KR20110016136A - Cleaning composition and process of cleaning panel using the composition - Google Patents

Abstract

PURPOSE: A cleaning composition is provided to ensure removal ability for organic materials and particle on the surface of glass of a flat panel display substrate and easy handling due to a large amount of deionized water. CONSTITUTION: A cleaning composition for a flat panel display substrate comprises: an oxyamine compound represented by chemical formula 1; an additive containing single or two or more kinds selected from the group consisting of azole-based compounds, alkanol amine salt, and reducing agents; and water. In the chemical formula 1, R1 is C1~3 linear or chain type hydroxyalkyl group and C1~3 linear or chain type thiolalkyl group; R2 and R3 are hydrogen, C1~4 alkyl group, C1~4 hydroxy alkyl group, C6~10 aryl group, C1~4 alkoxyalkyl group, and C1~4 alkoxyalkanol group; and n is a natural number of 1-4.

Description

Cleaning liquid composition and cleaning method using the same {Cleaning Composition and Process of Cleaning Panel Using the Composition}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning liquid for a substrate for flat panel displays (hereinafter referred to as "FPD"), such as a liquid crystal display, a plasma display, and a flexible display, and a cleaning method using the same.

FPD represented by a liquid crystal display is manufactured like a semiconductor device through processes, such as film-forming, exposure, wiring etching, and the like. However, by such a process, adhesion contamination of very small particles having a size of 1 μm or less of various organic materials or inorganic materials occurs on the surface of the substrate. When the following process treatment is carried out with these contaminants 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 steps, and many proposals have been made for the cleaning liquid for this purpose. For example, Japanese Laid-Open Patent Publication No. 2005-154558 proposes a cleaning liquid containing H ₃ PO ₄ , HF, ammonia, and / or an amine. However, this patent is not only a cleaning liquid for semiconductor devices, but also includes a glass substrate, which is the most representative FPD substrate, and HF, which intensively etches Al, which is the most representative wiring material, and thus can be used to clean the FPD substrate. Can't.

Japanese Unexamined Patent Application Publication No. 2000-232063 proposes to use phosphoric acid and ammonium phosphate as corrosion inhibitors, but the application process is not only for removing resist residues, but also the pH of the used composition is used in an acidic range. Phosphorus organic matter, inorganic matters, etc., having a very small particle removal of less than 1 µm and insufficient corrosion resistance of aluminum wiring are insufficient.

On the other hand, Korean Patent Publication No. 10-0574607 proposed a cleaning solution containing deionized water, organic compounds and ammonium compounds in an acidic pH environment. However, as in the above patent, since the solution is in the acidic range, very small particles (particles) having a size of 1 μm or less, which is a basic characteristic of the initial stage of cleaning, is insufficient.

On the other hand, Korean Patent Publication No. 10-0599849 discloses an organic acid such as urea and / or ethylene urea, quaternary ammonium hydroxide, alkali components such as ammonia, citric acid (CITRIC ACID), malic acid (MALIC ACID), tartaric acid (TARTARIC ACID) And / or a salt thereof and a residual amount of the washing liquid containing deionized distilled water, but problems of precipitation of urea or ethylene urea may occur when used for a long time.

It is an object of the present invention to provide a cleaning liquid composition suitable for removing organic contaminants or particles present on a glass substrate in a process of manufacturing an FPD substrate and a cleaning method using the same.

Still another object of the present invention is to provide a cleaning liquid composition which does not corrode copper wiring, copper alloy wiring, aluminum wiring or aluminum alloy wiring formed on the FPD substrate and a cleaning method using the same.

The present invention is an oxyamine compound represented by the formula (1); Additives comprising one or two or more selected from the group consisting of azole compounds, alkanol amine salts and reducing agents; And it provides a cleaning liquid composition for a flat panel display substrate comprising water.

<Formula 1>

In Formula 1, R ₁ is a C ₁ ~ C ₃ linear or chain hydroxyalkyl group, C ₁ ~ C ₃ is a linear or chain thiolalkyl group, R ₂ and R ₃ are each independently hydrogen, C ₁ ~ and C ₄ Al kilgi, C ₁ ~ C ₄ hydroxyalkyl group, C ₆ ~ C ₁₀ aryl group, C ₁ ~ C ₄ alkoxyalkyl group, C alkoxy alkane olgi of ₁ ~ C ₄ of the, at this time, R ₁ and R ₂ may be bonded to each other to form a ring having 5 and 6 atoms, provided that R ₃ is not a C ₁ to C ₄ hydroxyalkyl group, and n is a natural number of 1 to 4.

The present invention also provides a method for cleaning a flat panel display substrate using the cleaning liquid composition.

The cleaning liquid composition of the present invention has excellent organic contamination and particle removal ability on the glass surface of the flat panel display substrate, excellent corrosion protection effect of copper and copper alloy wiring formed on the substrate, and contains a large amount of deionized water. It is easy to handle and has an environmentally beneficial effect.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The cleaning liquid composition for a flat panel display substrate of the present invention contains an oxyamine compound, an additive, and water.

The oxyamine compound contained in the cleaning liquid composition for flat panel display substrates of this invention is represented by following General formula (1).

<Formula 1>

In Formula 1, R ₁ is a C ₁ ~ C ₃ linear or chain hydroxyalkyl group, C ₁ ~ C ₃ is a linear or chain thiolalkyl group, R ₂ and R ₃ are each independently hydrogen, C ₁ ~ alkyl group of C _4, C ₁ ~ C _4, and a hydroxyalkyl group, C ₆ ~ C ₁₀ aryl group, C ₁ ~ C ₄ alkoxyalkyl group, C alkoxy alkane olgi of ₁ ~ C ₄ of the, at this time, R ₁ and R _Two may combine with each other to form a ring having 5 and 6 atoms, provided that R ₃ is not a C ₁ to C ₄ hydroxyalkyl group, and n is a natural number of 1 to 4.

The oxyamine compound represented by Chemical Formula 1 is not only a basic material capable of removing particles and organic contaminants, but also has an oxy structure, and has an anti-corrosion effect of aluminum or copper when used in combination with other alkanolamines.

The oxyamine compound represented by Formula 1 is preferably included in the composition at 0.05 to 5% by weight, and more preferably 0.1 to 1% by weight based on the total weight. When included in the above-mentioned range, sufficient cleaning effect cannot be achieved, and when included in the above-mentioned range, the activity in the cleaning liquid is lowered to reduce particle removal effect or to be made of copper, copper alloy, aluminum or aluminum alloy. Corrosion to wiring increases.

The oxyamine compound represented by Formula 1 is aminoethoxyethanol, aminopropoxyethanol, aminobutoxyethanol, dimethylaminoethoxythiol, diethylaminoethoxythiol, dipropylaminoethoxythiol, dibutylaminoethoxy Thiol, dibutylaminoethoxyethanol dimethylaminoethoxyethanol, diethylaminoethoxyethanol, dipropylaminoethoxyethanol, dibutylaminoethoxyethanol, N- (methoxymethyl) morpholine, N- (ethoxy It is preferable that it is 1 type, or 2 or more types chosen from the group which consists of methyl) morpholine, N- (methoxyethanol) morpholine, N- (ethoxyethanol) morpholine, and N- (butoxyethanol) morpholine. Among these, aminoethoxy ethanol, dimethylamino ethoxy ethanol, etc. are more preferable.

The additive contained in the cleaning liquid composition for flat panel display substrates of this invention contains 1 type, or 2 or more types chosen from the group which consists of an azole compound, an alkanol amine salt, and a reducing agent. The additive minimizes corrosion of metal films such as aluminum, copper, or copper alloys and aluminum alloys.

The additive is included in an amount of 0.01 to 10% by weight, preferably 0.1 to 3% by weight, based on the total weight of the composition. When the above range is satisfied, damage to metal films such as aluminum, copper, or an aluminum alloy, a copper alloy is minimized and economical.

It is preferable that the said azole type compound contains a triazole ring. Non-covalent electron pairs of nitrogen atoms present in the triazole ring electronically bond with copper to control metal corrosion. The azole compound is tolytriazole, 1,2,3-benzotriazole, 1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole , 4-amino-4H-1,2,4-triazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 2-methylbenzotriazole, 5-methylbenzotriazole, benzotriazole-5 -Carboxylic acid, nitrobenzotriazole and 2- (2H-benzotriazol-2-yl) -4,6-di-tet-butylphenol, 2,2 '-[[[ethyl-1 hydrogen-benzotriazole It is preferable that it is 1 type (s) or 2 or more types chosen from the group which consists of -1-yl] methyl] imino] bisethanol.

The alkanol amine salt has a pH buffering effect that prevents corrosion of the metal and overetching of the oxide film during the cleaning process of the substrate having the metal pattern and the oxide film and suppresses the pH change of the cleaning solution. In the preparation of the alkanol amine salt, the temperature of the salt formation reaction is preferably maintained at 90 ° C or less.

The alkanol amine salt is preferably selected from alkanolamines wherein the alkyl moiety is usually lower alkyl, ie C1 to C5 alkyl. It is also preferable to use other lower alkanol amine salts, such as dimethyl methanolamine salt, since other substituents may be present in the amine group if one or more hydroxy groups remain. Specific examples of the alkanol amine salts include monoethanolamine salts, diethanolamine salts, triethanolamine salts, monoisopropanolamine salts, diisopropanolamine salts and triisopropanolamine salts. As the alkanol amine salt, a commercially available product may be used. Examples of commercially available products include AB RUST CM (product of LABEMA Co.), AB RUST A4 (product of LABEMA Co.), EMADOX-NA (product of LABEMA Co.), EMADOX-NB (product of LABEMA Co.), EMADOX-NCAL ( LABEMA Co.), EMADOX-102 (manufactured by LABEMA Co.), EMADOX-103 (manufactured by LABEMA Co.), EMADOX-D520 (manufactured by LABEMA Co.), and AB Rust at (manufactured by LABEMA Co.). .

The reducing agent serves to prevent corrosion of the metal wiring by inhibiting the formation of an oxide film, which may be referred to as the progress of corrosion of the metal wiring. The reducing agent is preferably one or two or more selected from the group consisting of elisorbic acid, vitamin C and alpha tocopherol.

The residual amount of water contained in the cleaning liquid composition for flat panel display substrates of this invention is contained. It is preferable that it is deionized water, and, as for the said water, it is more preferable that it is deionized distilled water. When the water is included, it is possible to provide an economical and environmentally friendly cleaning liquid composition.

The cleaning liquid composition for a flat panel display substrate of the present invention further comprises one or two or more selected from the group consisting of a chain alkanolamine, a polycarboxylic acid copolymer, a protic alkylene glycol monoalkyl ether compound and a surfactant. It is preferable to include.

The chain alkanolamines serve to remove particles and dissolve organic contaminants. The chain alkanolamine is preferably included in 0.05 to 5% by weight based on the total weight of the composition. If it is included below the above-mentioned range, particle removal or organic contaminant-removing effect is inferior. If it is included above the above-mentioned range, it causes corrosion of metal films such as aluminum and copper.

The chain alkanolamine compound is a group consisting of monoethanolamine, monopropanolamine, monoisopropanolamine, butanolamine, 2-propoxyethylamine, N-butylethanolamine, N-methyl ethanolamine and N-ethylethanolamine It is preferable that it is 1 type, or 2 or more types chosen from.

The polycarboxylic acid copolymer may form a protective layer on the surface of the metal to inhibit excessive reaction with alkali ions, thereby preventing corrosion of the metal, and serves as a pH adjusting agent. The polycarboxylic acid copolymer preferably includes a structural unit represented by the following formula (2).

<Formula 2>

In Chemical Formula 2,

R ₇ to R ₉ are each independently hydrogen, methyl group, ethyl group or (CH ₂ ) m ₂ COOM ₂ , and M ₁ and M ₂ are each independently hydrogen, alkali metal, alkaline earth metal, ammonium group, C ₁ to C ₁₀ It is an alkylammonium group of or C ₁ ~ C ₁₀ substituted alkylammonium group, m ₁ and m ₂ are each independently an integer of 0 to 2.

The polycarboxylic acid copolymer preferably comprises a monomer having a structural unit represented by the formula (2). Monomers having a structural unit represented by the formula (2) are acrylic acid, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, trimethyl acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, vinyl acetic acid, 4-phene It is preferable that it is 1 type (s) or 2 or more types chosen from the group which consists of tennic acids and their salts. Among them, acrylic acid, methyl (meth) acrylic acid and maleic acid are more preferable from the viewpoint of polishing the metal at high speed.

In addition, the polycarboxylic acid copolymer may use one kind or two or more kinds of other monomers copolymerizable with the monomer having the structural unit represented by the formula (2). Specific examples thereof include polyacrylic acid polymer (PAA), polymethyl (meth) acrylic acid copolymer (PMAA), polyacrylic acid maleic acid copolymer (PAMA), polymethyl acrylate (meth) acrylic acid copolymer (PAMAA), polymale Acid copolymer (PMA), polymethyl (meth) acrylic acid maleic acid copolymer (PMAMA), these salts, etc. are mentioned.

The polycarboxylic acid copolymer is preferably contained in an amount of 0.05% to 20% by weight, more preferably 0.05% to 5% by weight, and more preferably 0.1% to 1% by weight, based on the total weight of the composition. Most preferred.

The protic alkylene glycol monoalkyl ether compound serves as a solvent for dissolving organic contaminants. In addition to the function as a solvent, the proton alkylene glycol monoalkyl ether compound lowers the surface tension of the cleaning solution to increase the wettability on the glass substrate, thereby improving the cleaning power.

The protic alkylene glycol monoalkyl ether compound is ethylene glycol monobutyl ether (BG), diethylene glycol monomethyl ether (MDG), diethylene glycol monoethyl ether (carbitol), diethylene glycol monobutyl ether (BDG), With 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) It is preferable that it is 1 type, or 2 or more types chosen from the group which consists of.

The protic alkylene glycol monoalkyl ether compound is preferably contained in 0.05 to 20% by weight, more preferably in 0.5 to 10% by weight based on the total weight of the composition. When included below the above range, it is not possible to expect an increase in the solubility of the cleaning liquid composition to organic contaminants due to the addition of the protic alkylene glycol monoalkyl ether compound. If included beyond the above range, no further effect on the increase in wettability can be expected.

The surfactant increases the wettability of the substrate so that uniform cleaning is performed, and has an effect of preventing corrosion of the metal and over-etching of the oxide film during the cleaning process of the substrate including the metal pattern and the oxide film. It is preferable that the said surfactant is 1 type (s) or 2 or more types chosen from the group which consists of a negative surfactant, an amphoteric surfactant, and a nonionic surfactant. Among these, it is preferable to use nonionic surfactant which is excellent in wettability and has less bubble generation.

The nonionic surfactants are polyoxyethylene / polyoxypropylene glycol type, polyoxyethylene alkyl ether type, polyoxyethylene alkylphenyl ether type, polyoxyethylene / polyoxypropylene alkyl ether type, polyoxyethylene / polyoxybutylene Alkyl ether type, polyoxyethylene alkyl amino ether type, polyoxyethylene alkylamide ether type, polyethylene glycol fatty acid ester type, sorbitan fatty acid ester type, fatty acid ester type, glycerin fatty acid ester type, polyglycerol fatty acid ester type, glycerin ester type It is preferable that it is 1 type (s) or 2 or more types chosen from the group which consists of alkyramide type | mold, fatty acid amide type, and oxyethylene addition fatty acid amide type. Among these, polyoxyethylene / polyoxybutylene, which has an oxyethylene group (EO group) as a hydrophilic group in the structure of a surfactant molecule, and has an oxypropylene group (PO group) and or an oxy butylene group (ＢO group) as a hydrophobic group. It is preferable that it is an alkyl ether type copolymer. Here, the EO group is represented by -CH ₂ -CH ₂ -O-, the oxypropylene group is -CH (CH ₃ ) -CH ₂ -O- or -CH ₂ -CH (CH ₃ ) -O-, and the oxybutylene group -CH ₂ -CH ₂ -CH ₂ -CH ₂ -O-, -CH (CH ₃ ) -CH ₂ -CH ₂ -O-, -CH ₂ -CH (CH ₃ ) -CH ₂ -O-, or- CH ₂ -CH ₂ -CH (CH ₃ ) ₂ -O-. The copolymerization portion of the EO group, the PO group, and the PO group may be a block copolymer, a random copolymer, or a random polypolymer having block properties. In addition, the copolymer molecule may be a copolymer of an EO group or a PO group, a copolymer of an EO group or a PO group, or a copolymer of the EO group or a PO group or a BA group. As an abundance ratio in the surfactant molecule of the EO group of the hydrophilic group and the PO group or the BOH group of the hydrophilic group, X / (X + It is preferable that Y) is in the range of 0.05 to 0.7.

In addition, the terminal of the said nonionic surfactant may be 1 type, or 2 or more types chosen from the group which consists only of a hydrogen, a hydroxyl group, an alkyl group, and an alkenyl group. Moreover, the structure which added ethylene diamine and glycerol may be sufficient. Examples of such nonionic surfactants include polyoxyethylene / polyoxypropylene condensates, polyoxyethylene / polyoxybutylene condensates, polyoxyethylene / polyoxypropylene dicanylether condensates, polyoxyethylene / polyoxy Propylene decanyl ether condensates, polyoxyethylene / polyoxypropylene undecanyl ether condensates, polyoxyethylene / polyoxypropylene dodecanyl ether condensates, polyoxyethylene / polyoxypropylene tetradecanyl ether condensates, polyoxyethylene Polyoxybutylene decanyl ether condensate, polyoxyethylene / polyoxybutylene undecanyl ether condensate, polyoxyethylene / polyoxybutylene dodecanyl ether condensate, polyoxyethylene / polyoxybutylene tetradecanyl Ether condensates, polyoxyethylene / polyoxypropylene 2-ethylhexyl ether, polyoxyethylene / polyoxypropylene lauryl Le, polyoxyethylene / polyoxypropylene stearyl ether, glycerin addition polyoxyethylene / polyoxypropylene condensate, glycerin addition polyoxyethylene / polyoxybutylene condensate ethylenediamine addition polyoxyethylene / polyoxypropylene condensate, Ethylenediamine addition type polyoxyethylene / polyoxybutylene condensate polyoxyethylene / polyoxybutylene 2-ethylhexyl ether, polyoxyethylene / polyoxybutylene lauryl ether, polyoxyethylene / polyoxybutylene stearyl ether Etc. can be mentioned. Preferred are polyoxyethylene / polyoxypropylene condensates, polyoxyethylene polyoxybutylene condensates, glycerin added polyoxyethylene polyoxypropylene condensates and ethylenediamine added polyoxyethylene polyoxypropylene condensates, more preferably Is a polyoxyethylene polyoxypropylene condensate or an ethylenediamine addition polyoxyethylene polyoxypropylene condensate.

The surfactant is preferably included in 0.001 to 1.0% by weight, more preferably 0.01 to 0.5% by weight based on the total weight of the composition. If it is included in the above-described range, the effect of increasing the uniformity of cleaning of the glass substrate is insignificant. If it is included in the above-mentioned range, the uniformity of cleaning is constant but converges within a certain range without increasing more.

The pH of the cleaning liquid composition of the present invention is preferably in the range of pH 7 to pH 13, more preferably pH 8 to pH 11.

The cleaning method using the cleaning liquid composition of the present invention can be carried out by methods commonly known in the art. The cleaning method is preferably performed by one or two or more selected from the group consisting of a spray method, a spin method, a dipping method, and a dipping method using ultrasonic waves. The temperature at which the cleaning method of the present invention can exhibit the most excellent cleaning effect is 20 to 80 ° C, preferably 20 to 50 ° C. In addition, the cleaning method of the present invention is preferably carried out for 30 seconds to 10 minutes.

Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited only to a following example. The following examples set forth preferred compositions for the present invention as well as preferred methods for using the compositions of the present invention.

Examples 1 to 22 and Comparative Examples 1 to 3: Preparation of Cleaning Liquid Composition

The constituents shown in Table 1 were mixed with the remaining water in the composition shown in Table 1 and stirred to prepare a cleaning liquid composition.

Oxyamine compound Chain alkanol amines additive * GE Polycarboxylic acid
Copolymerization Surfactants Kinds weight% Kinds weight% Kinds weight% Kinds weight% Kinds weight% Kinds weight% Example 1 AEE 0.2 - - *One) 0.05 - - - - - - Example 2 AEE 0.2 - - *2) 0.2 - - - - - - Example 3 AEE 0.2 - - * 3) 0.2 - - - - - - Example 4 AEE 1.0 - - *One) 0.1 - - - - - - Example 5 DAEE 0.2 - - *One) 0.05 - - - - - - Example 6 DAEE 0.2 - - *2) 0.2 - - - - - - Example 7 DAEE 0.2 - - * 3) 0.2 - - - - - - Example 8 DAEE 1.0 - - *One) 0.1 - - - - - - Example 9 AEE 0.9 MEA 0.1 *One) 0.1 - - - - - - Example 10 AEE 0.9 MIPA 0.1 *2) 0.1 - - - - - - Example 11 DAEE 0.9 MEA 0.1 * 3) 0.1 - - - - - - Example 12 DAEE 0.9 MIPA 0.1 *One) 0.1 - - - - - - Example 13 AEE 1.0 - - *One) 0.1 *4) 0.5 - - - - Example 14 AEE 1.0 - - *One) 0.1 * 5) 0.5 - - - - Example 15 AEE 1.0 - - *One) 0.1 * 6) 0.5 - - - - Example 16 DAEE 1.0 - - *One) 0.1 *4) 0.5 - - - - Example 17 AEE 0.9 MEA 0.1 *One) 0.1 *4) 0.5 - - - - Example 18 DAEE 0.9 MEA 0.1 *One) 0.1 *4) 0.5 - - - - Example 19 AEE 0.9 MEA 0.1 *One) 0.1 - - * 7) 0.2 - - Example 20 DAEE 0.9 MEA 0.1 *One) 0.1 - - *8) 0.2 - - Example 21 AEE 1.0 - - *One) 0.1 - - - - * 9) 0.02 Example 22 AEE 1.0 - - *One) 0.1 - - - - * 10) 0.1 Comparative Example 1 TMAH 1.0 - - *2) 0.3 - - - - - - Comparative Example 2 NH4OH 1.0 - - - - - - - - - - Comparative Example 3 MEA 1.0 - - - - - - - - - -

AEE: aminoethoxyethanol

DAEE: Dimethylaminoethoxyethanol

MEA: monoethanolamine

MIPA: monoisopropanolamine

TMAH: Tetramethylammonium Hydroxide

NH ₄ OH: ammonium hydroxide

* 1): 2,2 '-[[[ethyl-1 hydrogen-benzotriazol-1-yl] methyl] imino] bisethanol

* 2): EMADOX-NA

* 3): Ascorbic acid

* GE: protic alkylene glycol monoalkyl ether

* 4) diethylene glycol monomethyl ether

* 5) diethylene glycol monobutyl ether

* 6): triethylene glycol monoethyl ether

* 7): polyacrylic acid polymer (PAA)

* 8): polymethyl (meth) acrylic acid copolymer (PMAA)

* 9): polyoxyethylene / polyoxypropylene glycol

* 10): polyoxyethylene / polyoxypropylene ethylenediamine condensate

Test Example: Evaluation of Characteristics of Cleaning Liquid Composition

1) copper etch rate evaluation

First, a glass substrate having a copper thickness of 2500 kPa was dipped into the cleaning liquid compositions of Examples 1 to 12 and Comparative Examples 1 to 3 for 30 minutes. At this time, the temperature of the cleaning liquid is 40 ℃ and the thickness of the copper film is measured before and after dipping, the dissolution rate of the copper film is calculated by calculating from the change in the thickness of the copper film. The results are shown in Table 2.

2) Evaluation of Organic Pollutant Removal Capacity-1

In order to evaluate the removal power of organic contaminants, the human body is stained with a fingerprint or an organic signature pen on a glass substrate formed of 5 cm x 5 cm, and the contaminated substrate is carried out at 40 ° C. for 2 minutes using a spray glass substrate cleaning device. It wash | cleaned with the cleaning liquid composition of Example 4, Example 8, Example 9, Example 11, and Example 13-22. After washing for 30 seconds in ultrapure water and dried with nitrogen.

At this time, the presence or absence of the organic contaminants in Table 2, when removed, was indicated by x, when not removed. In addition, the organic contaminant removal results according to Example 13 are shown in FIGS. 1 to 4. 1 is a photograph showing a glass substrate contaminated with an organic sign pen mark 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 liquid composition according to Example 13 of the present invention. 3 is a photograph showing a glass substrate contaminated with human fingerprints among organic contaminants. 4 is a photograph showing a result of removing a fingerprint component of a human from organic contaminants using the cleaning liquid composition according to Example 13 of the present invention.

3) Evaluation of Organic Pollutant Removal Capacity-2

In addition, the glass substrate is left in the air for 24 hours to contaminate various organic substances, inorganic substances, particles, and the like in the atmosphere, and then, using the spray-type glass substrate cleaning apparatus, the spraying glass substrate cleaning apparatus is used at 40 ° C. for Examples 4, 8 and 9 , Example 11, Example 13 to Example 22 was washed with the cleaning liquid composition, after washing 30 seconds in ultrapure water and then 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) Evaluation of organic pollutant removal-3

The glass substrates having the cleaning liquid compositions of Examples 4, 8, 17, 19 and 21 were contaminated with an organic particle solution were washed. That is, 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 washed with each cleaning liquid at 40 ° C. for 2 minutes using a spray-type glass substrate cleaning device. . 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 0.1 μm or more, and is shown in Table 2.

Cu etching rate
(Å / min) Organic fingerprint abandonment
Signature pen Contact angle Number of particles before cleaning Number of particles after cleaning Removal rate (%) Example 1 1.0 - - - - - - Example 2 1.5 - - - - - - Example 3 1.3 - - - - - - Example 4 0.8 ○ ○ 34 2925 439 85 Example 5 0.6 - - - - - - Example 6 1.2 - - - - - - Example 7 0.9 - - - - - - Example 8 0.7 ○ ○ 38 2965 563 81 Example 9 1.5 ○ ○ 30 - - - Example 10 1.5 - - - - - - Example 11 1.3 ○ ○ 31 - - - Example 12 1.2 - - - - - - Example 13 - ○ ○ 32 - - - Example 14 - ○ ○ 34 - - - Example 15 - ○ ○ 35 - - - Example 16 - ○ ○ 36 - - - Example 17 - ○ ○ 27 3012 331 89 Example 18 - ○ ○ 28 - - - Example 19 - ○ ○ 29 2913 350 88 Example 20 - ○ ○ 30 - - - Example 21 - ○ ○ 32 3019 497 84 Example 22 - ○ ○ 33 - - - Comparative Example 1 62 - - - - - - Comparative Example 2 70 - - - - - - Comparative Example 3 66 - - - - - -

Referring to Table 2, the cleaning liquid compositions of Examples 1 to 12 had an anticorrosion effect on copper. However, in the case of Comparative Examples 1 to 3 containing only the oxyamine compound and the additive, corrosion phenomenon of copper was observed.

In addition, the cleaning liquid compositions of Examples 4, 8, 9, 11, and 13-22 all showed the ability to remove organic contaminants, and the contact angles were 20 ° to 40 °. The ability to remove organic contaminants was shown.

When cleaning the glass substrate contaminated with the organic particle solution with the cleaning liquid compositions of Examples 4, 8, 17, 19 and 21, the particle removal ability was 80% or more.

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 liquid composition according to Example 15 of the present invention.

3 is a photograph showing a glass substrate contaminated with human fingerprints among organic contaminants.

4 is a photograph showing a result of removing a fingerprint component of a human from organic contaminants using the cleaning liquid composition according to Example 15 of the present invention.

Claims (14)

An oxyamine compound represented by Formula 1 below; Additives comprising one or two or more selected from the group consisting of azole compounds, alkanol amine salts and reducing agents; And A cleaning liquid composition for flat panel display substrates comprising water: <Formula 1>

In Chemical Formula 1, R ₁ is a C ₁ to C ₃ straight or chained hydroxyalkyl group, C ₁ to C ₃ straight or chained thiolalkyl group, R ₂ and R ₃ are each independently hydrogen, C ₁ -C ₄ alkyl group, C ₁ -C ₄ hydroxyalkyl group, C ₆ -C ₁₀ aryl group, C ₁ -C ₄ alkoxyalkyl group, C _1- C ₄ is an alkoxyalkanol group, wherein R ₁ and R ₂ may be bonded to each other to form a ring having 5 and 6 atoms, provided that R ₃ is not a C ₁ to C ₄ hydroxyalkyl group, n is a natural number of 1 to 4. The method according to claim 1, Regarding the total weight of the composition, 0.05 to 5% by weight of the oxyamine compound represented by Formula 1; 0.01 to 10 wt% of the additive; And Cleaning liquid composition for a flat panel display substrate comprising the remaining amount of water. The method according to claim 1, The oxyamine compound represented by Formula 1 is aminoethoxyethanol, aminopropoxyethanol, aminobutoxyethanol, dimethylaminoethoxythiol, diethylaminoethoxythiol, dipropylaminoethoxythiol, dibutylaminoethoxy Thiol, dibutylaminoethoxyethanol dimethylaminoethoxyethanol, diethylaminoethoxyethanol, dipropylaminoethoxyethanol, dibutylaminoethoxyethanol, N- (methoxymethyl) morpholine, N- (ethoxy Methyl) morpholine, N- (methoxyethanol) morpholine, N- (ethoxyethanol) morpholine and N- (butoxyethanol) morpholine, characterized in that one or two or more selected from the group consisting of Cleaning liquid composition for flat panel display substrates. The method according to claim 1, The additive is tolytriazole, 1,2,3-benzotriazole, 1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 4 -Amino-4H-1,2,4-triazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 2-methylbenzotriazole, 5-methylbenzotriazole, benzotriazole-5-car Main acid, nitrobenzotriazole and 2- (2H-benzotriazol-2-yl) -4,6-di-tet-butylphenol, 2,2 '-[[[ethyl-1 hydrogen-benzotriazole-1 -Yl] methyl] imino] bisethanol, monoethanolamine salt, diethanolamine salt, triethanolamine salt, monoisopropanolamine salt, diisopropanolamine salt, triisopropanolamine salt, elisorbic acid, vitamin C and alpha tocopherol It is 1 type (s) or 2 or more types chosen from the group, The cleaning liquid composition for flat panel display substrates characterized by the above-mentioned. The method according to claim 1, For a flat panel display substrate further comprising one or two or more selected from the group consisting of a chain alkanolamine, a polycarboxylic acid copolymer, a protic alkylene glycol monoalkyl ether compound and a surfactant. Cleaning liquid composition. The method according to claim 5, 0.05 to 5% by weight of the chain alkanolamine compound; 0.05 to 20% by weight of the polycarboxylic acid copolymer; 0.05-20 wt% of the protic alkylene glycol monoalkyl ether compound; And The surfactant is a cleaning liquid composition for a flat panel display substrate, characterized in that contained in 0.001 to 1.0% by weight. The method according to claim 5, The chain alkanolamine compound is a group consisting of monoethanolamine, monopropanolamine, monoisopropanolamine, butanolamine, 2-propoxyethylamine, N-butylethanolamine, N-methylethanolamine and N-ethylethanolamine Cleaning liquid composition for a flat panel display substrate, characterized in that one or two or more selected from. The method according to claim 5, The polycarboxylic acid copolymer as a cleaning liquid composition for a flat panel display substrate comprising a structural unit represented by the formula (2). <Formula 2>

In Chemical Formula 2, R ₇ to R ₉ are each independently hydrogen, a methyl group, an ethyl group, or (CH ₂ ) m ₂ COOM ₂ , M ₁ and M ₂ are each independently hydrogen, an alkali metal, an alkaline earth metal, an ammonium group, a C ₁ to C ₁₀ alkylammonium group or a C ₁ to C ₁₀ substituted alkylammonium group, m ₁ and m ₂ are each independently an integer of 0 to 2. The method according to claim 5, The protic alkylene glycol monoalkyl 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) The cleaning liquid composition for flat panel display substrates which is 1 type (s) or 2 or more types selected from the group. The method according to claim 1, PH of the cleaning liquid composition for a flat panel display substrate is 7 to 13, the cleaning liquid composition for a flat panel display substrate. A method for cleaning a flat panel display substrate using the cleaning liquid composition of claim 1. The method of claim 11, The cleaning method may be performed using one or two or more selected from the group consisting of a spray method, a spin method, a dipping method, and a dipping method using ultrasonic waves. The method of claim 11, The cleaning method is characterized in that the washing at a temperature of 20 to 80 ℃. The method of claim 11, The cleaning method is characterized in that the cleaning for 30 seconds to 10 minutes.

Images