KR20120133077A - Detergent composition for flat panel display device - Google Patents

Abstract

PURPOSE: A cleansing composition is provided to remove organic and inorganic pollutants or particles on a glass substrate, electrode, or wire, and to have excellent cleansing effect without corrosion of an electrode or wire. CONSTITUTION: A cleansing composition for a flat display device comprises 0.01-10 weight% of a quaternary ammonium salt, 0.01-10 weight% of a glycolether compound, 0.01-10 weight% of a phosphate compound, 0.01-5 weight% of a glycerin compound, 0.01-1 weight% of a contact angle reducer, and residual water. The quaternary ammonium salt is one or more kinds selected from tetramethylammmonium hydroxide, tetramethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabuthylamonium hydroxide.

Description

Cleaner composition for flat panel display device {DETERGENT COMPOSITION FOR FLAT PANEL DISPLAY DEVICE}

The present invention relates to a cleaning composition for a flat panel display device.

Flat panel display devices, like semiconductor devices, are manufactured through processes such as film formation, exposure, and etching. However, by such a manufacturing process, adhesion contamination occurs due to very small particles having various organic and inorganic substances having a size of 1 μm or less on the substrate surface. When the following process treatment is performed while these particles are attached, pinholes and pits of the film, disconnection and bridges of the wiring are generated, and the production yield of the product is reduced.

Therefore, cleaning to remove contaminants is performed between the respective processes, and much research has been conducted on cleaning agents for this purpose. Korean Patent Laid-Open No. 2008-0038161 discloses a release agent composition for a semiconductor device composed of organic amine, organic phosphonic acid, linear sugar alcohol and water. However, the disclosed patent is limited to the use as a semiconductor device, there is a disadvantage that there is no anticorrosive ability for the wiring made of copper and copper alloy. Korean Patent Laid-Open Publication No. 2004-0035368 discloses a cleaning composition for a semiconductor and a TFT-LCD composed of an alkanol amine, an organic solvent, a chelating compound, and water. However, the disclosed patent lacks the ability to remove organic contaminants and particles, and may cause precipitation problems during long-term use due to catechol or gallic acid, which are polyhydroxy benzene-based chelate compounds. Korean Patent Laid-Open Publication No. 2006-0127098 discloses a cleaning agent for a semiconductor device substrate comprising an organic acid component, an organic alkali component, a surfactant component, and water. However, since the cleaning agent of the published patent is an acidic solution, it is insufficient to remove particles of very small particles having a size of 1 μm or less, which is a basic characteristic of the initial stage of cleaning. And, there is a disadvantage that only the anticorrosive effect on the copper wiring.

An object of the present invention is to provide a cleaning composition for a flat panel display device capable of removing organic-inorganic contaminants or particles present on a glass substrate, an electrode or a wiring.

SUMMARY OF THE INVENTION An object of the present invention is to provide a cleaning composition for a flat panel display device that exhibits a cleaning effect without corroding an electrode or wiring made of a metal containing copper used in the flat panel display device.

An object of the present invention is to provide a cleaning composition for a flat panel display device, which is economical and environmentally friendly, without causing a rinse problem.

The present invention is 0.01 to 10% by weight of the quaternary ammonium salt compound based on the total weight of the composition; 0.01 to 10% by weight of a glycol ether compound; 0.01-10 weight% of a phosphate ester compound; 0.01 to 5% by weight glycerin compound; 0.01 to 1% by weight of a contact angle reducing agent; And it provides a cleaning composition for a flat panel display device comprising a residual amount of water.

The cleaning composition for a flat panel display device of the present invention can remove organic-inorganic contaminants or particles present on a glass substrate, an electrode, or a wiring. The cleaning composition for a flat panel display device of the present invention can exert a cleaning effect without corroding an electrode or a wiring made of a metal containing copper used in the flat panel display device. The cleaning composition for a flat panel display device of the present invention lowers the possibility of rinsing problems by using a large amount of water. In addition, the cleaning composition for a flat panel display device of the present invention is economical and environmentally friendly.

1 is a photograph showing a glass substrate contaminated with organic sign pen marks among organic contaminants.
Figure 2 is a photograph showing the result of removing the organic sign pen marks in the organic contaminants using the cleaning composition according to Example 4 of the present invention.
3 is a photograph showing a copper substrate contaminated with fingerprints among organic contaminants.
4 is a photograph showing a result of removing fingerprint contamination components from organic contaminants using the cleaning composition according to Example 4 of the present invention.

Hereinafter, the present invention will be described in detail.

The cleaning composition for a flat panel display device of the present invention includes a quaternary ammonium salt compound, a glycol ether compound, a phosphate ester compound, a glycerin compound, a contact angle reducing agent and water.

The quaternary ammonium salt compound included in the cleaning composition for a flat panel display device of the present invention provides excellent cleaning ability against organic-inorganic contaminants and particles, and provides excellent anticorrosion ability for an electrode or wiring made of a metal including copper.

The quaternary ammonium salt compound is included in an amount of 0.01 to 10% by weight and 0.05 to 5% by weight based on the total weight of the composition. When the above-mentioned range is satisfied, the cleaning ability is excellent with respect to organic-inorganic contaminants and particles, and the anticorrosion ability with respect to the electrode or the wiring which consists of metal containing copper becomes excellent.

The quaternary ammonium salt compound is selected from the group consisting of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH) and tetrabutylammonium hydroxide (TBAH) It is preferable that it is 1 type, or 2 or more types.

The glycol ether compound included in the cleaning composition for a flat panel display device of the present invention increases the dissolving power to organic and inorganic contaminants and particles, and provides economic and environmental advantages.

The glycol ether compound is preferably included in an amount of 0.01 to 10% by weight, and 0.05 to 5% by weight based on the total weight of the composition. When the above-mentioned range is satisfied, the dissolving power to organic-inorganic contaminants and particles is increased, and the problem of remaining of the cleaning agent does not occur after the cleaning process is completed, and economical and environmental benefits may be provided.

The glycol ether compound is ethylene glycol monobutyl ether (BG), diethylene glycol monomethyl ether (MDG), diethylene glycol monoethyl ether (carbitol), diethylene glycol monobutyl ether (BDG), dipropylene glycol monomethyl ether (DPM), dipropylene glycol monoethyl ether (MFDG), triethylene glycol monobutyl ether (BTG), triethylene glycol monoethyl ether (MTG) and propylene glycol monomethyl ether (MFG) Or it is preferable that it is 2 or more types.

The phosphate ester compound included in the cleaning composition for a flat panel display device of the present invention functions as a cosolvent of proton and aprotic solvents, and provides an excellent cleaning effect on organic contaminants and organic-based stains on a substrate. And, even in a small amount, it has an excellent ability to remove organic contaminants.

It is preferable that the said phosphate ester compound is contained in 0.01 to 10 weight% with respect to the total weight of a composition, and is contained in 0.05 to 5 weight%. If the above-mentioned range is satisfied, it is possible to provide an excellent cleaning effect on organic contaminants and organic-based stains located on the substrate.

It is preferable that the said phosphate ester compound is represented by following General formula (1).

≪ Formula 1 >

In Formula 1,

R ₁ to R ₃ are each independently a hydrogen atom, a C ₁ to C ₁₀ linear or branched alkyl group. The alkyl group is preferably a methyl group, an ethyl group, a propyl group or a butyl group.

Examples of the phosphate ester compound represented by Formula 1 include methyl phosphate, dimethyl phosphate, trimethyl phosphate, ethyl phosphate, diethyl phosphate, triethyl phosphate, tripropyl phosphate and tributyl phosphate.

The said phosphate ester compound can be used individually or in mixture of 2 or more types.

The glycerin compound included in the cleaning composition for a flat panel display device of the present invention prevents corrosion of an electrode or wiring made of a metal containing copper and improves organic cleaning power.

The glycerin compound is contained in 0.01 to 5% by weight, and preferably contained in 0.05 to 2% by weight based on the total weight of the composition. When the above-mentioned range is satisfied, the anticorrosive property for the electrode or the wiring made of a metal containing copper is excellent without lowering the cleaning power for organic contaminants.

The contact angle reducing agent included in the cleaning composition for a flat panel display device of the present invention is included to secure the hydrophilicity of the substrate after the cleaning process, and prevents the metal including copper from corroding.

The contact angle reducing agent is included in 0.01 to 1% by weight, preferably 0.01 to 0.5% by weight based on the total weight of the composition. If the above-described range is satisfied, it is easier to secure the hydrophilicity of the substrate after the cleaning process, and the anticorrosive characteristics of the electrode or the wiring made of a metal including copper can be improved.

It is preferable that the said contact angle reducing agent is thioglycerine.

The water contained in the cleaning composition for a flat panel display device of the present invention includes the remaining amount so that the total weight of the composition is 100% by weight. The water is used for the semiconductor process, preferably deionized water of 18 ㏁cm or more.

The cleaning composition for a flat panel display device of the present invention can impart anticorrosion ability to an electrode or a wiring made of a metal containing copper without using a triazole-based compound. When the triazole-based compound is used, the anti-corrosion ability is excellent, but there is a problem that the triazole-based compound is adsorbed on the copper surface.

The present invention provides a flat panel display device made of the cleaning composition for the flat panel display device. Examples of the flat panel display include an organic light emitting display device and a liquid crystal display.

The cleaning composition for a flat panel display device of the present invention can remove organic-inorganic contaminants or particles present on a glass substrate, an electrode, or a wiring. The cleaning composition for a flat panel display device of the present invention can exert a cleaning effect without corroding an electrode or a wiring made of a metal containing copper used in the flat panel display device. The cleaning composition for a flat panel display device of the present invention lowers the possibility of rinsing problems by using a large amount of water. In addition, the cleaning composition for a flat panel display device of the present invention is economical and environmentally friendly.

Hereinafter, the present invention will be described in more detail with reference to Examples and Test Examples. However, the scope of the present invention is not limited by the following examples and test examples.

Examples 1-12, Comparative Examples 1-5: Preparation of Cleaning Composition

In the mixing tank equipped with a stirrer, the components shown in Table 1 were mixed according to the composition ratios shown in Table 1, and stirred at a speed of 500 rpm for 1 hour at room temperature to prepare a cleaning composition.

Quaternary Ammonium Compound Glycol ether Phosphate Ester glycerin Thioglycerine water Kinds weight% Kinds weight% Kinds weight% weight% weight% Example 1 TMAH 0.1 BG 1.0 TMP 1.0 0.5 0.1 Balance Example 2 TMAH 0.5 MDG 1.0 TBP 1.0 0.5 0.1 Balance Example 3 TMAH 1.0 MTG 1.0 TPP 1.0 0.5 0.1 Balance Example 4 TMAH 2.0 BDG 1.0 TEP 1.0 1.0 0.5 Balance Example 5 TMAH 2.0 BG 0.5 TMP 1.0 1.0 0.5 Balance Example 6 TMAH 2.0 MDG 1.5 TBP 1.0 1.0 0.5 Balance Example 7 TMAH 2.0 MTG 2.0 TPP 1.0 0.5 0.1 Balance Example 8 TMAH 2.0 BDG 2.5 TEP 1.0 0.5 0.1 Balance Example 9 TEAH 2.0 BG 1.5 TMP 0.5 0.5 0.1 Balance Example 10 TEAH 2.0 MDG 1.5 TBP 1.5 1.0 0.5 Balance Example 11 TEAH 2.0 MTG 1.5 TPP 2.0 1.0 0.5 Balance Example 12 TEAH 2.0 BDG 1.5 TEP 2.5 1.0 0.5 Balance Comparative Example 1 - - BDG 1.5 TEP 2.5 1.0 0.5 Balance Comparative Example 2 TEAH 0.05 - - TEP 2.5 1.0 0.5 Balance Comparative Example 3 TEAH 0.05 BDG 0.5 - - 1.0 0.5 Balance Comparative Example 4 TEAH 0.05 BDG 0.5 TEP 0.5 - - Balance Comparative Example 5 TEAH 8 BDG 15 TEP 15 10 2 Balance

TMAH: tetramethylammonium hydroxide TEAH: tetraethylammonium hydroxide

BG: Ethylene Glycol Monobutyl Ether MDG: Diethylene Glycol Monomethyl Ether

BDG: diethylene glycol monobutyl ether MTG: triethylene glycol monoethyl ether

TMP: trimethyl phosphate TBP: tributyl phosphate

TPP: Tripropyl Phosphate TEP: Triethyl Phosphate

Test Example: Evaluation of Characteristics of Cleaning Composition

1) copper etch rate evaluation

First, a glass substrate having a copper thickness of 2500 kV is immersed in the cleaning composition of Examples 1 to 12 and Comparative Examples 1 to 5 for 30 minutes. At this time, the temperature of the cleaning agent is 25 ℃ and is measured before and after immersing the thickness of the copper film, it is measured by calculating the dissolution rate of the copper film from the change in the thickness of the copper film. The results are shown in Table 2.

2) Contaminant Removability Evaluation-1

In order to evaluate the removal power of organic contaminants, the glass substrate and the copper substrate formed of 2 cm x 2 cm were contaminated with organic sign pens and fingerprints. It washed with the cleaning composition of Examples 1-12 and Comparative Examples 1-5. After washing, it was washed with ultrapure water for 30 seconds and then dried with nitrogen.

※ Evaluation criteria for the removal of organic sign pens (drying for 24 hours after contamination with organic sign pens)

○: When removed, X: When not removed

※ Evaluation criteria for removing fingerprints on copper substrate

10: When completely removed, 0: When not removed

3) Pollutant removal power evaluation-2

In addition, the copper substrate is left in the air for 24 hours to contaminate various organic substances, inorganic substances, particles, and the like in the air, and then, using a spray-type copper substrate cleaning apparatus, at a temperature of 25 ° C. for 1 minute, Examples 1 to 12 and Comparative Example 1 To the cleaning composition of Comparative Example 5. After washing for 30 seconds in ultrapure water and dried with nitrogen. 0.5 μl of ultrapure water was dropped on the glass substrate to measure the contact angle after washing. The results are shown in Table 2.

4) Particle Removal

Cleaning was performed on the glass substrate contaminated with the inorganic particle solution with the cleaning agent compositions of Examples 1 to 12 and Comparative Examples 1 to 5. More specifically, the glass substrate was contaminated with an organic particle solution having an average particle size of 0.8 μm, spin dried at 3000 rpm for 1 minute, and then sprayed at 25 ° C. for 1 minute using a spray glass substrate cleaner. Washed with detergent. After washing, it was washed with ultrapure water for 30 seconds and then dried with nitrogen. The number of particles before and after cleaning was measured by a particle size measuring instrument (Topcon WM-1500) of 0.1 μm or more, which is shown in Table 2.

Cu etching rate
(Å / min) abandonment
Signature pen Fingerprint contamination Contact angle particle
Removal rate (%) Example 1 0.7 ○ 8 28 82 Example 2 1.1 ○ 8 26 80 Example 3 0.9 ○ 8 29 87 Example 4 1.0 ○ 9 28 91 Example 5 1.0 ○ 8 30 88 Example 6 0.9 ○ 9 31 85 Example 7 0.9 ○ 8 29 86 Example 8 0.9 ○ 8 31 84 Example 9 1.1 ○ 9 31 88 Example 10 1.4 ○ 9 30 89 Example 11 1.1 ○ 9 28 91 Example 12 0.8 ○ 9 29 89 Comparative Example 1 0.9 △ 2 56 62 Comparative Example 2 1.1 △ 4 31 84 Comparative Example 3 1.8 X One 31 85 Comparative Example 4 62 ○ 7 61 81 Comparative Example 5 198 ○ 9 63 80

Referring to Table 2, it can be seen that the cleaning composition of Examples 1 to 12 according to the present invention is excellent in anticorrosive performance for copper, and also excellent in removal ability against organic sine pen and air pollutant.

On the other hand, Figure 1 is a photograph showing a glass substrate contaminated with organic sign pen marks of organic contaminants. Figure 2 is a photograph showing the result of removing the organic sign pen marks in the organic contaminants using the cleaning composition according to Example 4 of the present invention. 3 is a photograph showing a copper substrate contaminated with fingerprints among organic contaminants. 4 is a photograph showing a result of removing fingerprint contamination components from organic contaminants using the cleaning composition according to Example 4 of the present invention.

1 to 4, it can be seen that using the cleaning composition of Example 4, the cleaning ability against organic contaminants is excellent.

On the other hand, in the case of Comparative Example 1, Comparative Example 2, Comparative Example 3, it can be seen that the cleaning power for organic siphon, fingerprint contamination, air pollutants and the like is not excellent. In the case of Comparative Example 4, it can be seen that the corrosion resistance to copper is not excellent, and the cleaning power to air pollutants is not excellent. In the case of Comparative Example 5, the anticorrosive performance against copper was not excellent, and the removal ability to air pollutants was also not excellent.

Claims (7)

With respect to the total weight of the composition,
0.01-10% by weight of quaternary ammonium salt compound;
0.01 to 10% by weight of a glycol ether compound;
0.01-10 weight% of a phosphate ester compound;
0.01 to 5% by weight glycerin compound;
0.01 to 1% by weight of a contact angle reducing agent; And
Cleaning composition for a flat panel display comprising a residual amount of water. The method according to claim 1,
The quaternary ammonium salt compound is selected from the group consisting of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH) and tetrabutylammonium hydroxide (TBAH) The cleaning composition for a flat panel display device which is 1 type or 2 or more types. The method according to claim 1,
The glycol ether compound is ethylene glycol monobutyl ether (BG), diethylene glycol monomethyl ether (MDG), diethylene glycol monoethyl ether (carbitol), diethylene glycol monobutyl ether (BDG), dipropylene glycol monomethyl ether (DPM), dipropylene glycol monoethyl ether (MFDG), triethylene glycol monobutyl ether (BTG), triethylene glycol monoethyl ether (MTG) and propylene glycol monomethyl ether (MFG) Or two or more kinds of cleaning composition for a flat panel display device. The method according to claim 1,
The phosphate ester compound is a detergent composition for a flat panel display characterized in that represented by the formula (1):
≪ Formula 1 >

In Chemical Formula 1,
R ₁ to R ₃ are each independently a hydrogen atom, a C ₁ to C ₁₀ linear or branched alkyl group. The method of claim 4,
The phosphate ester compound is one or two or more selected from the group consisting of methyl phosphate, dimethyl phosphate, trimethyl phosphate, ethyl phosphate, diethyl phosphate, triethyl phosphate, tripropyl phosphate and tributyl phosphate Detergent composition for the device. The method according to claim 1,
The contact angle reducing agent is a cleaning composition for a flat panel display, characterized in that thioglycerine. A flat panel display comprising a cleaning composition for a flat panel display according to claim 1.

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