KR20120029526A - Metal-cleaning composition for manufacturing flat panel display - Google Patents

Abstract

PURPOSE: An environment-friendly metal cleaning composition is provided to have excellent removing force of metal attached on a metal mask and a metal substrate, especially alkaline earth metal, and to be easy to handle by including a plurality of deionized water. CONSTITUTION: An environment-friendly metal cleaning composition comprises 0.1-80 weight% of inorganic alkali, 0.1-50 weight% of organic acid, 0.01-10 weight% of azole based compound, 0.01-10 weight% of phosphoric acid or salt thereof, and water residue, on the basis of total weight of the composition. The inorganic alkali is one or more kinds selected from a group consisting of ammonium hydroxide, sodium hydroxide, potassium hydroxide and their mixtures.

Description

Metal cleaning composition for manufacturing flat panel display device {METAL-CLEANING COMPOSITION FOR MANUFACTURING FLAT PANEL DISPLAY}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal mask and a metal substrate cleaning composition in a flat panel display (FPD) manufacturing process, particularly in an organic light emitting display (OLED) manufacturing process.

A flat panel display (FPD), which is represented by a liquid crystal display, is manufactured through processes such as film formation, exposure, and etching, and in each manufacturing process, very small particles having a size of 1 μm or less, such as various organic materials and inorganic materials, on the substrate surface. Are attached, causing contamination. Since contamination by these particles lowers the yield of the device, it is necessary to reduce as much as possible before entering the post-process.

Therefore, cleaning to remove contaminants is performed between the steps, and many proposals have been made for cleaning liquids for this purpose.

In particular, Korean Patent Laid-Open Publication No. 2008-0046632 discloses a method for cleaning a metal mask, which comprises washing the metal mask with an organic solvent that dissolves organic substances adhered to the metal mask, and vacuum drying the metal mask washed with pure water. Is disclosed. However, this method is not effective for removing metal adhered to the metal mask, organic solvents tend to remain due to the use of organic solvents, and vacuum drying is required for the drying process of the metal mask. There are a lot of disadvantages.

The present invention is excellent in the removal of metal attached to the metal mask and the metal substrate during the organic material deposition process in the manufacturing process of the flat panel display (FPD), in particular the organic light emitting display (OLED) manufacturing process, the metal does not corrode the lower metal plate It is an object to provide a cleaning composition.

Thus, the present invention provides a metal cleaning composition comprising an inorganic alkali, an organic acid, an azole compound, an organic phosphoric acid or a salt thereof, and water.

The cleaning liquid composition of the present invention is excellent in removing the metal attached to the metal mask and the metal substrate during the manufacturing process of the flat panel display device, inter alia, alkaline earth metal and copper group elements, excellent corrosion protection effect on the lower metal plate, such as stainless, It contains a large amount of deionized water, which is easy to handle and environmentally beneficial.

1 is a SEM photograph of a metal substrate on which Invar is deposited by cosputtering magnesium and silver.
2 is an SEM photograph of a metal substrate having a residue of Comparative Example 3. FIG.
3 is an SEM photograph of a metal substrate having no residue and almost no damage in Example 5. FIG.

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

The metal cleaning liquid composition of the present invention is characterized by containing an inorganic alkali, an organic acid, an azole compound, an organic phosphoric acid or a salt thereof, and water.

The inorganic alkali is a main component for cleaning the metal, and the content of the inorganic alkali is 0.1 to 80% by weight, preferably 1 to 50% by weight based on the total weight of the composition.

If the content of the inorganic alkali is less than 0.1% by weight, the cleaning power is poor, and the removal of the metal film is not easy. If the content of the inorganic alkali exceeds 80% by weight, there is a possibility of corrosion of the metal. May cause.

The inorganic alkali is preferably at least one selected from the group consisting of ammonium hydroxide, sodium hydroxide, potassium hydroxide and mixtures thereof.

The organic acid is another main component for cleaning the metal film, and the content of the organic acid is 0.1 to 50% by weight, preferably 0.5 to 20% by weight based on the total weight of the composition.

If the content of the organic acid is less than 0.1% by weight, it is not easy to remove the metal film. If the content of the organic acid is more than 50% by weight, there is a possibility of corrosion of silicon and metal, and the manufacturing cost of the cleaning solution is increased, resulting in low economical efficiency and environmental problems. have.

The organic acid is preferably an acid containing a carboxyl group, for example, formic acid, acetic acid, propionic acid, glyoxylic acid, pyruvic acid, gluconic acid, 2-ketogulonic acid, 1,3-acetone dicarboxylic acid, oxalic acid, malonic acid, Succinic acid, glutaric acid, adipic acid, pimer acid, maleic acid, formic acid, phthalic acid, hydroxybutyric acid, p-toluenesulfonic acid, lactic acid, salicylic acid, malic acid, tartaric acid, citric acid, aspartic acid and glutamic acid. .

The azole compound is a corrosion preventing component of the metal substrate, and serves to prevent damage to the lower metal substrate by the cleaning power of the inorganic alkali and organic acid. It also acts as an auxiliary cleaner to help clean the metal film.

The content of the azole compound is 0.01 to 10% by weight based on the total weight of the composition.

If the content of the azole compound is less than 0.01% by weight, the corrosion protection is lowered, damaging the lower metal film or the insulating film, and the metal cleaning power is also reduced. If it is more than 10% by weight, the cleaning power is drastically lowered and economical efficiency is lowered due to environmental problems and rising costs.

The azole compound is tolyltriazole, benzotriazole, triazole, aminotriazole, aminotetrazole, imidazole, hydroxybenzotriazole, methylbenzotriazole, benzotriazole carboxylic acid, nitrobenzotriazole, pyri It is preferably one or two or more selected from the group consisting of midine, pyrrole, pyrrolidine, pyrroline and butylphenol, but is not limited thereto.

The organic phosphoric acid or a salt thereof is a corrosion preventing component of the metal substrate, and serves to prevent damage of the lower metal substrate due to the cleaning power of the alkali alkali and the organic acid. It also acts as a sub-cleaner to help clean metal substrates.

The content of the organic phosphoric acid or salts thereof is 0.01 to 10% by weight, based on the total weight of the composition.

If the content of the organic phosphoric acid or its salt is less than 0.01% by weight, the corrosion protection is lowered, damaging the lower metal substrate or the insulating film, and the metal cleaning power is also reduced.

In addition, when the content of the organic phosphoric acid or its salt is more than 10% by weight, the cleaning power is sharply lowered, causing environmental problems, and the cost is lowered due to the increased cost.

The organic phosphoric acid or salt thereof is methyldiphosphonic acid, aminotri (methylenephosphonic acid), ethylidenediphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxypropylidene-1 , 1-diphosphonic acid, 1-hydroxybutylidene-1,1-diphosphonic acid, ethylaminobis (methylenephosphonic acid), 1,2-propylenediaminetetra (methylenephosphonic acid), dodecylaminobis ( Methylenephosphonic acid), nitrotris (methylenephosphonic acid), ethylenediaminebis (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), hexenediaminetetra (methylenephosphonic acid) and diethylenetriaminepenta (methylenephosphonic acid) , Cyclohexanediaminetetra (methylenephosphonic acid) and salts thereof are preferably one or two or more selected from the group consisting of, but is not limited thereto. Here, the salt of the organophosphoric acid is preferably a potassium salt or a sodium salt.

The water is contained in the remaining amount relative to the total weight of the composition, and as deionized water, it is preferable that there is no metallic impurities.

The cleaning liquid composition of the present invention can be produced by a conventionally known method, and preferably has a purity for a semiconductor process.

The cleaning method to which the metal cleaning composition according to the present invention is applied is not particularly limited, and can be applied to methods such as immersion cleaning, rocking cleaning, ultrasonic cleaning, shower-spray cleaning, puddle cleaning, brush cleaning, and stirring cleaning. In the present invention, an immersion cleaning method or an ultrasonic cleaning method is particularly preferable.

The metal to be cleaned in the present invention is a metal attached to a metal mask and a metal substrate during the organic material deposition process in a flat panel display (FPD) manufacturing process, in particular, an organic electroluminescent display (OLED) manufacturing process, in particular alkaline earth metal and copper It is a group element. The cleaning composition of the present invention is excellent for the removal of the metal and does not corrode the lower metal plate such as stainless.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are intended to illustrate the present invention more specifically, but the scope of the present invention is not limited by the following examples.

Example  1 to 10 and Comparative example  1-4 : Preparation and Cleaning of Metal Cleaning Composition

It mixed and stirred with the component and composition of Table 1, and prepared the cleaning composition.

Inorganic alkali Organic acid Azole compound Organophosphate or salt water Kinds weight% Kinds weight% Kinds weight% Kinds weight% Example 1 NaOH 30 *One) 0.5 * 9) 0.01 * 14) 0.01 Balance Example 2 NaOH 10 *One) 0.5 * 10) One * 15) One Balance Example 3 NaOH 30 *2) 10 * 13) 0.01 * 17) 0.01 Balance Example 4 NaOH 10 *2) 10 * 10) One * 14) One Balance Example 5 KOH 15 * 3) 10 * 11) One * 15) One Balance Example 6 KOH 15 * 3) 10 * 9) One * 14) One Balance Example 7 KOH 15 *4) 15 * 12) One * 16) 3 Balance Example 8 KOH 20 * 5) 15 * 11) One * 17) 3 Balance Example 9 KOH 20 * 6) 20 * 13) 3 * 16) 3 Balance Example 10 KOH 20 * 7) 20 * 11) 3 * 17) 3 Balance Comparative Example 1 NaOH 0.05 *One) 10 * 9) One * 14) One Balance Comparative Example 2 NaOH 10 *2) 0.05 * 10) One * 15) One Balance Comparative Example 3 KOH 20 * 3) 10 * 11) 0.001 * 16) One Balance Comparative Example 4 KOH 20 *4) 10 * 12) One * 17) 0.001 Balance

* 1): citric acid

* 2): glyoxylic acid

* 3): Gluconic Acid

* 4): Oxalic acid

* 5): Succinic acid

* 6): salicylic acid

* 7): p-toluenesulfonic acid

* 8): maleic acid

* 9): Benzotriazole

* 10) aminotriazole

* 11) aminotetrazole

* 12): imidazole

* 13): Pyrrole

* 14): 1-hydroxypropylidene

* 15) 1,2-propylenediaminetetra (methylenephosphonic acid)

* 16): ethylenediaminebis (methylenephosphonic acid)

* 17): diethylenetriamine penta (methylenephosphonic acid)

Test Example : Evaluation of Properties of Metal Cleaning Composition

In order to evaluate the properties of the cleaning composition of the present invention, a metal substrate co-deposited with magnesium (Mg) and silver (Ag) on Invar was used (FIG. 1). By the immersion method, each of the cleaning compositions prepared in Examples 1 to 10 and Comparative Examples 1 to 4 were put, and the temperature was set to 20 to 80 ° C., followed by heating, and the metal substrate was immersed. Then, the metal film was taken out, washed with deionized water, and dried using a drying apparatus. After cleaning and drying, the surface roughness, residues such as corrosion and damage of the surface and residues were analyzed by using an electron scanning microscope and energy dispersion spectroscopy (SEM and EDS: manufactured by Hitachi, model name: S-4700). 2 is shown.

room
city
Yes
One room
city
Yes
2 room
city
Yes
3 room
city
Yes
4 room
city
Yes
5 room
city
Yes
6 room
city
Yes
7 room
city
Yes
8 room
city
Yes
9 room
city
Yes
10 ratio
School
Yes
One ratio
School
Yes
2 ratio
School
Yes
3 ratio
School
Yes
4 Residue
The presence or absence ○ ○ ○ ○ ○ ◎ ◎ ◎ ◎ ◎ × × △ △ damaged
The presence or absence △ ○ △ ○ ○ ○ ○ ○ ○ ○ △ ○ X X

◎: very good ○: excellent

△: Good X: Poor (metal film disappeared and residues occurred)

As shown in Table 2, the cleaning composition according to the present invention was excellent in the cleaning power for the metal, it was confirmed that does not cause damage, such as corrosion of the metal substrate.

Claims (9)

A composition for cleaning metals comprising an inorganic alkali, an organic acid, an azole compound, an organic phosphoric acid or a salt thereof, and a residual amount of water. The method according to claim 1, wherein the total weight of the composition, the content of the inorganic alkali is 0.1 to 80% by weight, the content of the organic acid is 0.1 to 50% by weight, the content of the azole-based is 0.01 to 10% by weight, The organic phosphoric acid or its salt content is 0.01 to 10% by weight of the metal cleaning composition. The composition for cleaning metals according to claim 1, wherein the inorganic alkali is at least one selected from the group consisting of ammonium hydroxide, sodium hydroxide, potassium hydroxide and mixtures thereof. The composition for cleaning metals according to claim 1, wherein the organic acid is an acid containing a carboxyl group. The method according to claim 1, wherein the organic acid Formic acid, acetic acid, propionic acid, glyoxylic acid, pyruvic acid, gluconic acid, 2-ketogulonic acid, 1,3-acetonedicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, mare Phosphoric acid, formic acid, phthalic acid, hydroxybutyric acid, p-toluenesulfonic acid, lactic acid, salicylic acid, malic acid, tartaric acid, citric acid, aspartic acid and glutamic acid. The method of claim 1, wherein the azole compound is tolyltriazole, benzotriazole, triazole, aminotriazole, aminotetrazole, imidazole, hydroxybenzotriazole, methyl benzotriazole, benzotriazole carboxylic acid, nitro Metal composition for cleaning metal, characterized in that one or two or more selected from the group consisting of benzotriazole, pyrimidine, pyrrole, pyrrolidine, pyrroline and butylphenol. The method of claim 1, wherein the organic phosphoric acid or a salt thereof is methyldiphosphonic acid, aminotri (methylenephosphonic acid), ethylidenediphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydride Oxypropylidene-1,1-diphosphonic acid, 1-hydroxybutylidene-1,1-diphosphonic acid, ethylaminobis (methylenephosphonic acid), 1,2-propylenediaminetetra (methylenephosphonic acid), Dodecylaminobis (methylenephosphonic acid), nitrotris (methylenephosphonic acid), ethylenediaminebis (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), hexenediaminetetra (methylenephosphonic acid) and diethylenetriaminepenta (Methylenephosphonic acid), cyclohexanediaminetetra (methylenephosphonic acid) and salts thereof. The metal cleaning composition, characterized in that one or two or more selected from the group consisting of. The metal cleaning composition of claim 1, wherein the metal is a metal attached to a metal mask and a metal substrate during a flat panel display manufacturing process. The composition of claim 8, wherein the metal is an alkaline earth metal or a copper group element.

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