KR101219053B1

KR101219053B1 - Etch solution composition

Info

Publication number: KR101219053B1
Application number: KR1020090112782
Authority: KR
Inventors: 임철규; 권경일
Original assignee: 타코마테크놀러지 주식회사
Filing date: 2009-11-20
Publication date: 2013-01-07

Abstract

The present invention discloses an etchant composition comprising a bulky ammonium salt represented by the following formula (1).

Formula 1

Wherein R ₁ , R ₂ and R ₃ are the same as or different from each other, and are an alkyl group or benzyl group having 1 to 14 carbon atoms, and A is an alkylene group or alkylene oxide group having 1 to 5 carbon atoms which is optionally substituted with a hydroxyl group. X is -OH, -COOH, -COOR (where R is an alkyl group having 1 to 3 carbon atoms), -N ⁺ R ₁ R ₂ R ₃ (wherein R ₁ , R ₂ and R ₃ are as above. ) Or a halogen atom.

The etchant composition is an etchant prepared by lowering the content of the fluorine-containing compound as compared to the general etchant composition, and when etching the glass substrate using this, it is possible to increase the surface quality of the etched glass substrate, in particular the polishing process proceeds after the etching process It can represent the surface quality that does not have to be in parallel, and can minimize the generation of sludge during etching. In addition, it is possible to improve the reuse rate of the etching solution by improving the etching ability. This can contribute to the thin-large technology of organic substrates.

Description

Etching composition

The present invention relates to an etchant composition, and relates to an etchant composition used for slimming a glass substrate.

Glass substrates are the core material of panels used as substrates such as TFT array and color filters, which are the components of TFT LCD panels. In general, the alkali component in the glass substrate degrades the TFT function. Therefore, the glass substrate for TFT LCD uses alkali-free glass with almost no alkali component, and the glass substrate has a flat surface that cannot be distinguished by the naked eye and deformation due to heat. It requires high quality properties such as not being present.

In the manufacture of glass substrates, the processing technology of melting and molding raw materials such as silica and alumina is the most important, and glass substrate products must have precise glass surface quality, no deformation by heat, and strong heat resistance to maintain glass quality even at high temperatures. Is required. The glass substrate manufacturing method uses about 60% of the fusion method, which has better surface quality than other processes, and the other method uses the float method.

Meanwhile, as TFT LCD panels become thin and thin, glass substrates are also required to be enlarged, slimmed, and lightweight. To this end, investments in new technologies such as the fusion method and excellent molding and processing technologies are under way. As a part of this, technology development for manufacturing a lighter glass by reducing the density of the glass, reducing the weight of the panel and uniformizing the glass thickness to 0.5 mm or less, etc., has recently been performed by chemically using an etchant. The way to reduce this trend is on the rise.

The etching process technology for display panels can be largely divided into equipment technology and etching solution technology. In terms of equipment technology, technology development is focused on etching technology of large panels, and technology development is focused on low concentration, recycling, and etching speed in terms of etching liquid technology. Recently, developments using various organic additives are in progress. It is becoming.

Japanese Patent Laid-Open Publication No. 2005-179132 discloses an etching solution containing hydrofluoric acid, ammonium bifluoride, phosphoric acid, ammonium phosphate salt, and aluminum halide as a technique for roughening a glass surface, and Japanese Laid-Open Patent Publication No. 2003-313049 The problem that loading occurs in a filtration process, piping, or a tank by the gel-like solid substance formed in etching liquid, and the etching liquid which added the barium compound to the etching liquid containing hydrofluoric acid for easy regeneration use of etching liquid are described.

Korean Patent No. 0677052 describes an etching solution having excellent cleaning ability to remove various defects such as defects and sealants, roll marks, and hand marks generated during etching, which is 1.5 to 10% by weight of hydrofluoric acid, phosphoric acid or ethylene. 25 to 45% by weight glycol, 20 to 40% by weight nitric acid and the composition comprising water so that the total weight of the total composition is 100% by weight.

In addition, Korean Patent No. 0868228 discloses an etching solution for a glass substrate that can etch the surface of the glass substrate smoothly and has a high etching speed with respect to the glass substrate, and also has excellent durability of etching ability. 45 weight percent, 1 to 10 weight percent of inorganic salts containing fluorine ions, 1 to 10 weight percent of one or more inorganic acids selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid and perchloric acid, and 100 weight percent of total composition It contains water.

The present invention is to provide an etchant composition that can increase the surface quality of the etched glass while minimizing sludge generation while reducing the content of hydrofluoric acid which is a strong acid.

The present invention also provides an etchant composition that can improve the reuse rate of the etchant.

The present invention is a fluorine-containing compound 7 to 20% by weight; 1 to 10% by weight of hydrochloric or nitric acid and 10 to 40% by weight of sulfuric acid as inorganic acid; 0.1 to 10% by weight bulky ammonium salt represented by the following formula (1); 0.1 to 5 wt% surfactant; And it provides a glass substrate etching liquid composition comprising an amount of water so that the total weight of the total composition is 100% by weight.

Formula 1

In the etching liquid composition according to one specific embodiment, the bulky ammonium salt represented by Formula 1 is A is -CH _2- , -CH ₂ CH _2- , -CH ₂ CH (OH)-, -CH ₂ CH (OH) CH _2- , CH ₂ CH ₂ -O- or-(CH ₂ CH ₂ O) ₂ -CH ₂ CH _2- ; X may be -OH, -COOH, -COOCH ₃ , -N ⁺ (CH ₃ ) ₃ or -Cl.

In the etching solution composition according to an embodiment of the present invention, the surfactant is monoethylene glycol, monopropylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether, di It may be at least one selected from ethylene glycol monobutyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, polyethylene glycol, low molecular weight polypropylene glycol, and glycerin.

In the etching solution composition according to an embodiment of the present invention, the fluorine-containing compound is at least one compound selected from the group consisting of HF, NaF, KF, KBF _4, Tetramethylammonium fluoride (TMAF), Tetrabutylammonium fluoride (TBAF) and NaBF ₄ Can be.

An exemplary embodiment of the present invention includes an etching process including a substrate etching process using the etchant composition according to the embodiments, and does not require a separate polishing process for the substrate after performing the etching process.

The etchant composition according to an embodiment of the present invention can increase the surface quality of the etched glass substrate when the glass substrate is etched using the same while lowering the content of the fluorine-containing compound as compared to the general etchant composition, in particular, after the etching process It is possible to exhibit the surface quality that does not have to be a parallel polishing process, it is possible to minimize the generation of sludge during etching. In addition, it is possible to improve the reuse rate of the etching solution by improving the etching ability. As a result, the etchant composition of the present invention may contribute to the thin-large-size technique of the organic substrate.

Hereinafter, the present invention will be described in detail.

The present invention relates to an etching liquid composition, in particular, a composition used for etching a glass substrate, wherein the term "glass substrate" includes all materials based on glass, for example, not only a glass substrate for LCD but also a PDP. Of course, it includes all glass substrates used for displays such as Plasma Display Panel (ELD) and Electroluminescent Display (ELD).

The etchant composition according to the present invention is 7 to 20% by weight of the fluorine-containing compound; 10 to 50% by weight of at least one inorganic acid selected from sulfuric acid, hydrochloric acid and nitric acid; 0.1 to 10% by weight bulky ammonium salt represented by the following formula (1); 0.1 to 5 wt% surfactant; And an amount of water such that the total weight of the total composition is 100% by weight.

Formula 1

Wherein R ₁ , R ₂ and R ₃ are the same as or different from each other, and are an alkyl group or a benzyl group having 1 to 14 carbon atoms,

A is an alkylene group or alkylene oxide group having 1 to 5 carbon atoms which is unsubstituted or substituted with a hydroxyl group,

X is -OH, -COOH, -COOR (where R is an alkyl group having 1 to 3 carbon atoms), -N ⁺ R ₁ R ₂ R ₃ (wherein R ₁ , R ₂ and R ₃ are the same as above) or It is a halogen atom.

Fluorine-containing compounds include, for example, HF, NaF, KF, KBF4, Tetramethylammonium fluoride (TMAF), Tetrabutylammonium fluoride (TBAF), NaBF ₄ , and these alone or in combination of two or more. It is also possible to use. Preferably, the fluorine-containing compound is HF.

The fluorine-containing compound may be included in an amount of 7 to 20% by weight, preferably 10 to 18% by weight, based on the total weight of the etchant composition. If the content is less than 10% by weight of the total etching solution composition, the etching rate is too slow, if the content is more than 18% by weight, the etching rate is faster, but the surface of the glass substrate is not smooth and the durability of the etching solution is poor.

The etchant composition of the present invention includes an inorganic acid, the inorganic acid serves to remove the residue generated during the etching of the glass substrate, thereby increasing the etching rate. As a specific example, containing 1 to 10% by weight of hydrochloric acid or nitric acid and 10 to 40% by weight of sulfuric acid based on the total weight of the etching solution composition increases the oxidation power of the etching solution to efficiently remove the residues generated during etching, while the etching rate It may be more desirable in terms of acting to increase the.

Meanwhile, the etchant composition of the present invention includes a bulky ammonium salt represented by Chemical Formula 1, which prevents dregs during etching, thereby improving etching ability and also smoothing the surface of the glass substrate.

The bulky ammonium salt represented by Formula 1 prevents the generation of glass slurries composed of silicon fluoride in bulk compared to inorganic salts known to be included in the etchant composition, and consequently prevents sludge generation during etching. can do.

The bulky ammonium salt may be added in an amount of up to 10% by weight based on the total weight of the etching liquid composition, specifically 0.1 to 10% by weight, preferably 0.1 to 5% by weight. If more than 10% by weight may be a slow etching rate, less than 0.1% by weight the role is negligible and as a result can not prevent the occurrence of debris during etching, ultimately it is difficult to improve the surface quality of the glass substrate.

Bulk ammonium salt represented by Formula 1 according to a specific embodiment is A is -CH _2- , -CH ₂ CH _2- , -CH ₂ CH (OH)-, -CH ₂ CH (OH) CH _2- , CH ₂ CH ₂ —O— or — (CH ₂ CH ₂ O) ₂ —CH ₂ CH ₂ —; X may be -OH, -COOH, -COOCH ₃ , -N ⁺ (CH ₃ ) ₃ or -Cl.

The etchant composition of the present invention includes a surfactant, which inhibits dissolution assistance and rapid acidity change of the etchant and has an effect of lowering the adhesion of sludge to the glass surface. Examples of the surfactant include glycols, and specific examples of the surfactant include monoethylene glycol, monopropylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, and diethylene glycol monoethyl. It may be at least one selected from ether, diethylene glycol monobutyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, polyethylene glycol, low molecular weight polypropylene glycol and glycerin. Preferred surfactants may be monoethylene glycol or glycerin. The surfactant is used in 0.1 to 5% by weight of the total etchant composition, preferably may be included in 1 to 3% by weight. If the content is less than 0.1% by weight of the total etching solution composition, the effect is insignificant, and if the content is 5% by weight or more, the glass substrate surface property is reduced.

The method of preparing the etchant composition from the above-described components is not particularly limited, and the etchant composition may be obtained when the total weight of the etchant is 100% by weight including water together with the above-described components.

The etching method to which the etchant composition of the present invention is applied is not particularly limited. For example, in the etching method, a dip-bubble method and a large size (3rd generation size or more) applied to glass of smaller size (2nd generation size or less, 370x470, 590x670) according to the size of the glass substrate to be processed There is a spray method applied to glass. The dip-bubble method is a method in which an object to be treated is immersed in an etch bath that is being aerated. Generally, the process is performed by applying the elevated temperature according to etching without maintaining a constant temperature. Etching is performed while spraying glass and maintaining a constant temperature.

The etchant composition of the present invention can be applied by all such etching methods to maintain the quality of the etching rate, the etching ability and the etching target.

In the etching method using the etching solution composition of the present invention, the surface quality of the substrate is excellent even if the polishing process is not performed after the etching process for the substrate.

As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated and described in detail in the detailed description. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

Hereinafter, the present invention will be illustrated by the following examples, but the protection scope of the present invention is not limited only to the following examples.

Comparative Example 1

An 18 wt% aqueous solution of hydrofluoric acid was prepared as a glass etchant.

Comparative Example 2

A 20 wt% aqueous solution of hydrofluoric acid was prepared as a glass etchant.

Examples 1 to 13 and Comparative Examples 3 to 5

Next, an etchant composition was prepared using the same ingredients and blending ratios as those shown in Table 1. In Table 1, the content unit is weight% of 100% by weight of the total composition, and the remainder is water content.

division HF Inorganic acids Surfactants Formula 1 compound Sulfuric acid Hydrochloric acid nitric acid A X R ₁ , R ₂ , R ₃ content Comparative Example 3 18 20 - - One - - - - Comparative Example 4 16 18 4 - One - - - - Comparative Example 5 12 15 - 4.5 One - - - - Example 1 16 17 - 4 1.5 -CH ₂ CH _2- -OH All CH ₃ CH _2- 1.5 Example 2 15 20 - 2 One -CH ₂ CH _2- -OH All CH ₃ CH _2- 0.5 Example 3 16 18 1.5 4 One -CH ₂ CH _2- -OH All CH ₃ CH _2- 3 Example 4 16 18 One 3 0.5 -CH ₂ CH _2- -COOH All CH _3- 1.5 Example 5 16 18 - 5 One -CH ₂ CH _2- -COOH All CH _3- 2.5 Example 6 16 18 - 3 2 -CH _2- -COOH All CH _3- 3 Example 7 16 18 - 4 2 -CH ₂ CH (OH)- -Cl All CH _3- One Example 8 15 20 1.5 5 3 -CH ₂ CH (OH) CH _2- -COOH All CH _3- 2 Example 9 16 18 - 4 One -CH ₂ CH ₂ -COOCH ₃ All CH _3- 1.5 Example 10 16 18 - 4.5 2.5

All CH _3- 0.5 Example
11 15 20 2 2.5 1.5 -CH ₂ CH (OH)- -COOH All CH _3- 1.5 Example
12 16 18 - 3.5 One

-OH R ₁ , R ₂ = CH _3- , R ₃ =-(CH ₂ ) ₁₃ CH ₃ 0.8 Example
13 16 18 - 3.5 One -CH ₂ CH ₂ -OH R ₁ , R ₂ = CH _3- , R ₃ =

One

Experimental Example 1: Spray etching

The etching rate, the surface quality after etching, and the etching ability of the glass substrate were evaluated using the etching solution compositions obtained from the above Examples and Comparative Examples.

The substrate to be etched is an etch-free alkali glass (Samsung Corning's Eagle 2000, size: 370 x 470mm, thickness: 1.2T) in which the upper and lower plates are bonded and the liquid crystal is added in the LCD process, to remove contaminants. The thickness of each portion was determined and measured by micrometer.

With the temperature maintained at 25 ° C. to 28 ° C., the prepared substrates were added to the compositions prepared by the above examples and comparative examples, respectively. After etching for 10 minutes, the etching power is measured and the etching liquid composition is sprayed and etched for a time corresponding to the required etching amount (1.2T → 0.6T), and the etched glass is washed with a pure water in a washing machine and dried. After passing through, the thickness of each part was measured to measure the etching rate (the ratio of the changed thickness to the etching time), and the results are shown in Table 2 below.

On the other hand, the etching retention ability was evaluated by comparing the longevity when the constant etching rate (5.0㎛ / min) at a constant etching rate (5.0㎛ / min) by using the same etching solution to evaluate the etching retention ability, the etching solution for 1 hour after completion of etching The amount of sludge accumulated in the stagnation was measured to compare the relative values, and the results are shown in Table 2 below.

Etching defects were also observed using a three-wavelength lamp. Observation of the panel at an angle compared the etch staining and transparency. The surface quality of the etched glass substrate was evaluated and the results are shown in Table 2 below.

The criteria for judging each evaluation result are as follows.

◎: Very good, ○: Good, △: Normal, X: Bad

◎: 600 sheets or more

○: 500 sheets or more

△: 400 sheets or more

X: 400 or less

◎: unchecked stain

○: less than 5% stain

△: less than 15% of stain

X: more than 15% of stain

◎: slurry ratio less than 10%

○: slurry ratio less than 10% to 30%

△: slurry ratio less than 30% to 50%

X: slurry ratio 50% or more

Etch solution Etching rate
(μm / min) Etch maintenance ability Surface quality Residue Comparative Example 1 8 X △ X Comparative Example 2 14 X X X Comparative Example 3 12 X X X Comparative Example 4 15 △ X X Comparative Example 5 12 X △ △ Example 1 16 ◎ ◎ ◎ Example 2 13.5 ○ ◎ ○ Example 3 15 ◎ ◎ ○ Example 4 14.3 ◎ ◎ ○ Example 5 15.2 ◎ ◎ ○ Example 6 15 ◎ ○ ○ Example 7 15.8 ◎ ○ ○ Example 8 14.5 ◎ ◎ ○ Example 9 14 ◎ ◎ ○ Example 10 14.8 ○ ◎ ○ Example 11 13.8 ○ ◎ ○ Example 12 14.6 ○ ◎ ○ Example 13 15 ○ ○ ○

From the results of Table 2, the etching solution composition of the present invention did not decrease the etching rate even though the content of the fluorine-containing compound was lowered, and the etching ability and the quality of the etched glass substrate also showed a result.

Experimental Example 2: Dipping Etching

With the temperature maintained at 25 ° C. to 28 ° C., the prepared substrate was added to each of the compositions prepared by the above Examples and Comparative Examples. After etching for 10 minutes, the etching power is measured and the etching liquid composition is sprayed and etched for a time corresponding to the required etching amount (1.2T → 0.6T), and the etched glass is washed with a pure water in a washing machine and dried. After passing through, the thickness of each part was measured to measure the etching rate (the ratio of the changed thickness with respect to the etching time), and the results are shown in Table 3 below.

On the other hand, the etching retention ability was evaluated by comparing the longevity when the constant etching rate (5.0㎛ / min) at a constant etching rate (5.0㎛ / min) by using the same etching solution to evaluate the etching retention ability, the etching solution for 1 hour after completion of etching The amount of sludge accumulated in the stagnation was measured and the relative numerical comparison was performed. The results are shown in Table 3 below.

Etching defects were also observed using a three-wavelength lamp. Observation of the panel at an angle compared the etch staining and transparency. The surface quality of the etched glass substrate was evaluated and the results are shown in Table 3 below.

Each evaluation result judgment criteria are the same as in Experimental Example 1.

Etch solution Etching rate
(μm / min) Etch maintenance ability Surface quality Residue Comparative Example 1 6 X △ X Comparative Example 2 11 X X X Comparative Example 3 8 X X X Comparative Example 4 12.5 △ X X Comparative Example 5 9 X △ X Example 1 13.5 ◎ ◎ ◎ Example 2 11 ○ ◎ ○ Example 3 11.5 ○ ◎ ○ Example 4 11 ◎ ◎ ○ Example 5 12 ◎ ◎ ○ Example 6 11.5 ◎ ◎ ○ Example 7 12.5 ◎ ◎ ○ Example 8 11.8 ○ ◎ ○ Example 9 11.5 ○ ◎ ○ Example 10 13.2 ○ ◎ ○ Example 11 12.5 ○ ○ ○ Example 12 12.8 ○ ◎ ○ Example 13 13.2 ○ ○ ○

From the results of Table 3, the etching solution composition of the present invention did not decrease the etching rate even though the content of the fluorine-containing compound was lowered, and the etching ability and the quality of the etched glass substrates were also improved. It can be seen that these results are independent of the etching method.

On the other hand, after the etching using a dipping method using a non-bonded Eagle 2000 glass using the embodiment of the above embodiment confirmed the surface roughness deviation using AFM (Atomic Force Microscope, XE-70, Parksystems) It was. The results of measuring the surface of the etched glass by AFM are shown in Table 4 and FIGS. 1 to 6, respectively.

1 is an AFM photograph of Comparative Example 2, FIG. 2 is Comparative Example 3, FIG. 3 is Example 1, FIG. 4 is Example 5, FIG. 5 is Example 7, and FIG. 6 is AFM photograph of Example 11. .

Etch solution Ra (nm) Comparative Example 2 9.534 Comparative Example 3 4.071 Example 1 1.182 Example 5 1.532 Example 7 1.177 Example 11 1.201

Table 4 and the results of FIGS. 1 to 6, the etching liquid composition of the present invention, despite the lower content of the fluorine-containing compound, the average roughness (Roughness) value of the glass surface is measured to be less excellent surface uniformity It can be confirmed that the quality of the glass substrate also showed an improvement. This result is independent of the etching method.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims. It will be understood that the invention may be varied and varied without departing from the scope of the invention.

1 is an AFM photograph of Comparative Example 2.

2 is an AFM photograph of Comparative Example 3.

3 is an AFM photograph of Example 1. FIG.

4 is an AFM photograph of Example 5. FIG.

5 is an AFM photograph of Example 7. FIG.

6 is an AFM photograph of Example 11. FIG.

Claims

Fluorine-containing compound 7 to 20% by weight;

As the inorganic acid, 1 to 10% by weight of hydrochloric or nitric acid and 10 to 40% by weight of sulfuric acid;

0.1 to 10% by weight bulky ammonium salt represented by the following formula (1);

0.1 to 5 wt% surfactant; And

A glass substrate etching liquid composition comprising an amount of water such that the total weight of the total composition is 100% by weight.

Formula 1

A is -CH _2- , -CH ₂ CH _2- , -CH ₂ CH (OH)-, -CH ₂ CH (OH) CH _2- , CH ₂ CH ₂ -O- or-(CH ₂ CH ₂ O) ₂ -CH ₂ CH _2- ,

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The method of claim 1, wherein the surfactant is monoethylene glycol, monopropylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, di A glass substrate etching liquid composition comprising at least one selected from propylene glycol, dipropylene glycol monomethyl ether, polyethylene glycol, low molecular weight polypropylene glycol, and glycerin.

The glass substrate etchant composition of claim 1, wherein the fluorine-containing compound is at least one compound selected from the group consisting of HF, NaF, KF, KBF _4, Tetramethylammonium fluoride (TMAF), Tetrabutylammonium fluoride (TBAF), and NaBF ₄ . .

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