WO2011014027A2 - Cleaning fluid composition and a cleaning method for a panel using the same - Google Patents

Abstract

The present invention relates to a cleaning fluid composition for flat-panel display devices, comprising: (a) between 0.05 and 5 wt.% of an amine compound; (b) from 0.01 to 10 wt.% of an additive comprising one or two or more components selected from the group consisting of azole-based compounds, alkanol amine salts and reducing agents; and (c) a balance of water.

Description

Cleaning liquid composition and cleaning method of panel using same

The present invention relates to a cleaning liquid composition and a cleaning method using the same. The present invention relates to Korean Patent Application Nos. 10-2009-0069505 and 10-2009-0069506 filed to the Korean Patent Office on July 29, 2009, and Korean Patent Application No. Claims the benefit of the filing date of 10-2009-0073683, the entire contents of which are incorporated herein.

A flat panel display device (hereinafter referred to as "FPD") represented by a liquid crystal display device, like a semiconductor device, is manufactured through a process such as film formation, exposure and etching. However, when such a process is performed, very small particles having a size of 1 μm or less of various organic materials or inorganic materials may be attached to the surface of the substrate. When the following steps are carried out with these particles attached, pinholes or pits of the film, disconnection or bridges of the wires are generated, and the production yield of the product is lowered.

Thus, cleaning to remove particles is performed between each process. Many proposals have also been made for cleaning liquids for cleaning. 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, the cleaning liquid of this patent cannot be used for cleaning FPD substrates because it contains a glass substrate, which is the most representative FPD substrate, and HF, which intensively etches Al, the most representative wiring material. . In addition, Japanese Patent Application Laid-Open No. 2000-232063 proposes to use phosphoric acid and ammonium phosphate as corrosion inhibitors. However, this patent is for removing resist residues and the pH of the composition is in the acidic range. Therefore, it is difficult to satisfy both the removal of very small particles having a size of 1 μm or less, which is a basic characteristic of the initial stage of cleaning, and the corrosion protection of aluminum wiring. In addition, Korean Patent Publication No. 10-0574607 proposes a cleaning solution containing deionized water, an organic compound and an ammonium compound in an acidic pH environment. However, since the cleaning solution of this patent is an acidic solution, the removal ability of very small particles having a size of 1 μm or less, such as organic or inorganic substances, which is a basic characteristic of the initial stage of cleaning, is not excellent. In addition, Korean Patent Publication No. 10-0599849 discloses an organic acid such as urea and / or an alkaline component such as urea urea, quaternary ammonium hydroxide, ammonia, citric acid (CITRIC ACID), malic acid (MALIC ACID), and tartaric acid (TARTARIC ACID). And / or a salt thereof, and a washing liquid containing residual deionized distilled water. However, the cleaning solution of this patent may cause the problem of precipitation of urea or ethylene urea with prolonged use.

An object of the present invention is to provide a cleaning liquid composition suitable for removing particles such as organic or inorganic substances present on a substrate used in a flat panel display.

It is also an object of the present invention to provide a cleaning liquid composition which does not corrode wiring including copper and wiring including aluminum used in a flat panel display.

The present invention relates to a total weight of the composition, (a) 0.05 to 5% by weight of an amine compound represented by any one of the following Formulas 1 to 5; (b) 0.01 to 10% by weight of an additive including one or two or more selected from the group consisting of an azole compound, an alkanol amine salt, and a reducing agent; And (c) provides a cleaning liquid composition for a flat panel display comprising a residual amount of water.

<Formula 1>

<Formula 2>

<Formula 3>

<Formula 4>

<Formula 5>

In Chemical Formulas 1 to 5,

R ₁ , R ₄ , and R ₅ are each independently a C ₁ to C ₁₀ linear or branched alkylene group,

R ₂ , R ₃ , and R ₆ are each independently hydrogen, a C ₁ to C ₁₀ straight or branched alkyl group,

R _7, R _8, R ₁₀ are each independently hydrogen, C ₁ ~ C ₁₀ straight-chain or branched-chain alkyl group, C ₆ ~ C ₁₀ aryl group, C ₁ ~ a C ₁₀ linear or branched alkyl group, C ₁ and - a C ₁₀ straight or branched chain hydroxyalkyl group, C ₁ ~ C ₁₀ straight or branched chain of an alkyl benzene group or an amino group,

R ₉ and R ₁₁ are hydrogen, a C ₁ to C ₁₀ straight or branched alkyl group, C ₆ to C ₁₀ aryl group, C ₁ to C ₁₀ straight or branched chain alkylamino group or amino group,

R ₁₂ is a C ₁ to C ₄ straight or branched hydroxyalkyl group, or C ₁ to C ₄ straight or branched thiolalkyl group,

R ₁₃ and R ₁₄ are each independently a C ₁ to C ₅ straight or branched chain alkyl group, C ₁ to C ₄ straight or branched chain hydroxyalkyl group, C ₆ to C ₁₀ aryl group or C ₁ to C ₄ An alkoxyalkyl group, R ₁₃ and R ₁₄ may combine to form a heterocycle,

n ₁ and n ₃ are each independently an integer of 0 or 1,

n ₂ and n ₄ are each independently an integer of 0 to 4,

n ₅ is an integer of 1 or 2,

n ₆ is an integer from 1 to 4,

n ₇ is an integer of 0 to 4,

X ₁ is S, O or N,

X ₂ is N,

X ₃ is CH or N,

Y is a hydroxyl group or an amino group.

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

The cleaning liquid composition of the present invention is excellent in the ability to remove particles such as organic or inorganic substances present on the surface of the substrate used in the flat panel display device. In addition, the cleaning liquid composition of the present invention is excellent in the anti-corrosion effect on the wiring including copper and the wiring including aluminum located on the substrate. In addition, the cleaning liquid composition of the present invention contains a large amount of water is easy to handle and environmentally friendly.

1 is a photograph showing a glass substrate contaminated with organic sign pen marks among organic contaminants.

FIG. 2 is a photograph showing a result of removing the organic sign pen marks shown in FIG. 1 by using the cleaning solution composition of Example 16. FIG.

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

Figure 4 is a photograph showing the result of removing the fingerprint component of the person shown in Figure 3 using the cleaning liquid composition according to Example 16.

5 is a photograph showing a glass substrate contaminated with an organic sign pen mark among organic contaminants.

FIG. 6 is a photograph showing a result of removing the organic sign pen marks shown in FIG. 5 using the cleaning liquid composition of Example 32. FIG.

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

8 is a photograph showing the result of removing the fingerprint component of the person shown in FIG. 6 by using the cleaning liquid composition according to Example 32.

9 is a photograph showing a glass substrate contaminated with organic sign pen marks among organic contaminants.

FIG. 10 is a photograph showing the result of removing the organic sign pen marks shown in FIG. 9 using the cleaning solution composition of Example 51. FIG.

11 is a photograph showing a glass substrate contaminated with a human fingerprint of organic contaminants.

12 is a photograph showing the result of removing the fingerprint component of the person shown in FIG. 11 using the cleaning liquid composition according to Example 51. FIG.

Hereinafter, the present invention will be described in detail.

The cleaning liquid composition for a flat panel display device of this invention contains (a) an amine compound, (b) additive, and (c) water.

The (a) amine compound included in the cleaning liquid composition for a flat panel display of the present invention is represented by any one of the following Chemical Formulas 1 to 5.

<Formula 1>

<Formula 2>

<Formula 3>

<Formula 4>

<Formula 5>

In Chemical Formulas 1 to 5,

R ₁ , R ₄ , and R ₅ are each independently a C ₁ to C ₁₀ linear or branched alkylene group,

R ₂ , R ₃ , and R ₆ are each independently hydrogen, a C ₁ to C ₁₀ straight or branched alkyl group,

R _7, R _8, R ₁₀ are each independently hydrogen, C ₁ ~ C ₁₀ straight-chain or branched-chain alkyl group, C ₆ ~ C ₁₀ aryl group, C ₁ ~ a C ₁₀ linear or branched alkyl group, C ₁ and - a C ₁₀ straight or branched chain hydroxyalkyl group, C ₁ ~ C ₁₀ straight or branched chain of an alkyl benzene group or an amino group,

R ₉ and R ₁₁ are hydrogen, a C ₁ to C ₁₀ straight or branched alkyl group, C ₆ to C ₁₀ aryl group, C ₁ to C ₁₀ straight or branched chain alkylamino group or amino group,

R ₁₂ is a C ₁ to C ₄ straight or branched hydroxyalkyl group, or C ₁ to C ₄ straight or branched thiolalkyl group,

R ₁₃ and R ₁₄ are each independently a C ₁ to C ₅ straight or branched chain alkyl group, C ₁ to C ₄ straight or branched chain hydroxyalkyl group, C ₆ to C ₁₀ aryl group or C ₁ to C ₄ An alkoxyalkyl group, R ₁₃ and R ₁₄ may combine to form a heterocycle,

n ₁ and n ₃ are each independently an integer of 0 or 1,

n ₂ and n ₄ are each independently an integer of 0 to 4,

n ₅ is an integer of 1 or 2,

n ₆ is an integer from 1 to 4,

n ₇ is an integer of 0 to 4,

X ₁ is S, O or N,

X ₂ is N,

X ₃ is CH or N,

Y is a hydroxyl group or an amino group.

The (a) amine compound is preferably contained in 0.05 to 5% by weight, 0.1 to 3% by weight based on the total weight of the composition. If it is included in less than the above-described range, it is not possible to implement a sufficient cleaning effect. When included in excess of the above-mentioned range, the activity in the cleaning liquid is lowered to reduce the particle removal effect or to increase corrosion to the wiring including copper or the wiring including aluminum.

The amine compound represented by Formula 1 is N- (2-hydroxyethyl) piperazine, N- (2-hydroxypropyl) piperazine, N- (2-hydroxybutyl) piperazine, 1- (2- Hydroxyethyl) -4-methylpiperazine, 1- (2-hydroxypropyl) -4-methylpiperazine, 1- (2-hydroxybutyl) -4-methylpiperazine, 1- (2-hydroxy Ethyl) -4-ethylpiperazine, 1- (2-hydroxyethyl) -4-propylpiperazine, 1- (2-hydroxyethyl) -4-butylpiperazine, 1- (2-hydroxypropyl) -4-methylpiperazine, 1- (2-hydroxypropyl) -4-ethylpiperazine, 1- (2-hydroxypropyl) -4-propylpiperazine, 1- (2-hydroxypropyl) -4 -Butyl piperazine, 1- (2-hydroxybutyl) -4-methylpiperazine, 1- (2-hydroxybutyl) -4-ethylpiperazine, 1- (2-hydroxybutyl) -4-propyl Piperazine, 1- (2-hydroxybutyl) -4-butylpiperazine, N- (2-hydroxyethyl) morpholine, N- (2-hydroxypropyl) morpholine, N-aminopropylmorpholine, Hydroxyethylpiperazine, hydroxy Be selected from the group consisting of propyl-piperazin-1- (N- methylpiperazine) ethanol is preferred.

The compound represented by Chemical Formula 2 is preferably selected from the group consisting of 1,4-piperazinediethanol (1,4-Piperazinediethanol) and 1,4-piperazinedimethanol (1,4-Piperazinedimethanol).

Compound represented by the formula (3) is N- (2-hydroxyethyl) -ethylene urea, N- (3-hydroxypropyl) -2-pyrrolidone, hydroxymethylpyrrolidone and 1- (2-hydroxy It is preferably selected from the group consisting of oxyethyl) -2-pyrrolidone.

The compound represented by the formula (4) is in the group consisting of N- (2-hydroxyethyl) piperidine, N- (2-hydroxypropyl) piperidine and N- (2-hydroxybutyl) piperidine It is preferred to be selected.

Compound represented by the formula (5) is amino ethoxy ethanol, amino propoxy ethanol, amino butoxy ethanol, dimethyl amino ethoxy thiol, diethyl amino ethoxy thiol, dipropyl amino ethoxy thiol, dibutyl amino ethoxy thiol, Dimethylaminoethoxyethanol, diethylaminoethoxyethanol, dipropylaminoethoxyethanol, dibutylaminoethoxyethanol, dimethylaminoethoxyethanethiol, diethylaminoethoxypropanethiol, dipropylaminoethoxybutanethiol, Dibutylaminoethoxyethanol, N- (methoxymethyl) morpholine, N- (ethoxymethyl) morpholine, N- (2-methoxyethanol) morpholine, N- (2-ethoxyethanol) morpholine And N- (2-butoxyethanol) morpholine.

The additive (b) contained in the cleaning liquid composition for a flat panel display device of the present invention includes one or two or more selected from the group consisting of an azole compound, an alkanol amine salt, and a reducing agent.

The additive (b) minimizes corrosion of the wiring including copper and the wiring including aluminum.

The additive is included in an amount of 0.01 to 10% by weight, and 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. A non-covalent electron pair of nitrogen atoms present in the triazole ring electronically bonds with copper to inhibit 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, and 2,2 '-[[[ethyl-1 hydrogen-benzotria It is preferable that it is 1 type (s) or 2 or more types chosen from the group which consists of sol-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. product), EMADOX-102 (made by LABEMA Co.), EMADOX-103 (made by LABEMA Co.), EMADOX-D520 (made by LABEMA Co.), and AB Rust at (made by LABEMA Co.), and the like. .

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.

(C) Water contained in the cleaning liquid composition for flat panel display devices of this invention is preferably deionized water, and more preferably deionized distilled water. When the water (c) is included, it is possible to provide an economical and environmentally friendly cleaning liquid composition. The water (c) is contained in the remaining amount so that the content of the cleaning liquid composition of the present invention is 100% by weight.

The cleaning liquid composition for a flat panel display device of the present invention preferably further includes a polycarboxylic acid copolymer, a proton alkylene glycol monoalkyl ether compound, and a surfactant.

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 (6).

<Formula 6>

In Chemical Formula 6,

R ₁₅ to R ₁₇ are each independently hydrogen, a C ₁ to C ₃ straight or branched alkyl 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 polycarboxylic acid copolymer preferably includes a monomer having a structural unit represented by Chemical Formula 6. Monomers having a structural unit represented by the formula (6) 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 preferably selected from the group consisting of tenic acid and salts thereof. 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 (6). 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 included in an amount of 0.01% to 10% by weight, more preferably 0.05% to 5% by weight, and 0.1% to 1% by weight, based on the total weight of the composition. Most preferably.

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), 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 preferably selected from the group.

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 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 It is represented by 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 the ratio of the number of moles of the EO group to X, the number of moles of the PO group or the BOH group as Y, 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 / polyoxypropylene 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 Condensate, 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 cleaning uniformity increase effect of the glass substrate is insignificant. If it is included in the above-mentioned range, the cleaning uniformity is constant but converges within a certain range without increasing more.

The cleaning method using the cleaning liquid composition for a flat panel display device of the present invention may be performed by a method 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, the present invention will be described in more detail with reference to Examples. However, the scope of the present invention is not limited by the following examples.

Examples 1 to 19 and Comparative Examples 1 to 3: Preparation of Cleaning Liquid Composition

Washing liquid compositions were prepared by mixing and stirring with the ingredients and compositions shown in Table 1.

Table 1

	Cyclic amine compounds		additive		* GE		Polycarboxylic Acid Copolymerization 쳬		Surfactants		water
	Kinds	weight%	Kinds	weight%	Kinds	weight%	Kinds	weight%	Kinds	weight%
Example 1	NHEP1	0.2	*One)	0.05	-	-	-	-	-	-	Remaining amount
Example 2	NHEP1	0.2	*2)	0.2	-	-	-	-	-	-	Remaining amount
Example 3	NHEP1	0.2	* 3)	0.2	-	-	-	-	-	-	Remaining amount
Example 4	NHEP1	1.0	*One)	0.1	-	-	-	-	-	-	Remaining amount
Example 5	HEMP	0.2	*One)	0.05	-	-	-	-	-	-	Remaining amount
Example 6	HEMP	0.2	*2)	0.2	-	-	-	-	-	-	Remaining amount
Example 7	HEMP	0.2	* 3)	0.2	-	-	-	-	-	-	Remaining amount
Example 8	HEMP	1.0	*One)	0.1	-	-	-	-	-	-	Remaining amount
Example 9	NHEM	0.2	*One)	0.05	-	-	-	-	-	-	Remaining amount
Example 10	NHEM	0.2	*2)	0.2	-	-	-	-	-	-	Remaining amount
Example 11	NHEM	0.2	* 3)	0.2	-	-	-	-	-	-	Remaining amount
Example 12	NHEM	1.0	*One)	0.1	-	-	-	-	-	-	Remaining amount
Example 13	NHEP	1.0	*One)	0.1	*4)	0.5	-	-	-	-	Remaining amount
Example 14	NHEP	1.0	*One)	0.1	* 5)	0.5	-	-	-	-	Remaining amount
Example 15	NHEP	1.0	*One)	0.1	* 6)	0.5	-	-	-	-	Remaining amount
Example 16	NHEP	1.0	*One)	0.1	-	-	* 7)	0.2	-	-	Remaining amount
Example 17	NHEP	1.0	*One)	0.1	-	-	*8)	0.2	-	-	Remaining amount
Example 18	NHEP	1.0	*One)	0.1	-	-	-	-	* 9)	0.02	Remaining amount
Example 19	NHEP	1.0	*One)	0.1	-	-	-	-	* 10)	0.02	Remaining amount
Comparative Example 1	TMAH	1.0	*2)	0.3	-	-	-	-	-	-	Remaining amount
Comparative Example 2	NH 4 OH	1.0	-	-	-	-	-	-	-	-	Remaining amount
Comparative Example 3	MEA	1.0	-	-	-	-	-	-	-	-	Remaining amount

NHEP 1: N- (2-hydroxyethyl) piperazine

HEMP: 1- (2-hydroxyethyl) -4-methylpiperazine

NHEM: N- (2-hydroxyethyl) morpholine

TMAH: Tetramethylammonium Hydroxide

NH ₄ OH: ammonium hydroxide

MEA: Monoethanol Amine

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

* 2): EMADOX-NA (trade name: LABEMA Co.)

* 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): polymethylacrylic acid copolymer (PMAA)

* 9): polyoxyethylene / polyoxypropylene glycol

* 10): Ethylenediamine-Added Polyoxyethylene / Polyoxypropylene Condensate

Test Example 1 Evaluation of Characteristics of Cleaning Liquid Composition

1) copper etch rate evaluation

First, a glass substrate having a copper thickness of 2500 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, and Example 12-19. 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 16 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. FIG. 2 is a photograph showing a result of removing the organic sign pen marks shown in FIG. 1 using the cleaning liquid composition according to Example 16 of the present invention. 3 is a photograph showing a glass substrate contaminated with human fingerprints among organic contaminants. Figure 4 is a photograph showing the result of removing the fingerprint component of the person shown in Figure 3 using the cleaning liquid composition according to Example 16 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, etc. in the air, and then, using the spray-type glass substrate cleaning apparatus, the sample is carried out at 40 ° C. for 2 minutes. Examples 4, 8 and 12 To the cleaning liquid composition of Example 19 to 30 seconds after washing 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, 12, 13, 16 and 18 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 solution at 40 ° C. for 2 minutes using a spray-type glass substrate cleaner. . 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.

TABLE 2

	Cu etching rate (ms / min)	Organic fingerprint	Organic sign pen	Contact angle	Number of particles before cleaning	Number of particles after cleaning	% Removal
Example 1	1.0	-	-	-	-	-	-
Example 2	1.6	-	-	-	-	-	-
Example 3	1.3	-	-	-	-	-	-
Example 4	0.8	○	○	35	2851	484	83
Example 5	0.7	-	-	-	-	-	-
Example 6	1.4	-	-	-	-	-	-
Example 7	0.9	-	-	-	-	-	-
Example 8	0.6	○	○	39	2936	675	77
Example 9	0.6	-	-	-	-	-	-
Example 10	1.2	-	-	-	-	-	-
Example 11	0.8	-	-	-	-	-	-
Example 12	0.5	○	○	38	2987	627	79
Example 13	-	○	○	32	2913	407	86
Example 14	-	○	○	34	-	-	-
Example 15	-	○	○	34	-	-	-
Example 16	-	○	○	38	3012	542	82
Example 17	-	○	○	38	-	-	-
Example 18	-	○	○	33	3187	478	85
Example 19	-	○	○	32	-	-	-
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 in which an alkaline compound other than the cyclic amine compound was contained, corrosion phenomenon of copper was observed.

In addition, all of the cleaning liquid compositions of Examples 4, 8, 12, 13, and 16-19 were shown to have the ability to remove organic contaminants, and the contact angles were 20 ° to 40 °. The ability to remove organic contaminants was shown.

Particle removal force of 77-86% when cleaning the glass substrate contaminated with the organic particle solution with the cleaning liquid compositions of Examples 4, 8, 12, 13, 16 and 18 Indicated.

Examples 20-38 Preparation of Cleaning Liquid Compositions

Washing liquid compositions were prepared by mixing and stirring with the ingredients and compositions shown in Table 3.

TABLE 3

	Cyclic amine compounds		additive		* GE		Polycarboxylic Acid Copolymerization 쳬		Surfactants		water
	Kinds	weight%	Kinds	weight%	Kinds	weight%	Kinds	weight%	Kinds	weight%
Example 20	NHEP2	0.2	*One)	0.05	-	-	-	-	-	-	Remaining amount
Example 21	NHEP2	0.2	*2)	0.2	-	-	-	-	-	-	Remaining amount
Example 22	NHEP2	0.2	* 3)	0.2	-	-	-	-	-	-	Remaining amount
Example 23	NHEP2	1.0	*One)	0.1	-	-	-	-	-	-	Remaining amount
Example 24	NHPP2	0.2	*One)	0.05	-	-	-	-	-	-	Remaining amount
Example 25	NHPP2	0.2	*2)	0.2	-	-	-	-	-	-	Remaining amount
Example 26	NHPP2	0.2	* 3)	0.2	-	-	-	-	-	-	Remaining amount
Example 27	NHPP2	1.0	*One)	0.1	-	-	-	-	-	-	Remaining amount
Example 28	HEP	0.2	*One)	0.05	-	-	-	-	-	-	Remaining amount
Example 29	HEP	0.2	*2)	0.2	-	-	-	-	-	-	Remaining amount
Example 30	HEP	0.2	* 3)	0.2	-	-	-	-	-	-	Remaining amount
Example 31	HEP	1.0	*One)	0.1	-	-	-	-	-	-	Remaining amount
Example 32	NHEP	1.0	*One)	0.1	*4)	0.5	-	-	-	-	Remaining amount
Example 33	NHEP	1.0	*One)	0.1	* 5)	0.5	-	-	-	-	Remaining amount
Example 34	NHEP	1.0	*One)	0.1	* 6)	0.5	-	-	-	-	Remaining amount
Example 35	NHEP	1.0	*One)	0.1	-	-	* 7)	0.2	-	-	Remaining amount
Example 36	NHEP	1.0	*One)	0.1	-	-	*8)	0.2	-	-	Remaining amount
Example 37	NHEP	1.0	*One)	0.1	-	-	-	-	* 9)	0.02	Remaining amount
Example 38	NHEP	1.0	*One)	0.1	-	-	-	-	* 10)	0.02	Remaining amount

NHEP2: N- (2-hydroxyethyl) piperidine

NHPP: N- (2-hydroxypropyl) piperidine

HEP: 1- (2-hydroxyethyl) -2-pyrrolidone

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

* 2): EMADOX-NA (trade name: LABEMA Co.)

* 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): polymethylacrylic acid copolymer (PMAA)

* 9): polyoxyethylene / polyoxypropylene glycol

* 10): polyoxyethylene / polyoxypropylene ethylenediamine condensate

Test Example 2: Evaluation of Characteristics of Cleaning Liquid Composition

1) copper etch rate evaluation

First, a glass substrate having a copper thickness of 2500 was dipped into the cleaning liquid compositions of Examples 20 to 31 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, and 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 4.

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 23, Example 27, and Example 31-38. 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 4, when removed, was indicated by x, when not removed. In addition, the results of removing organic contaminants according to Example 35 are shown in FIGS. 5 to 8. 5 is a photograph showing a glass substrate contaminated with an organic sign pen mark among organic contaminants. FIG. 6 is a photograph showing a result of removing the organic sign pen marks shown in FIG. 5 using the cleaning liquid composition according to Example 32 of the present invention. FIG. 7 is a photograph showing a glass substrate contaminated with human fingerprints among organic contaminants. 8 is a photograph showing the result of removing the fingerprint component of the person shown in FIG. 7 by using the cleaning liquid composition according to Example 32 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, etc. in the air, and then, at 23 ° C. for 2 minutes using a spray-type glass substrate cleaning device, Examples 23, 27 and 31 are used. After washing with the cleaning liquid composition of Example 38 After washing 30 seconds in ultrapure water and then dried with nitrogen. 0.5 μl of ultrapure water was dropped on the glass substrate, and the contact angle after washing was measured. The results are shown in Table 4.

4) Evaluation of organic pollutant removal-3

The glass substrates of Example 23, Example 27, Example 31, Example 32, Example 35, and Example 37 were cleaned and contaminated with the organic particle solution. 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 solution at 40 ° C. for 2 minutes using a spray-type glass substrate cleaner. . After washing for 30 seconds in ultrapure water and dried with nitrogen. Particle number before and after cleaning was measured by the particle count (Topcon WM-1500) particle size of 0.1㎛ or more, are shown in Table 4.

Table 4

	Cu etching rate (ms / min)	Organic fingerprint	Organic sign pen	Contact angle	Number of particles before cleaning	Number of particles after cleaning	% Removal
Example 20	1.0	-	-	-	-	-	-
Example 21	1.6	-	-	-	-	-	-
Example 22	1.3	-	-	-	-	-	-
Example 23	0.8	○	○	38	2851	627	80
Example 24	0.7	-	-	-	-	-	-
Example 25	1.4	-	-	-	-	-	-
Example 26	0.9	-	-	-	-	-	-
Example 27	0.6	○	○	37	2936	675	80
Example 28	0.6	-	-	-	-	-	-
Example 29	1.2	-	-	-	-	-	-
Example 30	0.8	-	-	-	-	-	-
Example 31	0.5	○	○	36	2987	627	81
Example 32	-	○	○	35	2913	582	82
Example 33	-	○	○	36	-	-	-
Example 34	-	○	○	36	-	-	-
Example 35	-	○	○	39	3056	611	80
Example 36	-	○	○	39	-
Example 37	-	○	○	35	3201	544	83
Example 38	-	○	○	36	-

Referring to Table 4, the cleaning liquid compositions of Examples 20 to 31 had an anticorrosion effect on copper. In addition, all of the cleaning liquid compositions of Examples 27, 31, 32, and 35 to 38 showed the ability to remove organic contaminants, and the contact angles were 20 ° to 40 ° to remove organic contaminants. Demonstrated ability. In addition, when the cleaning liquid compositions of Examples 23, 27, 31, 32, 35, and 37 were washed on the glass substrate contaminated with the organic particle solution, the cleaning liquid composition was close to 77-86%. Particle removal was shown.

Examples 39 to 60 and Comparative Examples 1 to 3 Preparation of Cleaning Liquid Composition

The constituents described in Table 5 were mixed with the remaining water in the composition described in Table 5 and stirred to prepare a cleaning liquid composition.

Table 5

	Oxyamine Compound		Chain alkanol amines		additive		* GE		Polycarboxylic Acid Copolymerization 쳬		Surfactants
	Kinds	weight%	Kinds	weight%	Kinds	weight%	Kinds	weight%	Kinds	weight%	Kinds	weight%
Example 39	AEE	0.2	-	-	*One)	0.05	-	-	-	-	-	-
Example 40	AEE	0.2	-	-	*2)	0.2	-	-	-	-	-	-
Example 41	AEE	0.2	-	-	* 3)	0.2	-	-	-	-	-	-
Example 42	AEE	1.0	-	-	*One)	0.1	-	-	-	-	-	-
Example 43	DAEE	0.2	-	-	*One)	0.05	-	-	-	-	-	-
Example 44	DAEE	0.2	-	-	*2)	0.2	-	-	-	-	-	-
Example 45	DAEE	0.2	-	-	* 3)	0.2	-	-	-	-	-	-
Example 46	DAEE	1.0	-	-	*One)	0.1	-	-	-	-	-	-
Example 47	AEE	0.9	MEA	0.1	*One)	0.1	-	-	-	-	-	-
Example 48	AEE	0.9	MIPA	0.1	*2)	0.1	-	-	-	-	-	-
Example 49	DAEE	0.9	MEA	0.1	* 3)	0.1	-	-	-	-	-	-
Example 50	DAEE	0.9	MIPA	0.1	*One)	0.1	-	-	-	-	-	-
Example 51	AEE	1.0	-	-	*One)	0.1	*4)	0.5	-	-	-	-
Example 52	AEE	1.0	-	-	*One)	0.1	* 5)	0.5	-	-	-	-
Example 53	AEE	1.0	-	-	*One)	0.1	* 6)	0.5	-	-	-	-
Example 54	DAEE	1.0	-	-	*One)	0.1	*4)	0.5	-	-	-	-
Example 55	AEE	0.9	MEA	0.1	*One)	0.1	*4)	0.5	-	-	-	-
Example 56	DAEE	0.9	MEA	0.1	*One)	0.1	*4)	0.5	-	-	-	-
Example 57	AEE	0.9	MEA	0.1	*One)	0.1	-	-	* 7)	0.2	-	-
Example 58	DAEE	0.9	MEA	0.1	*One)	0.1	-	-	*8)	0.2	-	-
Example 59	AEE	1.0	-	-	*One)	0.1	-	-	-	-	* 9)	0.02
Example 60	AEE	1.0	-	-	*One)	0.1	-	-	-	-	* 10)	0.1

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 3 Evaluation of Characteristics of Cleaning Liquid Composition

1) copper etch rate evaluation

First, a glass substrate having a copper thickness of 2500 was dipped into the cleaning liquid compositions of Examples 38 to 50 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, and 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 6.

2) Evaluation of Organic Pollutant Removal Capacity-1

In order to evaluate the removal power of organic contaminants, the human body is stained with fingerprint marks or organic component pens on a glass substrate formed 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 42, Example 46, Example 47, Example 49, and Examples 51-60. 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 6, when removed, was indicated by x, when not removed. In addition, the results of removing organic contaminants according to Example 51 are shown in FIGS. 9 to 12. Here, FIG. 9 is a photograph showing a glass substrate contaminated with an organic sign pen mark among organic contaminants. 10 is a photograph showing a result of removing an organic sign pen mark from organic contaminants using the cleaning liquid composition according to Example 51 of the present invention. 11 is a photograph showing a glass substrate contaminated with a human fingerprint of organic contaminants. 12 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 51 of the present invention.

3) Evaluation of Organic Pollutant Removal Capacity-2

In addition, the glass substrate was left in the air for 24 hours to contaminate various organic substances, inorganic substances, particles, and the like in the atmosphere, and then, at 42 ° C. for 2 minutes using a spray-type glass substrate cleaning device, Examples 42, 46 and 47 were used. , Example 49, and Example 51 to Example 60 was washed with the cleaning liquid composition. After washing, it was washed with ultrapure water for 30 seconds 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 6.

4) Evaluation of organic pollutant removal-3

The glass substrates having the cleaning liquid compositions of Examples 42, 46, 55, 57 and 59 were contaminated with the organic particle solution. 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 solution at 40 ° C. for 2 minutes using a spray-type glass substrate cleaner. . After washing for 30 seconds in ultrapure water and dried with nitrogen. Particle number before and after cleaning was measured by a particle size measuring instrument (Topcon WM-1500) 0.1㎛ or more particles are shown in Table 6.

Table 6

	Cu etching rate (ms / min)	Organic fingerprint	Organic sign pen	Contact angle	Number of particles before cleaning	Number of particles after cleaning	% Removal
Example 39	1.0	-	-	-	-	-	-
Example 40	1.5	-	-	-	-	-	-
Example 41	1.3	-	-	-	-	-	-
Example 42	0.8	○	○	34	2925	439	85
Example 43	0.6	-	-	-	-	-	-
Example 44	1.2	-	-	-	-	-	-
Example 45	0.9	-	-	-	-	-	-
Example 46	0.7	○	○	38	2965	563	81
Example 47	1.5	○	○	30	-	-	-
Example 48	1.5	-	-	-	-	-	-
Example 49	1.3	○	○	31	-	-	-
Example 50	1.2	-	-	-	-	-	-
Example 51	-	○	○	32	-	-	-
Example 52	-	○	○	34	-	-	-
Example 53	-	○	○	35	-	-	-
Example 54	-	○	○	36	-	-	-
Example 55	-	○	○	27	3012	331	89
Example 56	-	○	○	28	-	-	-
Example 57	-	○	○	29	2913	350	88
Example 58	-	○	○	30	-	-	-
Example 59	-	○	○	32	3019	497	84
Example 60	-	○	○	33	-	-	-

Referring to Table 6, the cleaning liquid compositions of Examples 39 to 50 had an anticorrosion effect on copper. In addition, all of the cleaning liquid compositions of Examples 42, 46, 47, 49, and 51 to 60 showed removal ability of organic contaminants, and the contact angles were 20 ° to 40 °. The ability to remove organic contaminants was shown. Further, when cleaning the glass substrate contaminated with the organic particle solution with the cleaning liquid compositions of Examples 42, 46, 55, 57, and 59, the particle removal ability was 80% or more.

Claims (18)

1. Regarding the total weight of the composition,

   (a) 0.05 to 5% by weight of an amine compound represented by any one of the following Formulas 1 to 5;

   (b) 0.01 to 10% by weight of an additive including one or two or more selected from the group consisting of an azole compound, an alkanol amine salt, and a reducing agent; And

   (c) a cleaning liquid composition for a flat panel display comprising a remaining amount of water:

   <Formula 1>

   

   <Formula 2>

   

   <Formula 3>

   

   <Formula 4>

   

   <Formula 5>

   

   In Chemical Formulas 1 to 5,

   R ₁ , R ₄ , and R ₅ are each independently a C ₁ to C ₁₀ linear or branched alkylene group,

   R ₂ , R ₃ , and R ₆ are each independently hydrogen, a C ₁ to C ₁₀ straight or branched alkyl group,

   R _7, R _8, R ₁₀ are each independently hydrogen, C ₁ ~ C ₁₀ straight-chain or branched-chain alkyl group, C ₆ ~ C ₁₀ aryl group, C ₁ ~ a C ₁₀ linear or branched alkyl group, C ₁ and - a C ₁₀ straight or branched chain hydroxyalkyl group, C ₁ ~ C ₁₀ straight or branched chain of an alkyl benzene group or an amino group,

   R ₉ and R ₁₁ are hydrogen, a C ₁ to C ₁₀ straight or branched alkyl group, C ₆ to C ₁₀ aryl group, C ₁ to C ₁₀ straight or branched chain alkylamino group or amino group,

   R ₁₂ is a C ₁ to C ₄ straight or branched hydroxyalkyl group, or C ₁ to C ₄ straight or branched thiolalkyl group,

   R ₁₃ and R ₁₄ are each independently a C ₁ to C ₅ straight or branched chain alkyl group, C ₁ to C ₄ straight or branched chain hydroxyalkyl group, C ₆ to C ₁₀ aryl group or C ₁ to C ₄ An alkoxyalkyl group, R ₁₃ and R ₁₄ may combine to form a heterocycle,

   n ₁ and n ₃ are each independently an integer of 0 or 1,

   n ₂ and n ₄ are each independently an integer of 0 to 4,

   n ₅ is an integer of 1 or 2,

   n ₆ is an integer from 1 to 4,

   n ₇ is an integer of 0 to 4,

   X ₁ is S, O or N,

   X ₂ is N,

   X ₃ is CH or N,

   Y is a hydroxyl group or an amino group.
2. The method according to claim 1,

   The amine compound represented by Formula 1 is N- (2-hydroxyethyl) piperazine, N- (2-hydroxypropyl) piperazine, N- (2-hydroxybutyl) piperazine, 1- (2- Hydroxyethyl) -4-methylpiperazine, 1- (2-hydroxypropyl) -4-methylpiperazine, 1- (2-hydroxybutyl) -4-methylpiperazine, 1- (2-hydroxy Ethyl) -4-ethylpiperazine, 1- (2-hydroxyethyl) -4-propylpiperazine, 1- (2-hydroxyethyl) -4-butylpiperazine, 1- (2-hydroxypropyl) -4-methylpiperazine, 1- (2-hydroxypropyl) -4-ethylpiperazine, 1- (2-hydroxypropyl) -4-propylpiperazine, 1- (2-hydroxypropyl) -4 -Butyl piperazine, 1- (2-hydroxybutyl) -4-methylpiperazine, 1- (2-hydroxybutyl) -4-ethylpiperazine, 1- (2-hydroxybutyl) -4-propyl Piperazine, 1- (2-hydroxybutyl) -4-butylpiperazine, N- (2-hydroxyethyl) morpholine, N- (2-hydroxypropyl) morpholine, N-aminopropylmorpholine, Hydroxyethylpiperazine, hydroxy Propyl piperazine and 1- (N- methyl piperazine), a cleaning liquid composition for a flat panel display device is selected from the group consisting of ethanol.
3. The method according to claim 1,

   The compound represented by the formula (2) is 1,4-piperazinediethanol (1,4-Piperazinediethanol) and 1,4-piperazinedimethanol (1,4-Piperazinedimethanol) characterized in that the plate is selected from the group consisting of Cleaning liquid composition for a display device.
4. The method according to claim 1,

   Compound represented by the formula (3) is N- (2-hydroxyethyl) -ethylene urea, N- (3-hydroxypropyl) -2-pyrrolidone, hydroxymethylpyrrolidone and 1- (2-hydroxy Roxyethyl) -2-pyrrolidone cleaning liquid composition for a flat panel display characterized in that it is selected from the group consisting of.
5. The method according to claim 1,

   The compound represented by the formula (4) is in the group consisting of N- (2-hydroxyethyl) piperidine, N- (2-hydroxypropyl) piperidine and N- (2-hydroxybutyl) piperidine The cleaning liquid composition for a flat panel display characterized by the above-mentioned.
6. The method according to claim 1,

   Compound represented by the formula (5) is amino ethoxy ethanol, amino propoxy ethanol, amino butoxy ethanol, dimethyl amino ethoxy thiol, diethyl amino ethoxy thiol, dipropyl amino ethoxy thiol, dibutyl amino ethoxy thiol, Dimethylaminoethoxyethanol, diethylaminoethoxyethanol, dipropylaminoethoxyethanol, dibutylaminoethoxyethanol, dimethylaminoethoxyethanethiol, diethylaminoethoxypropanethiol, dipropylaminoethoxybutanethiol, Dibutylaminoethoxyethanol, N- (methoxymethyl) morpholine, N- (ethoxymethyl) morpholine, N- (2-methoxyethanol) morpholine, N- (2-ethoxyethanol) morpholine And N- (2-butoxyethanol) morpholine.
7. The method according to claim 1,

   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, 2- (2H-benzotriazol-2-yl) -4,6-di-tet-butylphenol and 2,2 '-[[[ethyl-1 hydrogen-benzotriazole -1-yl] methyl] imino] bisethanol. A cleaning liquid composition for a flat panel display device.
8. The method according to claim 1,

   The alkanol amine salt is a monoethanol amine salt, diethanol amine salt, triethanol amine salt, monoisopropanol amine salt, diisopropanol amine salt and triisopropanol amine salt selected from the group consisting of a cleaning liquid composition for a flat panel display device.
9. The method according to claim 1,

   The reducing agent is a cleaning liquid composition for a flat panel display device, characterized in that one or two or more selected from the group consisting of elisorbic acid, vitamin C and alpha tocopherol.
10. The method according to claim 1,

    A cleaning liquid composition for a flat panel display device, further comprising one selected from the group consisting of a chain alkanol amine, a polycarboxylic acid copolymer, a protic alkylene glycol monoalkyl ether compound, and a surfactant.
11. The method according to claim 10,

    The chain alkanol amine is monoethanolamine, monopropanolamine, monoisopropanolamine, butanolamine, 2-propoxyethylamine, N-butylethanolamine, N-methylethanolamine and N-ethylethanolamine The cleaning liquid composition for a flat panel display characterized by the above-mentioned.
12. The method according to claim 10,

    The polycarboxylic acid copolymer as a cleaning liquid composition for a flat panel display device comprising a structural unit represented by the following formula (6).

    <Formula 6>

    

    In Chemical Formula 6,

    R ₁₅ to R ₁₇ are each independently hydrogen, a C ₁ to C ₃ straight or branched alkyl 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.
13. The method according to claim 10,

    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 a flat panel display device selected from the group.
14. The method according to claim 1,

    PH of the cleaning liquid composition for a flat panel display device is 7 to 13, the cleaning liquid composition for a flat panel display device.
15. A method for cleaning a flat panel display using the cleaning liquid composition of claim 1.
16. The method according to claim 15,

    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. Washing method.
17. The method according to claim 15,

    The cleaning method is a cleaning method of a flat panel display device, characterized in that for cleaning at a temperature of 20 to 80 ℃.
18. The method according to claim 15,

    The cleaning method may include cleaning for 30 seconds to 10 minutes.

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