KR20110121122A - A detergent composition for a glass substrate of flat panel display device - Google Patents

Abstract

PURPOSE: A cleaning composition is provided to ensure excellent removal power of organic contaminants and particles on the surface of the glass substrate of a flat panel display. CONSTITUTION: A cleaning composition for a glass substrate for a flat panel display comprises: non-ionic surfactants in which alkylene oxide is added to terpene-based oil represented by chemical formula 1; glycol ether-based organic solvents represented by chemical formula 2; alkali metal hydroxide; and water. The cleaning composition has pH of 12~14. In chemical formulas 1 and 2, AO is an oxyethylene group, an oxypropylene group, or a polyoxyethylene·polyoxypropylene block copolymer; n1 is 1~40; R1 is hydrogen, methyl group or ethyl group; R2 is hydrogen, methyl group, ethyl group or ethyl alcohol; n2 is 2~3; and X is 1~3.

Description

Cleaner composition for glass substrate of flat panel display device {A DETERGENT COMPOSITION FOR A GLASS SUBSTRATE OF FLAT PANEL DISPLAY DEVICE}

The present invention relates to a glass substrate cleaning composition of a flat panel display device which is a low-foaming aqueous cleaning agent.

A flat panel display device (FPD), like a semiconductor device, is 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 steps, and there have been many proposals for cleaning agents for this purpose. For example, Korean Patent Laid-Open Publication No. 2003-0039408 discloses an aqueous cleaner including a nonionic surfactant in which an alkylene oxide is added to an aromatic alcohol and a nonionic surfactant in which an alkylene oxide is added to a hydrocarbon alcohol. However, since a nonionic surfactant having an alkylene oxide added to a long chain hydrocarbon is used, bubbles are generated in a process such as spraying. In addition, Korean Patent No. 10-0574607 proposes a detergent containing deionized water, an organic compound and an ammonium compound in an acidic pH environment. However, since it is an acidic cleaner, it is insufficient to remove very small particles having a size of 1 μm or less, which is a basic characteristic of the initial stage of cleaning. In addition, Japanese Patent Application Laid-open No. Hei 7-133496 proposes a cleaning composition comprising a nonionic surfactant in which an alkylene oxide is added to a long-chain alcohol, a short-chain glycol ether solvent, a long-chain glycol ether, and a solvent paraffinic or olefinic hydrocarbon and water. It was. However, there is a possibility of flammability and drying problems when using hydrocarbon solvents. In addition, when the carbon number of the terminal alkyl group is increased, the viscosity of the detergent and the solubility in water may decrease.

It is an object of the present invention to provide a glass substrate cleaning composition for a flat panel display device which is a low-aqueous water-based cleaner which can increase the cleaning effect and productivity by completely removing contaminants present on the glass substrate.

The present invention is a nonionic surfactant to which the alkylene oxide is added to the terpene-based oil represented by the formula (1); A glycol ether organic solvent represented by Formula 2; Alkali metal hydroxides; And it provides water, and provides a cleaning composition for a flat panel display glass substrate, characterized in that the pH 12 ~ pH 14.

<Formula 1>

<Formula 2>

In Chemical Formula 1 and Chemical Formula 2,

AO is an oxyethylene group, an oxypropylene group, or a polyoxyethylene polyoxypropylene block copolymer, n1 is 1-40,

R ₁ is a hydrogen atom, a methyl group or an ethyl group, R ₂ is a hydrogen atom, a methyl group, an ethyl group or an ethyl alcohol, n ₂ is 2-3 and X is 1-3.

The cleaning composition of the present invention is excellent in removing organic contaminants and particles on the surface of the glass substrate of the flat panel display device. The detergent composition of the present invention is easy to handle and environmentally advantageous because it contains no residue after rinsing and contains a large amount of deionized water.

1 is a photograph showing a contact angle before cleaning using the cleaning composition of Example 9.
FIG. 2 is a photograph showing a contact angle after cleaning using the cleaning composition of Example 9. FIG.
3 is a photograph showing a glass substrate contaminated with oily pen marks before using the cleaning composition of Example 16.
Figure 4 is a photograph showing a glass substrate that was contaminated with oil pen marks after using the detergent composition of Example 16.

Hereinafter, the present invention will be described in detail.

The cleaning composition for glass substrates of the flat panel display device of this invention is pH12-pH14, and contains a nonionic surfactant, a glycol ether organic solvent, an alkali metal hydroxide, and water.

The nonionic surfactant contained in the glass substrate cleaning composition of the flat panel display device of the present invention is a nonionic surfactant in which alkylene oxide is added to a terpene-based oil represented by the following formula (1).

<Formula 1>

In Formula 1, AO is an oxyethylene group, an oxypropylene group or a polyoxyethylene polyoxypropylene block copolymer, and n ₁ is 1 to 40.

The nonionic surfactant represented by Chemical Formula 1 exhibits low foaming properties in the spraying process, and easily removes contaminants from the organic substrate by improving wet penetration.

Based on the total weight of the composition, the nonionic surfactant represented by Formula 1 is preferably included in 0.01 to 5% by weight, more preferably in 0.1 to 2% by weight. If it is included below the above range, it is difficult to quickly penetrate the cleaning agent to the interface between the glass substrate surface and the contaminants such as particles, so that there is a problem that the cleaning power to the contaminants is reduced. When the above-mentioned range is exceeded, the wet penetrating force is strong, and the cleaning composition remains on the surface of the glass substrate, and the surfactant remains on the substrate even in the rinsing step. In addition, the degree of foaming due to the increase in viscosity of the cleaning composition is severe, there is a problem that the workability is reduced in the process.

As the nonionic surfactant represented by Formula 1, a commercially available product may be used, and examples thereof include Rhodoclean ASP, Rhodoclean MSC, Rhodoclean EFC, and Rhodoclean HP (above, Rhodia products).

The glycol ether organic solvent contained in the glass substrate cleaning composition of the flat panel display device of the present invention is represented by the following formula (2).

<Formula 2>

In Formula 2, R ₁ is a hydrogen atom, a methyl group or an ethyl group, R ₂ is a hydrogen atom, a methyl group, an ethyl group or ethyl alcohol, n ₂ is 2 to 3, X is 1 to 3.

The glycol ether-based organic solvent represented by Chemical Formula 2 increases the wettability of the surface of the glass substrate, thereby improving the ability to remove oil components on the surface of the glass substrate, which is difficult to remove only by the nonionic surfactant represented by Chemical Formula 1, that is, cleaning ability. In addition, the glycol ether-based organic solvent improves the dissolving power and rinsing power of the cleaning composition of the present invention.

The total weight of the composition, the glycol ether organic solvent represented by the formula (2) is preferably contained in 0.05 to 40% by weight, more preferably contained in 0.5 to 20% by weight. If it is included in the above-described range, it is not possible to increase the dissolving power of the cleaning composition due to the addition of the glycol ether-based organic solvent to the organic contaminants. It is uneconomical.

The glycol ether-based organic solvent represented by the formula (2) is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl It is preferably selected from the group consisting of ether, propylene glycol monomethyl ether and dipropylene glycol monoethyl ether.

The alkali metal hydroxide contained in the glass substrate cleaning composition of the flat panel display device of the present invention has high alkalinity. This lowers the molecular weight of the organic contaminants or oily organic compounds of the polymer and increases the peelability to the glass substrate, thereby imparting cleaning power to the glass substrate.

The alkali metal hydroxide is preferably included in an amount of 0.05 to 5% by weight, and more preferably 0.1 to 2% by weight based on the total weight of the composition. If included below the above range, it is not easy to remove the particles or organic contaminants attached to the glass substrate. If the above-mentioned range is exceeded, the cleaning effect is no longer increased, and the price of the cleaning agent is increased, which may cause uneconomical and environmental problems.

The alkali metal hydroxide is preferably selected from the group consisting of KOH, NaOH and mixtures thereof. The reason is that it is easy to obtain and economical while giving high alkalinity.

The water included in the glass substrate cleaning composition of the flat panel display device of the present invention refers to deionized water, and is used for a semiconductor process. Preferably, water of 18 μs / cm or more is used. With respect to the total weight of the composition, the amount of water is included so that the total weight of the etchant composition of the present invention is 100% by weight.

The glass substrate cleaning composition of the present invention may further include a conventional additive in addition to the above components, and the additive may include a metal ion blocking agent, a pH adjusting agent, and the like.

The cleaning composition of the present invention is excellent in removing organic contaminants and particles on the surface of the glass substrate of the flat panel display device. The detergent composition of the present invention is easy to handle and environmentally advantageous because it contains no residue after rinsing and contains a large amount of deionized water.

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 1-16, Comparative Examples 1-4: 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.

Surfactant (wt%) Glycol Ether Organic Solvents
(weight%) Alkali Metal Hydroxide
(weight%) water Example 1 One) One EG 5 KOH One Balance Example 2 One) 0.5 EG 3 KOH One Balance Example 3 One) One EDG One KOH 0.5 Balance Example 4 One) 0.5 EDG 2 KOH One Balance Example 5 One) One MG 10 KOH 0.5 Balance Example 6 One) 0.5 MG 10 KOH One Balance Example 7 One) One MDG One KOH One Balance Example 8 2) 0.1 MDG One KOH 3 Balance Example 9 2) One MTG 5 KOH 2 Balance Example 10 2) 2 MTG 5 KOH 0.5 Balance Example 11 3) 0.05 EG 10 NaOH One Balance Example 12 3) 0.5 EG 2 NaOH 2 Balance Example 13 One) 2 EG One NaOH 0.5 Balance Example 14 One) 0.05 MG 10 NaOH 0.5 Balance Example 15 2) One EDG One NaOH One Balance Example 16 2) 0.5 MDG 5 NaOH 2 Balance Comparative Example 1 - - - - KOH 6 Balance Comparative Example 2 One) One EG 2 - - Balance Comparative Example 3 - - MG 0.05 KOH 0.1 Balance Comparative Example 4 2) 6 - - NaOH One Balance

Note 1) Rhodoclean ASP 2) Rhodoclean MSC

3) Rhodoclean EFC

EG: ethylene glycol monoethyl ether

EDG: diethylene glycol monoethyl ether

MG: ethylene glycol monomethyl ether

MDG: diethylene glycol monomethyl ether

MTG: triethylene glycol monomethyl ether

BG: Ethylene Glycol Monobutyl Ether

Test Example: Evaluation of Characteristics of Cleaning Composition

<Evaluation of pollutant removal in air>

100 ml of the cleaning composition of Examples 1 to 16 and Comparative Examples 1 to 4 were placed in a beaker with a volume of 250 ml, respectively. Meanwhile, in order to evaluate the removal power of the contaminants, the glass substrates having a size of 5 cm x 5 cm were left to stand in the air for 3 days for contamination.

The contaminated substrate was cleaned with the cleaning composition of Examples 1 to 16 and Comparative Examples 1 to 4 for 1 minute at room temperature using a spray glass substrate cleaning device (manufacturer: SEMES). After washing for 30 seconds in ultrapure water and dried with nitrogen. The degree of removal of contaminants was evaluated by the contact angle reduction before and after cleaning using a contact angle measuring device (model name: DSA100, manufacturer: KRUSS), and the results are shown in Table 2.

<Evaluation of Organic Pollutant Removal>

To assess the removal power of organic contaminants, stain the human fingerprint on the glass substrate 5 cm x 5 cm, and contaminate the contaminated substrate at room temperature for 1 minute using a spray glass substrate cleaner (manufacturer: SEMES). It washed with the cleaning composition of Examples 1-16 and Comparative Examples 1-4. After washing for 30 seconds in ultrapure water and dried with nitrogen. The results are shown in Table 2.

<Evaluation of Particle Removal>

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 subjected to Examples 5 and 6 at room temperature for 1 minute using a spray-type glass substrate cleaner. It wash | cleaned with the cleaning composition of Example 9, Example 10, Example 11, Example 16, and Comparative Example 2 and Comparative Example 3. After washing for 30 seconds in ultrapure water and dried with nitrogen. The number of particles before and after cleaning was measured by a particle size measuring instrument (Topcon WM-1500) of 0.3 ㎛ or more, the results are shown in Table 3.

<Evalence pen marks removal ability evaluation>

In order to evaluate the removal power of organic contaminants, the oil-based pen was contaminated on a glass substrate formed of 2 cm x 5 cm, and the contaminated substrate was cleaned at room temperature for 1 minute using a spray-type glass substrate cleaning apparatus. It wash | cleaned with the cleaning composition of 9, Example 10, Example 11, Example 16, and Comparative Example 2 and Comparative Example 3. After washing for 30 seconds in ultrapure water and dried with nitrogen. The results are shown in Table 3.

Air pollutant cleaning power Organic pollutant removal Example 1 ○ ○ Example 2 ○ ○ Example 3 ○ ○ Example 4 ○ ○ Example 5 ◎ ○ Example 6 ◎ ○ Example 7 ○ ○ Example 8 ○ ○ Example 9 ◎ ◎ Example 10 ◎ ○ Example 11 ◎ ○ Example 12 ○ ○ Example 13 ○ ○ Example 14 ○ ○ Example 15 ○ ○ Example 16 ◎ ◎ Comparative Example 1 ◎ △ Comparative Example 2 X △ Comparative Example 3 ○ X Comparative Example 4 ○ X

<Assessment of Pollutant Removal Capacity in the Air>

◎: excellent (40? Abnormal decrease), ○: good (40 ~ 30? Reduced)

(Triangle | delta): Inadequate (30-20 degree reduction), X: Defective (less than 20 degree reduction)

<Evaluation of Organic Pollutant Removal>

◎: excellent (contaminant remaining rate 0%), ○: good (contaminant remaining rate less than 20%)

△: Insufficient (contaminant remaining rate 20 to 50%) X: Poor (contaminant remaining rate 50% or more)

Number of particles before cleaning Number of particles after cleaning Removal rate (%) Meteor Penza International Castle Example 5 2644 265 90 ○ Example 6 2715 302 89 ○ Example 9 2755 237 91 ○ Example 10 2786 209 92 ○ Example 11 2805 192 93 ○ Example 16 2752 140 95 ○ Comparative Example 2 2708 760 72 x Comparative Example 3 2785 633 77 x

<Evalence pen marks removal ability evaluation>

○: Good (no oily pen marks) X: Bad (no oily pen marks removed)

Referring to Table 2, using the cleaning composition of Examples 1 to 16, it showed that there is a removal power of all contaminants, it can be seen that the contact angle is reduced by more than 30 ° exhibits the ability to remove organic contaminants. Moreover, it turns out that particle removal power is also excellent. On the other hand, in the case of the cleaning compositions of Comparative Examples 1 to 4 in which the alkali metal hydroxide, the ethylene glycol organic solvent, or the nonionic surfactant added with the alkylene oxide to the terpene oil was not added, it was found that the ability to remove contaminants decreased. Can be.

1 is a photograph which shows the contact angle before washing | cleaning using the detergent composition of Example 9. FIG. FIG. 2 is a photograph showing a contact angle after cleaning using the cleaning composition of Example 9. FIG.

1 and 2, it can be seen that the contact angle before and after cleaning is reduced to effectively remove the air pollutants.

Referring to Table 3, it can be seen that particles and oil pen marks are effectively removed using the cleaning compositions of Examples 5, 6, 9, 10, 11 and 16. On the other hand, using the cleaning composition of Comparative Example 2 and Comparative Example 3, it can be seen that the particle removal force is lowered, the oil pen is not removed.

On the other hand, Figure 3 is a photograph showing a glass substrate contaminated with oil-based pen marks before using the cleaning composition of Example 16. Figure 4 is a photograph showing a glass substrate that was contaminated with oil pen marks after using the detergent composition of Example 16.

3 and 4, it can be seen that the oil pen is effectively removed.

Claims (4)

Nonionic surfactant to which the alkylene oxide is added to the terpene-based oil represented by Formula 1;
A glycol ether organic solvent represented by Formula 2;
Alkali metal hydroxides; And
A flat panel display glass substrate cleaning composition comprising water and having a pH of 12 to pH 14:
<Formula 1>

<Formula 2>

In Chemical Formula 1 and Chemical Formula 2,
AO is oxyethylene group, an oxy-propylene group or a polyoxyethylene-polyoxypropylene block copolymer, n ₁ is 1-40,
R ₁ is a hydrogen atom, a methyl group or an ethyl group, R ₂ is a hydrogen atom, a methyl group, an ethyl group or an ethyl alcohol, n ₂ is 2-3 and X is 1-3. The method according to claim 1,
Regarding the total weight of the composition,
0.01 to 5% by weight of a nonionic surfactant having an alkylene oxide added to the terpene-based oil represented by Formula 1;
0.05 to 40% by weight of a glycol ether organic solvent represented by Formula 2;
0.05-5% by weight of the alkali metal hydroxide; And
The cleaning composition for a flat panel display glass substrate comprising the remaining amount of water. The method according to claim 1,
The glycol ether-based organic solvent represented by the formula (2) is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl A detergent composition for a flat panel display glass substrate, characterized in that selected from the group consisting of ether, propylene glycol monomethyl ether and dipropylene glycol monoethyl ether. The method according to claim 1,
The alkali metal hydroxide is selected from the group consisting of KOH, NaOH and mixtures of the flat panel display cleaner composition for a glass substrate.

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