KR102019052B1 - Manufacturing method of anti-reflective glass using screen printable anti-reflective coating composition - Google Patents

Abstract

The present invention, the step of screen printing and drying the antireflective coating composition on one side of the glass plate, the step of heat-treating the plate glass screen is printed on one surface of the anti-reflective coating composition, and the anti-reflective coating composition on the other side of the plate glass Screen printing and drying, and the antireflective coating composition comprises heat-treating the plate-printed plate glass on the other side, wherein the antireflective coating composition comprises tetraethyl orthosilicate silane solution synthesized by tetraethylorthosilicate and an alkoxy silane compound hydrolyzed and condensed; And organic vehicles including Texanol and Terpineol. According to the present invention, a screen printing method can be used, a large area anti-reflection film can be formed, and can be manufactured by a simple wet process, which is excellent in price competitiveness, excellent surface hardness and visibility The light transmittance is shown.

Description

Manufacturing method of anti-reflective glass using screen printable anti-reflective coating composition}

The present invention relates to a method of manufacturing antireflective glass using an antireflective coating composition, and more particularly, screen printing can be used, a large area antireflection film can be formed, and a simple process can be produced. The present invention relates to a method for producing a large-area antireflective glass using an antireflective coating composition having excellent price competitiveness and excellent surface hardness and visible light transmittance.

Functional antireflection coating or reflection to improve the efficiency of touch panel, liquid crystal display (LCD), plasma display panel (PDP), solar cell, etc. and to prevent light reflection and contamination The manufacture of a prevention film is calculated | required.

In order to manufacture an antireflection coating or an antireflection film, a CVD (Chemical Vapor Deposition) method, a sputtering method, or the like is used. However, CVD (Chemical Vapor Deposition) method, sputtering (Sputtering) method and the like have problems of expensive manufacturing cost, large area. Therefore, in order to overcome this problem, it is urgent to develop an anti-reflection film manufacturing technology by a wet process, which is advantageous to a large area, which is environmentally friendly and simple.

Anti-reflective coating method using the general wet process includes Sol-gel coating, Dip coating, Spin coating, Ultrasonic spray coating, Liquid phase deposition (LPD) ), LBL (layer-by-layer) method and the like.

In particular, by manufacturing the anti-reflection film by the screen printing (screen printing) method of the wet (Wet) coating method, it is possible to produce a large area antireflective (AR) coating film, dry process because the process is simple Compared with the manufactured antireflection film, the price is excellent. Accordingly, there is a need for the development of an antireflective coating composition capable of screen printing.

Republic of Korea Patent Registration No. 10-1205477

The problem to be solved by the present invention can be screen printing (screen printing) method, it is possible to form a large area anti-reflective film (anti-reflective film), can be manufactured in a simple process, excellent price competitiveness, surface The present invention provides a method for producing a large area antireflective glass using an antireflective coating composition exhibiting excellent hardness and visible light transmittance.

The present invention, the step of screen printing and drying the antireflective coating composition on one side of the glass plate, the step of heat-treating the plate glass screen is printed on one surface of the anti-reflective coating composition, and the anti-reflective coating composition on the other side of the plate glass Screen printing and drying, and the antireflective coating composition comprises heat-treating the plate-printed plate glass on the other side, wherein the antireflective coating composition is characterized in that tetraethylorthosilicate and an alkoxy silane compound are hydrolyzed and Silane solution synthesized by condensation reaction; And an organic vehicle including texanol and terpineol, wherein the alkoxy silane compound is methyltrimethoxysilane, methyltriethoxysilane, or phenyltrimethoxysilane. Phenyltrimethoxysilane, Phenyltriethoxysilane, Glycidoxypropyl trimethoxysilane, and Glycidoxypropyl triethoxysilane containing one or more materials selected from It provides a method for producing an antireflective glass, characterized in that.

The heat treatment is carried out at a heat treatment temperature of 640 ~ 720 ℃, it is preferable to quench the heat-treated plate glass at the heat treatment temperature.

The screen printing is preferably using a screen of 250 to 300 mesh.

The organic vehicle may further include butyl carbitol acetate. The butyl carbitol acetate is preferably contained in the organic vehicle 0.1 to 20 parts by weight based on 100 parts by weight of the total content of the terpinol and the texanol.

The organic vehicle may further include a butyl cellusolve. The butyl cellussolve is preferably contained in the organic vehicle 0.1 to 20 parts by weight based on 100 parts by weight of the total content of the terpinol and the texanol.

The organic vehicle may further include a cellulose binder. The cellulose-based binder is preferably contained 0.1 to 20 parts by weight based on 100 parts by weight of the total content of the terpinol and the texanol in the organic vehicle.

Preferably, the tetraethyl orthosilicate and the alkoxy silane compound are mixed in a weight ratio of 0.1: 1 to 10: 1 to be hydrolyzed and condensed.

The silane solution may be a solution in which water (H ₂ O) and an acid are dropped into a solvent in which the tetraethyl orthosilicate and the alkoxy silane compound are dissolved, and hydrolyzed and condensed.

The texanol and Terpineol are preferably mixed in a weight ratio of 1: 1 to 20: 1 and contained in the organic vehicle.

The organic vehicle and the silane solution preferably form a weight ratio of 4: 1 to 20: 1.

According to the present invention, a screen printing method can be used, a large area anti-reflection film can be formed, and can be manufactured by a simple wet process, so that the price is excellent, surface hardness and visibility The light transmittance is excellent.

1 is a graph showing a change in visible light transmittance of an antireflective glass specimen according to heat treatment conditions.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the following embodiments are provided to those skilled in the art to fully understand the present invention, and may be modified in various forms, and the scope of the present invention is limited to the embodiments described below. It doesn't happen.

Method for producing an antireflective glass according to a preferred embodiment of the present invention, the step of screen printing and drying the antireflective coating composition on one surface of the plate glass, the step of heat-treating the plate glass screen-printed on the antireflective coating composition and And screen printing and drying the antireflective coating composition on the other side of the pane and heat treating the plate glass on which the antireflective coating composition is screen printed on the other side, wherein the antireflective coating composition is tetraethyl ortho. Silane solution synthesized by hydrolysis and condensation reaction of silicate (tetraethylorthosilicate) and alkoxy silane compound; And an organic vehicle including texanol and terpineol, wherein the alkoxy silane compound is methyltrimethoxysilane, methyltriethoxysilane, or phenyltrimethoxysilane. Phenyltrimethoxysilane), phenyltriethoxysilane (Phenyltriethoxysilane), glycidoxypropyl trimethoxysilane (Glycidoxypropyl) trimethoxysilane and (Glycidoxypropyl) triethoxysilane selected from .

The heat treatment is carried out at a heat treatment temperature of 640 ~ 720 ℃, it is preferable to quench the heat-treated plate glass at the heat treatment temperature.

The screen printing is preferably using a screen of 250 to 300 mesh.

The organic vehicle may further include butyl carbitol acetate. The butyl carbitol acetate is preferably contained in the organic vehicle 0.1 to 20 parts by weight based on 100 parts by weight of the total content of the terpinol and the texanol.

The organic vehicle may further include a butyl cellusolve. The butyl cellussolve is preferably contained in the organic vehicle 0.1 to 20 parts by weight based on 100 parts by weight of the total content of the terpinol and the texanol.

The organic vehicle may further include a cellulose binder. The cellulose-based binder is preferably contained 0.1 to 20 parts by weight based on 100 parts by weight of the total content of the terpinol and the texanol in the organic vehicle.

Preferably, the tetraethyl orthosilicate and the alkoxy silane compound are mixed in a weight ratio of 0.1: 1 to 10: 1 to be hydrolyzed and condensed.

The silane solution may be a solution in which water (H ₂ O) and an acid are dropped into a solvent in which the tetraethyl orthosilicate and the alkoxy silane compound are dissolved, and hydrolyzed and condensed.

The texanol and Terpineol are preferably mixed in a weight ratio of 1: 1 to 20: 1 and contained in the organic vehicle.

The organic vehicle and the silane solution preferably form a weight ratio of 4: 1 to 20: 1.

Hereinafter, a method of manufacturing a large area antireflection glass according to a preferred embodiment of the present invention will be described in more detail.

A large area pane is prepared to coat the antireflection film. The plate glass may be prepared by cutting and chamfering the plate glass original to the desired size.

It is washed and dried to remove foreign substances on the surface of the pane. The washing may use water (H ₂ O), alcohol and the like. The drying is preferably carried out at a temperature higher than room temperature (for example, 40 ~ 100 ℃).

Screen printing and drying the antireflective coating composition on one surface of the pane. The drying is performed for at least 5 minutes (eg, 5 to 300 minutes) at a temperature of 100 ° C. or higher (eg, 100 to 200 ° C.), more preferably at a temperature of 150 ° C. or higher (eg, 150 to 200 ° C.). desirable. The screen printing is preferably using a screen of 250 to 300 mesh. Screen printing methods are generally well known and detailed descriptions thereof are omitted here.

The antireflective coating composition is a coating composition suitable for the screen printing coating method for forming an antireflection film having a low refractive index on a large area glass.

Anti-reflective coating method using wet process includes screen printing, Sol-gel coating, Dip coating, Spin coating, ultrasonic spray coating, liquid deposition (liquid phase deposition; LPD), LBL (layer-by-layer) method, and the like.

Anti-reflective film can be manufactured by screen printing method of wet coating method, so anti-reflective coating film R can be manufactured, and dry process because of simple process Compared with the manufactured antireflection film, the price is excellent.

The anti-reflective coating composition is an anti-reflective coating composition capable of screen printing, a silane solution synthesized by hydrolysis and condensation reaction of tetraethyl orthosilicate and an alkoxy silane compound, Texanol and terpinol Organic vehicles that include (Terpineol).

The silane solution is a solution synthesized by the hydrolysis and condensation reaction of tetraethyl orthosilicate and an alkoxy silane compound.

The alkoxy silane compound may be methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, glycidoxypropyltrimethoxysilane ( (Glycidoxypropyl) trimethoxysilane) and glycidoxypropyl triethoxysilane ((Glycidoxypropyl) triethoxysilane) and at least one material selected from.

Preferably, the tetraethyl orthosilicate and the alkoxy silane compound are mixed in a weight ratio of 0.1: 1 to 10: 1 to be hydrolyzed and condensed.

The silane solution may be a solution in which water (H ₂ O) and an acid are dropped into a solvent in which the tetraethyl orthosilicate and the alkoxy silane compound are dissolved, and hydrolyzed and condensed.

The solvent may include ethanol, methanol, isopropyl alcohol, etc., preferably ethanol is used. It is preferable that the total content of the tetraethyl orthosilicate and the alkoxy silane compound and the content of the solvent form a weight ratio of 0.5: 1 to 2: 1.

The acid may include nitric acid (HNO ₃ ), hydrochloric acid (HCl), acetic acid, and the like, and preferably nitric acid (HNO ₃ ) is used. The total content of the tetraethyl orthosilicate and the alkoxy silane compound and the acid are preferably in a weight ratio of 10: 1 to 30: 1. It is preferable to adjust the pH of the solution to about 5-7 by the addition of the acid.

The hydrolysis and condensation reaction is preferably carried out at a temperature of 45 ~ 70 ℃ higher than room temperature and lower than the boiling point of the solvent. The hydrolysis and condensation reaction is preferably carried out while stirring at 1 ~ 100rpm in order to enhance the reactivity.

A clear silane solution formed by the hydrolysis and condensation reactions is obtained.

In order to form the anti-reflection film (anti-reflective coating film) by using the screen printing method, a high viscosity coating paste is required, and thus an organic vehicle to be mixed with the silane solution is required.

The organic vehicle includes Texanol and Terpineol. The texanol and Terpineol are preferably mixed in a weight ratio of 1: 1 to 20: 1 and contained in the organic vehicle.

The organic vehicle may further include butyl carbitol acetate (BCA). The butyl carbitol acetate is preferably contained in the organic vehicle 0.1 to 20 parts by weight based on 100 parts by weight of the total content of the terpinol and the texanol.

The organic vehicle may further include butyl cellusolve (BC). The butyl cellussolve is preferably contained in the organic vehicle 0.1 to 20 parts by weight based on 100 parts by weight of the total content of the terpinol and the texanol.

The organic vehicle may further include a cellulose binder. The cellulose-based binder is preferably contained 0.1 to 20 parts by weight based on 100 parts by weight of the total content of the terpinol and the texanol in the organic vehicle. The cellulose-based binder may be ethyl cellulose, ethyl cellulose, a mixture thereof, or the like.

The organic vehicle is mixed with a raw material containing at least Texanol (Texanol) and terpineol (Texanol) and by applying heat of 90 ° C or more (e.g. 90 ~ 200 ° C higher than the melting temperature of the raw material and lower than the burning temperature) It can be synthesized by melting the raw material in the solid state.

The organic vehicle and the silane solution preferably form a weight ratio of 4: 1 to 20: 1.

The anti-reflective coating composition heat-treats the plate glass screen printed on one surface. The heat treatment is carried out at a heat treatment temperature of 640 ~ 720 ℃, it is preferable to quench the heat-treated plate glass at the heat treatment temperature. By the heat treatment, the organic component contained in the antireflective coating composition is removed. The quenching may use a method of quenching by blowing air.

Screen printing and drying the antireflective coating composition on the other side of the pane (opposite side of the one side). The drying is carried out for at least 5 minutes (eg, 5 to 300 minutes) at a temperature of at least 100 ° C (eg, 100 to 200 ° C), more preferably at a temperature of 150 ° C or more (eg, 150 to 200 ° C). desirable. The screen printing is preferably using a screen of 250 to 300 mesh. Screen printing methods are generally well known and detailed descriptions thereof are omitted here. The anti-reflective coating composition for screen printing on the other side of the pane is preferably the same as the anti-reflective coating composition for screen printing on one side of the pane.

The anti-reflective coating composition heat-treats the plate glass screen printed on the other side. The heat treatment is carried out at a heat treatment temperature of 640 ~ 720 ℃, it is preferable to quench the heat-treated plate glass at the heat treatment temperature. By the heat treatment, the organic component contained in the antireflective coating composition is removed. The quenching may use a method of quenching by blowing air.

The large-area antireflection glass thus manufactured has a form in which an antireflection film is formed on both surfaces (one side and the other side).

According to the present invention, by forming an antireflection film on a large area glass using a screen printing method of the wet coating method, a large area antireflection glass can be produced, and the process is simple. Compared with the anti-reflection film formed by the dry method, the price is excellent. The antireflection film formed according to the present invention exhibits excellent surface hardness and visible light transmittance.

Hereinafter, experimental examples according to the present invention are specifically presented, and the present invention is not limited to the following experimental examples.

In order to form an antireflection film having a low refractive index on the glass, a solution suitable for the screen printing coating method was developed, and the change in reflectance and visible light transmittance according to the refractive index and thickness of the antireflection film (antireflective coating film) was confirmed.

Experimental Example 1

Tetraethylorthosilicate (TEOS) and methyltrimethoxysilane (MTMS) were used as starting materials, respectively. TEOS: MTMS = 100: 0, 50:50, 0: A silane solution as a starting material was synthesized by mixing at a ratio of 100 (weight ratio). At this time, the content of the starting material was adjusted to 41.0wt% to 51.0wt% using ethanol as a solvent. Table 1 below shows the mixing ratio and the content of the starting material according to the content of the starting material.

designation Starting material content (wt%) Starting material AR-a 47.5 TEOS: MTMS = 50: 50 AR-b 51.0 MTMS = 100 AR-c 51.0 TEOS = 100

Hereinafter, the method of synthesizing the silane solution will be described in more detail. The sol-gel method was used to synthesize the silane solution, and the starting materials, ethanol, water, and acid solutions were used as starting materials. First, the starting material was dissolved in ethanol, and water (H ₂ O) and acid (acid) were added drop by drop for hydrolysis and condensation reactions. To promote the reaction, acid was used as a catalyst. At this time, the acid was adjusted to pH 6 of the final solution using nitric acid (HNO ₃ ) and finally the solution was reacted at 60 ° C. for 2 hours. The silane solution was synthesized.

In order to form an anti-reflection film (anti-reflective coating film) by using the screen printing method, since a high viscosity coating paste is required, an organic vehicle to be mixed with the silane solution is required. In order to prepare the organic vehicle, the five components were mixed by content, and heat was added at 90 ° C. or higher to melt the raw materials in the solid state, thereby synthesizing the organic vehicle. Table 2 below shows the contents of the raw materials for synthesizing the organic vehicle used in the experimental example.

ingredient Content (wt%) Terpineol 10 Butyl Carbitol Acetate (BCA) 10 Butyl Cellusolve (BC) 10 Texanol 60 Ethyl Cellulose 10

In order to form the anti-reflection film using the final screen printing, the silane solution was mixed at 8 wt% and the organic vehicle at 92 wt%, and the ambient temperature (27 ° C.) atmosphere condition was performed using the prepared coating paste (anti-reflective coating composition). After screen printing on the glass through the screen 250mesh mesh at each and dried and cured at 150 ℃, the anti-reflection glass specimens were prepared by heat-curing the dry cured glass at 650 ℃. After the heat treatment, the air was blown and quenched.

For the case of preparing a coating paste (anti-reflective coating composition) using a silane solution synthesized using TEOS and MTMS, a silane solution synthesized using MTMS alone, and a silane solution synthesized using TEOS alone, respectively. The characteristics were evaluated and shown in Table 3 below.

characteristic When manufacturing the coating paste using AR-a When manufacturing the coating paste using AR-b When manufacturing the coating paste using AR-c Surface air bubbles immediately after printing handful handful handful Coating surface color after heat treatment Violet Yellow Blue Transmittance (%) 94 93 95

When the coating paste is manufactured by using the silane solution (AR-c) synthesized using TEOS alone, the transmittance is improved, but the surface is rough and the hardness is weakened, and the silane synthesized using MTMS alone is used. When the coating paste is prepared using the solution (AR-b), the visible light transmittance improvement is slightly inferior, but the surface is smooth, resulting in a good surface hardness. When the coating paste was prepared using the silane solution synthesized using TEOS and MTMS, the surface hardness was excellent and the visible light transmittance was also excellent.

Experimental Example 2

92 wt% of the organic vehicle prepared according to Experimental Example 1, and 8 wt% of the silane solution synthesized by mixing TEOS and MTMS in a ratio of 50:50 according to Experimental Example 1 to prepare a coating paste (anti-reflective coating composition) It was.

The coating paste was screen printed onto a glass substrate using a 250mesh screen and then dried and cured at 150 ° C.

The antireflection glass specimens were prepared by heat treatment with different heat treatment conditions. At this time, the heat treatment condition was named AR-a-1 anti-reflective glass specimen heat-treated in a sequence up to 570 ℃ at room temperature (10 ℃ / min), AR-a-1, put the dried sample at 500 ℃ to the sequence (570 ℃) The antireflective glass specimen heat-treated at 10 ° C./min) was named AR-a-2, and the antireflective glass specimen heat-treated while being kept at 650 ° C. for 150 seconds was named AR-a-3. It was. After the heat treatment, the air was blown and quenched. The characteristics of the antireflective glass specimens according to the heat treatment conditions were evaluated and shown in Table 4 below. The visible light transmittance change of the antireflective glass specimen according to the heat treatment conditions is shown in FIG. 1.

Sample Heat treatment condition Visible light transmittance (%) Visible light average reflectance (%) Refractive index (@ 632nm) Coating film thickness (nm) 3.2T Substrate Glass 90.95 4.60 AR-a-1 Room temperature → 570 ℃ 91.67 2.89 1.494 90.50 AR-a-2 500 ℃ → 570 ℃ 93.57 1.02 1.345 93.40 AR-a-3 650 ° C (150 seconds hold) 93.70 0.80 1.294 116.39

The average transmittance of the glass used as the substrate was found to be 90.95% and the reflectance was 4.60%.

In the case of the antireflective glass specimen (AR-a-1) heat-treated in sequence from room temperature to 570 ° C, the refractive index of the antireflective coating was 1.494, the thickness was 90.5 nm, the average transmittance of visible light was 91.67%, and the average cross-sectional reflectance was about 2.89%. It became.

The refractive index of the antireflective film (AR-a-2) of the antireflective glass specimen (AR-a-2) heat-treated in the sequence up to 570 ° C. with the specimen dried at 500 ° C. was 1.345 and the thickness was 93.4 nm. As the heat treatment temperature increases, the antireflection film due to decomposition of the organic vehicle becomes more porous, and thus, the refractive index is determined to be lower. As a result, the antireflection property was improved to an average visible light transmittance of 93.57% and an average cross section reflectance of about 1.02%.

The anti-reflective glass specimen (AR-a-3) prepared by heat treatment at 150 ° C. and maintained for 150 seconds showed the lowest refractive index of 1.294, thickness of 115.39 nm, average transmittance of 93.70%, and average cross-sectional reflectance of about 1.294. It was measured at 0.80%. As the heat treatment temperature was sufficiently high, the antireflection film was porous, so that the refractive index of the final antireflection film was less than 1.30.

As mentioned above, although the preferred embodiment of this invention was described in detail, this invention is not limited to the said embodiment, A various deformation | transformation by a person of ordinary skill in the art within the scope of the technical idea of this invention is carried out. This is possible.

Claims (10)

Screen printing and drying the antireflective coating composition on one side of the pane;
Heat treating the plate glass screen-printed on one surface of the antireflective coating composition;
Screen printing and drying the antireflective coating composition on the other side of the pane; And
The anti-reflective coating composition comprises the step of heat-treating the plate glass screen printed on the other side,
The antireflective coating composition,
Silane solutions synthesized by hydrolysis and condensation reaction of tetraethylorthosilicate and alkoxy silane compounds; And
Organic vehicles including Texanol and Terpineol,
The alkoxy silane compound is methyltrimethoxysilane, methyltriethoxysilane, Methyltriethoxysilane, Phenyltrimethoxysilane, Phenyltriethoxysilane, Glycidoxypropyltrimethoxysilane ( (Glycidoxypropyl) trimethoxysilane) and glycidoxypropyl triethoxysilane ((Glycidoxypropyl) triethoxysilane) A method for producing an antireflective glass, characterized in that it comprises at least one material selected from.
According to claim 1, wherein the heat treatment is carried out at a heat treatment temperature of 640 ~ 720 ℃,
Method for producing an anti-reflective glass, characterized in that the heat-treating plate glass quenched at the heat treatment temperature.
The method of claim 1, wherein the screen printing is a method of manufacturing an anti-reflective glass, characterized in that using a screen of 250 to 300 mesh.
The method of claim 1, wherein the organic vehicle further comprises butyl carbitol acetate (Butyl carbitol acetate),
The butyl carbitol acetate is 0.1 to 20 parts by weight based on 100 parts by weight of the total content of the terpinol and the texanol in the organic vehicle.
The method of claim 1, wherein the organic vehicle further comprises a butyl cellusolve (Butyl cellusolve),
The butyl cellussolve is 0.1 to 20 parts by weight based on 100 parts by weight of the total content of the terpinol and the texanol in the organic vehicle.
The method of claim 1, wherein the organic vehicle further comprises a cellulose-based binder,
The cellulose-based binder is 0.1 to 20 parts by weight based on 100 parts by weight of the total content of the terpinol and the texanol in the organic vehicle.
The method of claim 1, wherein the tetraethyl orthosilicate and the alkoxy silane compound are mixed in a weight ratio of 0.1: 1 to 10: 1 to undergo hydrolysis and condensation reaction.
The solution of claim 1, wherein the silane solution is a solution in which water (H ₂ O) and an acid are dropped in a solvent in which the tetraethyl orthosilicate and the alkoxy silane compound are dissolved, and hydrolyzed and condensed. Method for producing an antireflective glass, characterized in that.
The method of claim 1, wherein the texanol and the terpineol are mixed in a weight ratio of 1: 1 to 20: 1 and included in the organic vehicle.
The method of claim 1, wherein the organic vehicle and the silane solution form a weight ratio of 4: 1 to 20: 1.

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