WO2011052988A2

WO2011052988A2 - Cleaner composition for glass substrate of flat panel display device

Info

Publication number: WO2011052988A2
Application number: PCT/KR2010/007416
Authority: WO
Inventors: 윤효중; 김성식; 고경준
Original assignee: 동우 화인켐 주식회사
Priority date: 2009-10-30
Filing date: 2010-10-27
Publication date: 2011-05-05
Also published as: CN102482616A; KR101673589B1; CN102482616B; JP2013509482A; JP5603948B2; TWI512099B; TW201127946A; KR20110047693A; WO2011052988A3

Abstract

The present invention relates to a cleaner composition for a glass substrate of a flat panel display device, and said composition comprises: a non-ionic surfactant in which alkylene oxide is added to oil; polyvalent alcohol compounds; alkali metal hydroxide; and water, wherein the cleaner composition has a pH range of 12 to 14.

Description

The name of the invention: Detergent composition for glass substrate of flat panel display

The present invention relates to a glass substrate cleaning composition of a flat tube display device which is a low-foaming aqueous cleaning agent. The present invention claims the benefit of the filing date of Korean Patent Application No. 10-2009-0104416 filed with the Korea Patent Office on October 30, 2009, the entire contents of which are incorporated herein.

Background

FPDC 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 a size of one or less of various organic materials and inorganic materials on the substrate surface. When the following process treatment is performed while these particles are attached, pinholes, pits, disconnection of wires or bridges are generated, and the yield of the product is reduced.

Therefore, cleaning to remove contaminants is performed between the processes, 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 non-ionic surfactant having an alkylene oxide added to an aromatic alcohol and a nonionic surfactant having an alkylene oxide 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 the process. In addition, Korean Patent No. 10-0574607 proposes a cleaning solution containing deionized water, an organic compound and an ammonium compound in an acidic pH environment. However, since it is an acidic cleaning solution, it is insufficient to remove very small particles having a size of l / m or less, which is a basic characteristic of the initial stage of cleaning. In addition, Japanese Patent Laid-Open No. 7-133496 discloses a cleaning composition comprising a nonionic surfactant in which alkylene oxide is added to a long chain alcohol, a short chain glycol ether solvent, a long chain glycol ether solvent, a paraffinic or olefinic hydrocarbon and water. Suggested. 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.

Content of Invention

Technical challenge

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

Technical solution

The present invention is a nonionic surfactant to which the alkylene oxide is added to the terpene-based oil represented by the formula (1); Alkali metal hydroxides; And water and a pH 12 to pH 14 cleaner for the flat panel display glass substrate. Provide a composition:

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

Favorable effect

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.

Brief description of the drawings

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. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

Glass substrate cleaning composition of the flat panel display device of the present invention is PH12 to pH14, and it contains a nonionic surfactant, a polyhydric alcohol type compound, 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).

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

The nonionic surfactant represented by Chemical Formula 1 is preferably included in 0.01 to 5 heavy rings, more preferably 0.1 to 2% by weight, based on the total weight of the composition. If it is contained below the above-mentioned range, it is difficult to quickly infiltrate the cleaning liquid into 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. If it exceeds the above-mentioned range, the wet penetrating force is strong so that the cleaning composition remains on the glass substrate surface. do. In the rinse process, the surfactant remains on the substrate. 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, commercially available products may be used, such as Rhodoclean ASP, Rhodoclean MSC, Rhodoclean EFC, and Rhodoclean HP (above, manufactured by Rhodia).

The polyhydric alcohol-based compound included in the glass substrate cleaning composition of the flat panel display device of the present invention increases the wettability of the surface of the glass substrate to remove oil components on the surface of the glass substrate that are difficult to remove only by the nonionic surfactant represented by Chemical Formula 1. Improve the ability, ie cleaning power. In addition, the polyhydric alcohol-based compound improves the dissolving and rinsing power of the cleaning composition of the present invention to water.

The polyhydric alcohol-based compound, based on the total weight of the composition, is preferably included in 0.01 to 5 heavy rings ¾, more preferably contained in 0.1 to 3 heavy rings ᅳ When included in less than the above range, wettability to the surface of the glass substrate Lack of grant If it exceeds the above-mentioned range, it is uneconomical.

The polyhydric alcohol compound is ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanedi, 2-methyl-1, 3 ᅳ propanediol, glycerol, trimethyl ethane, trimethylolpropane, pentaerythri, xylly, manny, sorby, erydri, adoni, tray, arabi, and tally It is preferable that it is 1 type, or 2 or more types chosen from.

Alkali contained in the cleaning composition for glass substrates of the flat panel display device of this invention. Metal hydroxides have 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 contained in 0.05 to 5% by weight, more preferably in 0.1 to 2% by weight of 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. When the above range is exceeded, the cleaning effect is no longer increased, and the price of the cleaning liquid is increased, which may cause uneconomical and environmental problems.

The alkali metal hydroxide is preferably one 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.

Water included in the glass substrate cleaning composition of the flat panel display device of the present invention means deionized water and is used for a semiconductor process, and preferably 18 ΜΩ. Water of αη or more is used. With respect to the total weight of the composition, the water is contained in a balance such that the total weight of the detergent 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 ρΗ control 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. After cleaning the cleaning composition of the present invention It is easy to handle and environmentally beneficial as it contains no residue and contains a large amount of deionized water. Mode for Carrying Out the Invention 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 to 17, Comparative Examples 1 to 4: Preparation of the cleaning composition In a mixing tank equipped with a stirrer, the components shown in Table 1 below were mixed according to the composition ratios shown in Table 1, and at room temperature for 1 hour. The cleaner composition was prepared by stirring at a speed of 500 rpm. Table 1 Surfactant Polyhydric Alcohol Compound Alkali Metal Hydroxide Water

(Medium) (Medium ¾¾) (Medium ¾)

Example 1 1) 1 a) 1 0H 1 remaining amount

Example 2 1) 1 a) 0.5 K0H 1 remaining amount

Example 3 1) 1 a) 3 K0H 1 remaining amount

Example 4 1) 0.5 a) 2 K0H 0.5 Remaining amount

Example 5 1) 1 b) 1 K0H 1 remaining amount

Example 6 1) 0.5 b) 0.5 K0H 2 Remaining amount

Example 7 1) 1 b) 0.1 K0H 4 Remaining amount

Example 8 2) 1 a) 1 K0H 1 remaining amount

Example 9 2) 1 b) 1 0H 1 Remaining amount

Example 10 2) 1 c) 1 K0H 1 remaining amount

Example 11 3) 1 c) 1 0.5 Residue

Example 12 3) 1 a) 1 謹 1 remaining amount

Example 13 3) 0.5 a) 2 Na (0.5 remaining amount of H)

Example 14 1) 2 a) 1 Naffl 0.5 Residue

Example 15 1) 0.2 b) 2 NaQH 1 remainder

Example 16 2) 1 c) 1 NaOH 1 remainder

Example 17 2) 0.5 c) 2 NaOH 1 remainder

Comparative Example 1 ᅳ---KOH 5 remaining

Comparative Example 2 1) 1 a) 2--Remaining amount

Comparative Example 3-a) 0.05 關 0.1 remaining amount

Comparative Example 4 2) 3 ᅳ-誦 1 remaining amount

A) sorbbi b) glycerol c) ethylene glycol 1) Rhodoclean ASP

2) Rhodoclean MSC 3) Rhodoclean EFC

TMAH: Tet r amethy 1 ammoni umhydroxi de

Test Example: Evaluation of Characteristics of Cleaning Composition

The detergent compositions 100 ^ of Examples 1-17 and Comparative Examples 1-4 were each placed in a beaker of a capacity of 250. Meanwhile, in order to evaluate the removal power of the contaminants, the glass substrate was formed in a 5 cm 5 cm size and left for 3 days to contaminate.

The contaminated substrate was cleaned with the cleaning composition of Examples 1 to 17 and Comparative Examples 1 to 4 for 1 minute at room temperature using a spray glass substrate cleaning apparatus. 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, and the results are shown in Table 2.

In order to evaluate the removal power of organic contaminants, the surface of the glass substrate formed by 5 cm x 5 cm was contaminated with human fingerprint marks, and the contaminated substrate was compared with Examples 1 to 17 in real conditions for 2 minutes using a spray glass substrate cleaning device. It wash | cleaned with the cleaning composition of Examples 1-4. 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, and 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, spin dried at 3000 rpm for 1 minute, and then sprayed at a room temperature for 2 minutes using a glass substrate cleaner. Examples 3, 4 and 4 It wash | cleaned with the cleaning composition of 9, Example 10, Example 17, the comparative example 2, and the comparative example 4. After washing for 30 seconds in ultrapure water and dried with nitrogen. The number of particles before and after cleaning was measured by the surface particle counter (Topcon 醫 -1500) and the number of particles above 0.¾ was shown in Table 3.

TABLE 2

Δ: Poor (20-10 ° decrease), X: Poor (less than 10 ° decrease) Table 3

Referring to Table 2 and Table 3, using the cleaning composition of Examples 1 to 17, 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. In addition, it can be seen that the particle removal ability is also excellent. On the other hand, in the case of the cleaning composition of Comparative Examples 1 to 4, it can be seen that there is a cleaning capacity only for a specific contaminant, not all contaminants. In addition, it can be seen that the particle removal rate is also not excellent.

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

Claims

Claim

Claim 1 The nonionic surfactant which the alkylene oxide added to the terpene-type oil represented by General formula (1);

Polyhydric alcohol compounds;

Alkali metal hydroxides; And

A flat panel display glass substrate cleaning composition comprising water and having a pH of 12 to 14:

In Chemical Formula 1,

AO is an oxyethylene group, an oxypropylene group or a polyoxyethylene polyoxypropylene block copolymer,

n is 1 to 40.

Claim 2 The method according to claim 1,

With respect to the total weight of the composition _, 0.01 to 5 of the nonionic surfactant in which the alkylene oxide is added to the terpene-based oil represented by Formula 1 ^

0.01 to 5 heavy rings of the polyhydric alcohol compound; 0.05 to 5 heavy rings of the alkali metal hydroxide; And

The cleaning composition for a flat panel display glass substrate comprising the remaining amount of water.

Claim 3 The method according to claim 1,

The polyhydric alcohol compound is ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanedi, 2-methyl-1, In the group consisting of 3-propanediol, glycerol, trimethylol ethane, trimethylolpropane, pentaerythritol, xylly, manny, solbi, erydri, adoni, tray, arabi and tally A cleaning composition for a flat panel display glass substrate, characterized in that one or two or more selected.

Claim 4 The method according to claim 1,

The alkali metal hydroxide is a cleaning composition for a flat panel display glass substrate, characterized in that one kind selected from the group consisting of KOH, NaOH and their mixtures.