used alone or as a mixture, or the silane may be selected as a silicon precursor selected from tetraalkoxysilane or a mixture with tetrachlorosilane. It features.

The aluminum precursor may be aluminum oxide (Al ₂ O ₃ ), aluminum trialkoxide (Al (OR) 3), aluminum trichloride alone or a mixture thereof.

The boron precursor is characterized in that any one or a mixture of boron oxide (B ₂ O ₃ ), boron trialkoxide (B (OR) ₃ ).

The aluminum precursor is characterized by using an aluminum content of 1 to 40 mol% with respect to the silicon of the silane precursor. The modulus of the thin film formed as a solution with the aluminum precursor is characterized in that 12 to 81GPa.

 The mechanical strength of the thin film formed from the aluminum precursor solution is characterized in that 1 to GPa. The dielectric constant of the thin film formed as a solution with the aluminum precursor is characterized in that 4 to 7.

The boron precursor is characterized by using a boron content of 1 to 40mol% with respect to the silicon of the silane. The modulus of the thin film formed of the boron precursor solution is characterized in that 14 to 20GPa. The mechanical strength of the thin film formed from the boron precursor solution is characterized in that 1 to 2GPa. The dielectric constant of the thin film formed of the boron precursor solution is characterized in that 2.40 to 3.23.

The binder (A) of the present invention may further include another binder component together with the silicate represented by Chemical Formula 1. In one embodiment, water glass (sodium silicate), 3-methacryloxypropyltrimethoxysilane, tetraethyl orthosilicate (TEOS), tetramethyl ortho silicate (TMOS) and the like can be used. These can be applied individually or in mixture of 2 or more types. In this case, the silicate represented by Chemical Formula 1 is used in 45 wt% or more, preferably 50 to 99 wt%, more preferably 75 to 90 wt% of the total binder components.

In addition, the binder (A) may be contained in 10 to 90% by weight of the total coating composition. In an embodiment 50-88% by weight, for example 75-85% by weight. Preferably it is 80-87 weight%.

(B) metal oxide particles

In the present invention, the metal oxide particles (B) may include at least one of SnO 2, W 2 O 3, SiO 2, TiO 2, Cu 2 O 3, and Fe 2 O 3. The SnO 2 or W 2 O 3 component is more preferable because it can block the infrared rays when applied with the silicate of the formula (1) structure.

In embodiments, the metal oxide particles (B) may have an average particle diameter of 4 to 80 nm. It has a higher infrared reflectance in the above range.

In the present invention, the metal oxide particles may further include other metal oxide particles in addition to SnO 2 and W 2 O 3. For example, SiO 2, TiO 2, Cu 2 O 3, Fe 2 O 3, or the like may be used, and these may be applied alone or by mixing two or more kinds. In this case, the SnO 2 or W 2 O 3 may be used in an amount of 10 wt% or more, preferably 10 to 50 wt%, of the total metal oxide particles (B).

In addition, the metal oxide particles (B) may be contained in 0.5 to 15% by weight of the total coating composition. For example 1.5 to 10% by weight, preferably 2 to 5% by weight.

(C) vehicle

In the present invention, the vehicle (C) is added to ensure viscosity, fairness and dispersibility. The vehicle (C) may be an organic solvent, water, or a combination thereof.

The organic solvent includes methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate (PGMEA), isopropyl ether (IPE), and the like, but is not necessarily limited thereto. The organic solvent may be contained in 3 to 15% by weight of the total coating composition. It has excellent viscosity and fairness in the above range, and can ensure compatibility with the metal oxide particles and other additives.

The water may be contained in 0 to 10% by weight of the total coating composition. It is possible to secure excellent dispersibility in the above range. In an embodiment from 1 to 5% by weight.

The antireflective coating solution of the present invention may further include additives such as viscosity modifiers, adhesion enhancers, antioxidants, flame retardants, pigments, dyes, heat stabilizers, weather stabilizers, antistatic agents and UV blockers. These additives can be used individually or in mixture of 2 or more types. The content of the additives may be contained in 0 to 30% by weight of the total coating composition.

The antireflective coating solution of the present invention may have a viscosity of 1.5 to 10 cps, preferably 1.8 to 9 cps, more preferably 3 to 7 cps. It is excellent in processability, hardness, reflectance and transmittance in the above range, and in particular, a uniform coating film can be obtained.

Anti-reflective coating layer and anti-reflective coating base

Another aspect of the invention relates to an antireflective coating layer formed from the antireflective coating solution.

The antireflective coating layer may be formed on the surface of the substrate by various coating methods. Examples include spray coating, spin coating, dip coating, slit die coating, and the like, but are not limited thereto. It may also be formed by a combination of the above coating method.

In one embodiment, after washing and pretreating the surface of the substrate to be coated, the anti-reflective coating liquid may be slit-die coated on the surface of the substrate.

The substrate may be various materials such as plastic, glass, metal, and the like, and preferably glass. In addition, the form of the substrate is not particularly limited, but may be in the form of a sheet, film, and the like.

The anti-reflection coating layer may be formed of a single layer or a plurality of layers. In an embodiment, the anti-reflective coating layer has a thickness of 50 to 300 nm, preferably 100 to 200 nm after drying. In the above range may have a transparency and antireflection effect.

Another aspect of the invention relates to an antireflective coating substrate comprising the antireflective coating layer. 1 is a cross-sectional view of an anti-reflective coating substrate 100 according to one embodiment of the present invention. As shown, the antireflective coating layer 10 is formed on the surface of the substrate 20. The anti-reflective coating layer 10 may be formed by a conventional coating method, preferably may be formed by a slit die coating. When applied in the coating method has excellent film uniformity. The substrate 20 may be a film, sheet, glass, or the like.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.

Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

Example

Specific specifications of the components used in the following Examples and Comparative Examples are as follows.

(A) Binder:

(A1) Triethoxysilane (150 mmol, 24.64 g) was diluted in tetrahydrofuran (THF, 30 g) solvent and kept at 0 ° C., followed by aluminum-tri-sec-butoxide and boron Aluminoborosilicates prepared by quantifying oxides (Boric oxide, B ₂ O ₃ ) to ₃ mol% based on silane were used as binders.

(A2) TEOS (tetra ethyl ortho silicate) was used.

(B) metal oxide particles

(B1) W2O3 particles having an average particle diameter of 30 nm were used.

(B2) SnO2 particles having an average particle diameter of 30 nm were used.

(B3) Silica particles having an average particle diameter of 30 nm were used.

(C) vehicle

(C1) organic solvent: isopropyl alcohol was used.

(C2) water

(D) additive

(D1) Thickener: A manufacturer BYK product was used.

Example  1-4 and Comparative example  1 ~ 2: Anti-reflective coating solution

Each component was added in the amounts shown in Table 1 below, and stirred at 800 rpm using a stirrer to prepare an antireflective coating solution. The anti-reflective coating solution was coated with a thickness of 5 to 30 μm on the glass by a slit coating method, dried and cured at 3 to 5 min at 200 ° C. NIR to form an anti-reflective coating layer on the glass surface. Physical properties of the antireflective coating layer were measured by the following method, and the results are shown in Table 1. In Example 1, the thermal stability was evaluated by comparing the transmittances before and after the strengthening process at 750 ° C., and are shown in FIG. 2. As shown in Figure 2 it can be seen that there is little change in transmittance before and after strengthening.

Property measurement method

(1) Viscosity: It measured at 25 degreeC with AND viscometer.

(2) Hardness: HB ~ 9H was measured using a mitsubishi pencil as an electric pencil hardness tester.

(3) Contact angle: measured by the contact angle measuring instrument of SEO.

(4) Reflectance, transmittance: measured by Scinco S-4100. (300 ~ 1100nm measurement)

Example Comparative example One 2 3 4 One 2 (A) binder (A1) 85 85 85 85 - 79 (A2) - - - - 85 - (B) metal oxide (B1) 3 - 1.5 - 1.5 3 (B2) - 3 1.5 - 1.5 3 (B3) 7 7 7 10 7 10 (C) vehicle (C1) 3 3 3 3 3 3 (C2) 1.5 1.5 1.5 1.5 1.5 1.5 (D) additive (D1) 0.5 0.5 0.5 0.5 0.5 0.5 Viscosity 9 8.6 9.2 8.8 8.9 11 Hardness > 8H > 8H > 8H > 8H > 3H > 6H Contact angle <5 ° <5 ° <5 ° <5 ° <5 ° > 11 ° reflectivity 3.8 3.5 3.9 3.3 3.8 3.2 Transmittance 89.6 90.5 90.1 89.9 90.3 89.1

As shown in Table 1, Examples 1 to 3 to which the specific silicate of the present invention and W 2 O 3 or SnO 2 are applied are compared with those of Example 4 which do not use W 2 O 3 or SnO 2, and the thermal stability, hardness, transmittance, self-cleaning function, reflectance and hardness. It can be confirmed that is excellent. On the contrary, in Comparative Example 1 in which TEOS was applied instead of the silicate of the present invention, it was confirmed that the hardness was lowered. In addition, Comparative Example 2 outside the viscosity range of the present invention it can be seen that the hardness, transmittance, and reflectance of the film are all reduced.

10: antireflection coating layer 20: glass
100: antireflection coating glass

Claims (11)

(A) a binder comprising a silicate represented by the following formula (1);
(B) metal oxide particles; And
(C) vehicle;
Including;
Antireflective coating liquid, characterized in that the viscosity is 1.5 to 10 cPs:
[Formula 1]
_{(HSiO 1 .5) x (MO} 1 .5) y
(Wherein M is Al, B, or a combination thereof, x is 0.99-0.60, y is 0.01-0.40, and x + y = 1).


The method of claim 1, wherein the binder (A) is selected from water glass (sodium silicate), 3-methacryloxypropyltrimethoxysilane (MPTS), tetraethyl orthosilicate (TEOS) and tetramethyl ortho silicate (TMOS) Anti-reflective coating liquid further comprising the above.
The anti-reflective coating liquid according to claim 1, wherein the silicate represented by Chemical Formula 1 is aluminoborosilicate.
The antireflective coating liquid according to claim 1, wherein the metal oxide particles (B) have an average particle diameter of 4 to 30 nm.
The antireflective coating liquid according to claim 1, wherein the metal oxide particles (B) include at least one of SnO 2, W 2 O 3, SiO 2, TiO 2, Cu 2 O 3, and Fe 2 O 3.
According to claim 1, wherein the antireflective coating liquid (A) 10 to 90% by weight of the binder; (B) 1 to 15% by weight of the metal oxide particles and (C) 3 to 75% by weight of the vehicle.
The antireflective coating liquid according to claim 1, wherein the vehicle (C) is an organic solvent, water, or a combination thereof.
The anti-reflective coating solution according to claim 1, wherein the anti-reflective coating solution comprises at least one additive selected from the group consisting of viscosity modifiers, adhesion enhancers, antioxidants, flame retardants, pigments, dyes, heat stabilizers, weather stabilizers, antistatic agents and UV blockers. Anti-reflective coating liquid.
An antireflective coating layer formed from the antireflective coating liquid of any one of claims 1 to 8.
materials; And
The antireflective coating layer of claim 9 formed on at least one surface of the substrate;
Antireflection coating material consisting of.
The antireflective coating substrate according to claim 10, wherein the antireflective coating layer is formed by spray coating, spin coating, roll coating, dip coating, slit die coating or a combination thereof.

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