KR101981127B1 - Screen printable anti-reflective coating composition and manufacturing method of anti-reflective coating film using the coating composition - Google Patents

Abstract

The present invention relates to an organic vehicle comprising a silane solution synthesized by hydrolysis and condensation reaction of tetraethylorthosilicate and an alkoxysilane compound and an organic vehicle comprising Texanol and terpineol, The alkoxysilane compound may be at least one selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, glycidoxypropyltrimethoxysilane ( (Glycidoxypropyl) trimethoxysilane, and (Glycidoxypropyl) triethoxysilane. The present invention also relates to a method of preparing an antireflective coating using the antireflective coating composition. According to the present invention, a screen printing method can be used, a large-area antireflection film can be manufactured, and a simple wet process can be used. Therefore, it is excellent in price competitiveness, And the light transmittance.

Description

TECHNICAL FIELD The present invention relates to an antireflective coating composition capable of screen printing and a method for producing an antireflective coating using the same.

The present invention relates to an antireflective coating composition and a method of preparing an antireflective coating using the same. More particularly, the present invention relates to an antireflective coating composition which can be screen printed and can produce a large-area antireflective film, And exhibits excellent surface competitiveness, excellent surface hardness and visible light transmittance, and a method for producing an antireflective coating using the antireflective coating composition.

In order to improve the efficiency of a touch panel, a liquid crystal display (LCD), a plasma display panel (PDP), a solar cell, and the like, and to prevent light reflection and contamination, A barrier film is required to be produced.

A CVD (Chemical Vapor Deposition) method, a sputtering method, or the like is used to produce an antireflection coating film or an antireflection film. However, the CVD (Chemical Vapor Deposition) method, the sputtering method, and the like have a problem of costly fabrication cost and large size. In order to overcome this problem, it is urgent to develop an antireflection film manufacturing technology by a wet process which is advantageous for a large area by an environmentally friendly and simple process.

The anti-reflection film fabrication method using a general wet process includes a method such as a sol-gel coating, a dip coating, a spin coating, an ultrasonic spray coating, a liquid phase deposition (LPD ) Method, and a layer-by-layer (LBL) method.

Particularly, it is possible to produce an antireflective (AR) coating film by producing an antireflection film by using a screen printing method among the wet coating method, and since the process is simple, Compared with the antireflection film produced, it has excellent price competitiveness. Accordingly, there is a demand for the development of antireflective coating compositions capable of screen printing.

Korean Patent Registration No. 10-1205477

A problem to be solved by the present invention is to provide an anti-reflective (AR) coating film which can use a screen printing method and can be manufactured by a simple process, , Surface hardness and visible light transmittance, and a method for producing an antireflective coating using the antireflective coating composition.

The present invention relates to an antireflective coating composition capable of screen printing, which comprises a silane solution synthesized by hydrolysis and condensation reaction of tetraethylorthosilicate and an alkoxysilane compound and a silane solution synthesized by Texanol and terpineol, Wherein the alkoxysilane compound is at least one selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, The present invention provides an antireflection coating composition comprising at least one material selected from the group consisting of glycidoxypropyl trimethoxysilane and glycidoxypropyl triethoxysilane.

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

The organic vehicle may further include butyl cellusolve. The butyl cellosolve is preferably contained in the organic vehicle in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the total amount of the terpineol and the texanol.

The organic vehicle may further comprise a cellulosic binder. The cellulose based binder is preferably contained in the organic vehicle in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the total amount of the terpineol and the texanol.

The tetraethyl orthosilicate and the alkoxysilane compound are preferably mixed in a weight ratio of 0.1: 1 to 10: 1 and hydrolyzed and condensed.

The silane solution may be a solution in which water (H ₂ O) and acid are dripped into the solvent in which the tetraethyl orthosilicate and the alkoxysilane compound are dissolved and subjected to hydrolysis and condensation reaction.

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 have a weight ratio of 4: 1 to 20: 1.

The present invention also relates to a method of coating a substrate, comprising screen printing the anti-reflective coating composition on a substrate, drying the anti-reflective coating composition coated on the substrate, heat treating the dried product, and quenching the heat- The method comprising the steps of:

The heat treatment is preferably performed at a temperature of 550 to 700 ° C.

According to the present invention, a screen printing method can be used, a large-area antireflection film can be manufactured, and since it can be manufactured by a simple wet process, it is excellent in price competitiveness, And exhibits excellent light transmittance.

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

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, it should be understood that the following embodiments are provided so that those skilled in the art will be able to fully understand the present invention, and that various modifications may be made without departing from the scope of the present invention. It is not.

An antireflection coating composition according to a preferred embodiment of the present invention is an antireflective coating composition capable of screen printing, which comprises a silane solution synthesized by hydrolysis and condensation reaction of tetraethylorthosilicate and an alkoxysilane compound, Wherein the alkoxysilane compound is selected from the group consisting of Methyltrimethoxysilane, Methyltriethoxysilane, Phenyltrimethoxysilane, and Phenyltrimethoxysilane. , Phenyltriethoxysilane, (Glycidoxypropyl) trimethoxysilane, and glycidoxypropyl triethoxysilane. The term " a "

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

The organic vehicle may further include butyl cellusolve. The butyl cellosolve is preferably contained in the organic vehicle in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the total amount of the terpineol and the texanol.

The organic vehicle may further comprise a cellulosic binder. The cellulose based binder is preferably contained in the organic vehicle in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the total amount of the terpineol and the texanol.

The tetraethyl orthosilicate and the alkoxysilane compound are preferably mixed in a weight ratio of 0.1: 1 to 10: 1 and hydrolyzed and condensed.

The silane solution may be a solution in which water (H ₂ O) and acid are dripped into the solvent in which the tetraethyl orthosilicate and the alkoxysilane compound are dissolved and subjected to hydrolysis and condensation reaction.

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 have a weight ratio of 4: 1 to 20: 1.

The method of manufacturing an antireflection coating according to a preferred embodiment of the present invention includes the steps of screen printing the antireflective coating composition on a substrate, drying the antireflective coating composition coated on the substrate, And quenching the heat-treated product.

The heat treatment is preferably performed at a temperature of 550 to 700 ° C.

Hereinafter, an antireflection coating composition according to a preferred embodiment of the present invention will be described in more detail.

The present invention provides a solution (coating composition) suitable for a screen printing coating method for producing an antireflection film having a low refractive index on a substrate.

Methods of preparing anti-reflective coatings using a wet process include screen printing, sol-gel coating, dip coating, spin coating, ultrasonic spray coating, liquid deposition (LPD) method, and a layer-by-layer (LBL) method.

Since anti-reflective coating film can be manufactured by using screen printing method among the wet coating method, it is possible to produce anti-reflective coating film R. Since the process is simple, Compared with the antireflection film produced, it has excellent price competitiveness.

An antireflection coating composition according to a preferred embodiment of the present invention is an antireflective coating composition capable of screen printing, which comprises a silane solution synthesized by hydrolysis and condensation reaction of tetraethylorthosilicate and an alkoxysilane compound, ≪ / RTI > Texanol, and Terpineol.

The silane solution is a solution synthesized by hydrolysis and condensation reaction of tetraethylorthosilicate and an alkoxysilane compound.

The alkoxysilane compound may be at least one selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, glycidoxypropyltrimethoxysilane (Glycidoxypropyl) trimethoxysilane), and glycidoxypropyl triethoxysilane.

The tetraethyl orthosilicate and the alkoxysilane compound are preferably mixed in a weight ratio of 0.1: 1 to 10: 1 and hydrolyzed and condensed.

The silane solution may be a solution in which water (H ₂ O) and acid are dripped into the solvent in which the tetraethyl orthosilicate and the alkoxysilane compound are dissolved and subjected to hydrolysis and condensation reaction.

The solvent may include ethanol, methanol, isopropyl alcohol and the like, preferably ethanol. It is preferable that the total content of the tetraethyl orthosilicate and the alkoxysilane compound and the content of the solvent satisfy 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, preferably nitric acid (HNO ₃ ). It is preferable that the total content of the tetraethyl orthosilicate and the alkoxysilane compound and the content of the acid satisfy a weight ratio of 10: 1 to 30: 1. It is preferable that the pH of the solution is adjusted to about 5 to 7 by the addition of the acid.

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

A transparent silane solution formed by the hydrolysis and condensation reaction is obtained.

In order to produce an antireflection coating (antireflection coating film) using a screen printing method, an organic vehicle to be mixed with the silane solution is required because a coating paste having a high viscosity 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 comprise butyl carbitol acetate (BCA). The butyl carbitol acetate is preferably contained in the organic vehicle in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the total amount of terpinol and texanol.

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

The organic vehicle may further comprise a cellulosic binder. The cellulose based binder is preferably contained in the organic vehicle in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the total amount of the terpineol and the texanol. The cellulose-based binder may be ethyl cellulose, methyl cellulose, a mixture thereof, or the like.

The organic vehicle is prepared by mixing raw materials containing at least Texanol and Terpineol and heating the mixture to 90 ° C or higher (for example, 90 ° C to 200 ° C, which is higher than the melting temperature of the raw material and lower than the burning temperature) It can be synthesized by dissolving the raw material in a solid state.

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

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

The antireflective coating composition is screen printed on a substrate. The substrate may be a glass substrate or the like, and there is no limitation as long as the object of the present invention is not impaired. The screen printing method is well known in general, and a detailed description thereof will be omitted here.

The anti-reflective coating composition coated on the substrate is dried. The drying is preferably performed at a temperature of about 80 to 200 ° C.

Heat the dried product. The heat treatment is preferably performed at a temperature of 550 to 700 ° C. The organic components contained in the antireflective coating composition are removed by the heat treatment.

Quench the heat treated product. The quenching may be performed by blowing air to quench the air.

According to the present invention, a large-area antireflection film can be produced by using the screen printing method of the wet coating method, and since the process is simple, Compared with the barrier film, it has excellent price competitiveness. The antistatic film produced according to the present invention exhibits excellent surface hardness and visible light transmittance.

Hereinafter, experimental examples according to the present invention will be specifically shown, and the present invention is not limited to the following experimental examples.

In order to fabricate an antireflection film having a low refractive index on a substrate, a solution suitable for a screen printing coating method was developed. The reflectance and the visible light transmittance according to the refractive index and thickness of the antireflection film (antireflection coating film) were confirmed.

<Experimental Example>

MTMS = 100: 0, 50:50, 0: 1) as the starting material, and tetraethylorthosilicate (TEOS) and methyltrimethoxysilane (MTMS) 100 (weight ratio) to synthesize a silane solution as a starting material. At this time, the content of the starting material was adjusted from 47.5 wt% to 51.0 wt% 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 for synthesizing the silane solution will be described in more detail. The starting material, ethanol, water, and acid solution were used as starting materials for the synthesis of the silane solution. First, the starting materials were dissolved in ethanol, and water (H ₂ O) and acid were added dropwise for hydrolysis and condensation reaction. In order to accelerate the reaction, acid was used as a catalyst. The pH of the final solution was adjusted to about 6 by using nitric acid (HNO ₃ ) as the acid, and finally the solution was reacted at 60 ° C. for 2 hours Silane solution was synthesized.

In order to prepare an antireflection coating (antireflection coating film) using a screen printing method, an organic vehicle to be mixed with the silane solution is required because a coating paste having a high viscosity is required. To prepare the organic vehicle, the organic vehicle was synthesized by mixing the five components by the respective contents and dissolving the materials in the solid state by heating at 90 ° C or more. Table 2 below shows the contents of raw materials for synthesizing the organic vehicle used in the experimental examples.

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

To prepare the antireflection film using the final screen printing, 8 wt% of the silane solution and 92 wt% of the organic vehicle were mixed. The coating paste (anti-reflection coating composition) , Screen printed on a glass substrate through a 250 mesh screen, dried and cured at 150 ° C, and heat cured at 650 ° C to prepare an antireflection film coated glass specimen. After the heat treatment, the air was blown by rapid cooling.

In the case where the coating paste (antireflection coating composition) was prepared by using the silane solution synthesized using TEOS and MTMS, the silane solution synthesized using MTMS alone, and the silane solution synthesized using TEOS alone Properties were evaluated and shown in Table 3 below.

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

When the coating paste is prepared by using the silane solution (AR-c) synthesized using TEOS alone, the transmittance is greatly improved, but the surface is coarse and the hardness is weak. When the coating paste is prepared using the solution (AR-b), the visible light transmittance is slightly improved, but the surface is smooth and the surface hardness is good. When the coating paste was prepared by 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% by weight of the organic vehicle prepared according to Experimental Example 1 and 8% by weight of the synthesized silane solution were mixed with TEOS and MTMS at a ratio of 50:50 according to Experimental Example 1 to prepare a coating paste (antireflection coating composition) Respectively.

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

The antireflective coating - coated glass specimens were prepared by heat treatment under different heat treatment conditions. In this case, the antireflection film-coated glass specimen, which was heat-treated at a temperature of 570 ° C from room temperature to 1070 ° C / min, was named AR-a-1. The specimen dried at 500 ° C was introduced into the specimen A-2, which was heat-treated at room temperature (10 ° C / min), was named AR-a-2. The glass specimen, which was heat- 3. After the heat treatment, the air was blown by rapid cooling. The properties of the antireflective coating-coated glass specimens according to the heat treatment conditions were evaluated and are shown in Table 4 below. The visible light transmittance of the antireflection film-coated glass specimen according to the heat treatment conditions is shown in FIG.

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

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

In the case of the antireflective coating-coated glass specimen (AR-a-1) thermally treated at room temperature to 570 ° C, the refractive index of the antireflective coating film was 1.494, the thickness was 90.5 nm, the visible light transmittance was 91.67% Respectively.

The refractive index of the antireflection coating film of the antireflection film-coated glass specimen (AR-a-2) thermally treated up to 570 ° C by introducing the dried specimen at 500 ° C was 1.345 and the thickness was 93.4 nm. It is considered that the refractive index of the antireflective coating film due to the decomposition of the organic vehicle becomes more porous as the heat treatment temperature becomes higher. As a result, the visible light average transmittance was 93.57%, and the cross-sectional average reflectance was about 1.02%, and the antireflection characteristics were improved.

(AR-a-3) prepared by heat treatment at 650 ° C. for 150 seconds, the refractive index of the antireflective coating film was 1.294, the thickness was 115.39 nm, the visible light average transmittance was 93.70% Was measured to be about 0.80%. The porosity of the antireflective coating film was increased as the heat treatment temperature was higher, and the refractive index of the final antireflective coating film was less than 1.30.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, This is possible.

Claims (10)

An antireflective coating composition capable of screen printing,
A silane solution synthesized by hydrolysis and condensation reaction of tetraethylorthosilicate and an alkoxysilane compound; And
An organic vehicle comprising Texanol and Terpineol,
The alkoxysilane compound may be at least one selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, glycidoxypropyltrimethoxysilane (Glycidoxypropyl) trimethoxysilane, and (Glycidoxypropyl) triethoxysilane.
The tetraethyl orthosilicate and the alkoxysilane compound are mixed at a weight ratio of 0.1: 1 to 10: 1, subjected to a hydrolysis and condensation reaction,
The silane solution is a solution in which water (H ₂ O) and acid are dripped into the solvent in which the tetraethyl orthosilicate and the alkoxysilane compound are dissolved and hydrolyzed and condensed,
Wherein the organic vehicle further comprises butyl cellusolve,
Wherein the butyl cellosolve is contained in the organic vehicle in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the total amount of the terpineol and the texanol,
The Texanol and terpineol are mixed in a weight ratio of 1: 1 to 20: 1 and contained in the organic vehicle,
Wherein the organic vehicle and the silane solution are in a weight ratio of 4: 1 to 20: 1.
The method of claim 1, wherein the organic vehicle further comprises butyl carbitol acetate,
Wherein the butyl carbitol acetate is contained in the organic vehicle in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the total amount of the terpineol and the texanol.
delete The method of claim 1, wherein the organic vehicle further comprises a cellulosic binder,
Wherein the cellulose-based binder is contained in the organic vehicle in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the total amount of the terpineol and the texanol.
delete delete delete delete Screen printing the anti-reflective coating composition of claim 1 on a substrate;
Drying the anti-reflective coating composition coated on the substrate;
Heat treating the dried product; And
And rapidly quenching the heat-treated resultant.
The method according to claim 9, wherein the heat treatment is performed at a temperature of 550 to 700 캜.

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