TWI500762B - Cleaning composition for electronic devices - Google Patents

Description

Cleaning liquid composition for an electronic device

The present application claims the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the present disclosure.

The present invention relates to a cleaning liquid composition for a substrate for a flat panel display (FPD) including a liquid crystal display, a plasma display, a flexible display or the like.

Like a semiconductor device, FPD which is exemplified by a liquid crystal display is generally manufactured by film formation, photographic exposure, line etching, or the like. During this procedure, particles having a size of no more than 1 micron, such as various organic or inorganic materials, may themselves adhere to the surface of the substrate and cause contamination of the substrate. In the case where the substrate is subjected to a subsequent procedure in a state in which the contaminant remains attached, pinholes or pits of the film, and line cutting or bridging may occur, and the yield of the product is drastically reduced. Therefore, a cleaning procedure for removing contaminants is carried out between the programs, and various cleaning liquids have been introduced.

Korean Patent Application No. 10-2008-7003568 discloses a scavenger composition for a semiconductor device comprising an organic amine, an organic phosphonic acid, a linear sugar alcohol, and the balance being water. However, the scavenger is limitedly used in semiconductor devices, and thus it is difficult to apply to various fields. Further, the scavenger cannot prevent copper (Cu) and Cu alloy wiring from being corroded, and thus it is difficult to apply to an FPD device including a Cu or Cu alloy wiring.

Korean Patent No. 10-0503231 discloses a detergent composition having the ability to prevent corrosion of a metal such as aluminum (Al), Cu, or the like, and a metal for TFT-LCD, which comprises a specific alkanolamine compound, an organic solvent, and a pliers. Mixture compounds, nonionic surfactants, and water. However, the detergent composition may have a poor ability to remove organic contaminants and particles by using only a combination of an alkanolamine and an organic solvent, and may be caused by long-term use of a catechol or gallic acid of a polyhydroxybenzene clamp compound. Deposition problems, so there is a problem.

Korean Patent Application No. 10-2006-7015165 discloses a substrate cleaning liquid for a semiconductor device which comprises an organic acid, an organic alkali component, a surfactant, and water, and has a pH of from 1.5 to less than 6.5. However, since the cleaning solution is an acidic solution, it is insufficient in the initial cleaning stage to remove very small organic or inorganic particles of no more than 1 micron.

Accordingly, the present invention has been made in mind the problems encountered in the above related art, and it is an object of the present invention to provide a cleaning liquid composition which has high ability to remove organic contaminants or particles contaminating a glass substrate or a metal layer during the manufacture of FPD, Further, the ability to prevent metal lines such as Al, Al alloy, Cu, and Cu alloy formed on the FPD substrate from being corroded is also high.

One aspect of the present invention provides a cleaning liquid composition comprising 0.05 to 20% by weight of a basic compound, 0.1 to 40% by weight of a water-soluble polar organic solvent, and 0.01 to 10 parts by weight based on the total weight of the composition. % organic phosphate compound, 0.01 to 10% by weight of a polycarboxylic acid copolymer, 0.001 to 10% by weight of an alkanolamine salt, 0.001 to 10% by weight of a pyrrole compound, and the balance being water.

Another aspect of the present invention provides a method of manufacturing a matrix substrate for a liquid crystal display, which comprises cleaning the substrate using the above cleaning liquid composition.

The invention is described in detail below.

According to the present invention, a cleaning liquid composition comprises 0.05 to 20% by weight of a basic compound, 0.1 to 40% by weight of a water-soluble polar organic solvent, 0.01 to 10% by weight of an organic phosphoric acid compound, based on the total weight of the composition. 0.01 to 10% by weight of the polycarboxylic acid copolymer, 0.001 to 10% by weight of the alkanolamine salt, 0.001 to 10% by weight of the pyrrole compound, and the balance being water.

The basic compound contained in the cleaning liquid composition according to the present invention may include a quaternary ammonium salt compound such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), Tetrabutylammonium hydroxide (TBAH) or the like; an organic basic compound including a primary amine such as methylamine, ethylamine, monoisopropylamine, etc., a secondary amine such as diethylamine, diisopropylamine, dibutylamine, etc. , tertiary amines such as trimethylamine, triethylamine, triisopropylamine, tributylamine, etc.; alkanolamines such as choline, monoethanolamine, diethanolamine, 2-aminoethanol, 2-(ethylamino)ethanol , 2-(methylamino)ethanol, N-methyldiethanolamine, dimethylaminoethanol, diethylaminoethanol, nitrogen triethanol, 2-(2-aminoethoxy)ethanol, 1-amine The base-2-propanol, triethanolamine, monopropanolamine, dibutanolamine or the like may be used singly or in combination of two or more thereof.

The basic compound may be used in an amount of from 0.05 to 20% by weight, and preferably from 0.1 to 10% by weight, based on the total mass of the composition. If the amount of the basic compound is less than 0.05% by weight, particulates, organic contaminants and inorganic contaminants cannot be sufficiently removed. Conversely, if the amount exceeds 20% by weight, the pH of the composition may increase, and thus metal line corrosion may increase.

The water-soluble polar organic solvent contained in the cleaning liquid composition according to the present invention may include N-methylpyrrolidone (NMP), 1,3-dimethyl-2-tetrahydroimidazolidone (DMI), dimethyl group. Acetone (DMSO), dimethylacetamide (DMAc), dimethylformamide (DMF), tetrahydrofurfuryl alcohol, isophorone, diethyl adipate, dimethyl glutarate, cyclobutane Anthracene, γ-butyrolactone (GBL), etc., which may be used singly or in a mixture of two or more thereof.

The water-soluble polar organic solvent may be used in an amount of 0.1 to 40% by weight, and preferably 0.5 to 20% by weight, based on the total mass of the composition. If the amount of the water-soluble polar organic solvent is less than 0.1% by weight, the ability of the cleaning liquid composition to dissolve the contaminant cannot be expected to increase due to an increase in the solvent. Conversely, if the amount exceeds 40% by weight, the economic benefit is degraded and environmental advantages cannot be expected.

The organophosphoric acid compound contained in the cleaning liquid composition according to the present invention is very effective in removing organic contaminants or particles from the upper surface of the glass substrate, and also controls the total pH of the cleaning liquid composition, thereby preventing corrosion and presentation of the metal Cleaning effects play an important role.

The organophosphorus compound may include an amine ginseng (methylene phosphonic acid), ethylene diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxypropylidene-1,1- Diphosphonic acid, 1-hydroxybutylidene-1,1-diphosphonic acid, ethylaminopurine (methylene phosphonic acid), 1,2-propylenediaminetetrakis (methylenephosphonic acid), dodecylamine Base (methylene phosphonic acid), nitrosyl (methylene phosphonic acid), ethylene diamine oxime (methylene phosphonic acid), ethylene diamine tetra (methylene phosphonic acid), hexamethylene diamine tetra ( Methylene phosphonic acid), diethylenetriamine penta (methylene phosphonic acid), cyclohexanediamine tetra (methylene phosphonic acid), hydroxyphosphoninoacetic acid, and 2-phosphinyl-butane -1,2,4-tricarboxylic acid, which may be used singly or in combination of two or more.

The organic phosphoric acid compound may be used in an amount of from 0.01 to 10% by weight, and preferably from 0.05 to 5% by weight, based on the total mass of the composition. If the amount of the organophosphoric acid compound is less than 0.01% by weight, the ability of the cleaning liquid composition to remove contaminants or particles may be lowered, and it is difficult to control the pH of the cleaning liquid composition. Conversely, if the amount exceeds 10% by weight, the pH of the composition may be lowered, and thus the ability to remove particles is lowered and metal line corrosion is increased.

The polycarboxylic acid copolymer contained in the cleaning liquid composition according to the present invention forms a protective layer on the metal surface to suppress an excessive reaction between the metal and the alkali ion, thus preventing the metal from being corroded, and functions as a pH controlling agent. The polycarboxylic acid copolymer may contain a monomer represented by the following formula 1.

In Formula 1, R ₁ to R ₃ are independently a hydrogen atom, a methyl group, an ethyl group, or a -(CH ₂ )m ₂ COOM ₂ , and the M ₁ and M ₂ systems are independently a hydrogen atom, an alkali metal, or an alkaline earth. The metal or ammonium group, and m ₁ and m ₂ are independently an integer of 0 to 2.

The term "ammonium group" refers to not only ammonium (NH ₄ ⁺ ) but also ammonium which is one of the hydrogen atoms bonded to the nitrogen atom or more substituted with other substituents. For example, the ammonium group can comprise an alkylammonium.

The alkali metal may include Li, Na, K, Rb, Cs, or Fr, and the alkaline earth metal may include Ca, Sr, Ba, or Ra.

Specific examples of the polycarboxylic acid copolymer may include polyacrylic acid polymer (PAA), poly(methyl)methyl acrylate copolymer (PMAA), polyacrylic acid-maleic acid copolymer (PAMA), polyacrylic acid. - poly(methyl) methacrylate copolymer (PAMAA), polymaleic acid copolymer (PMA), poly(methyl) methacrylate-maleic acid copolymer (PMAMA), and salts thereof It may be used singly or in combination of two or more.

The polycarboxylic acid copolymer may be used in an amount of from 0.01 to 10% by weight, and preferably from 0.05 to 5% by weight, based on the total mass of the composition. If the amount of the polycarboxylic acid copolymer is less than 0.01% by weight, the effect of preventing corrosion of the metal wiring may be poor, and the ability to remove organic contaminants may be degraded. Conversely, if the amount exceeds 10% by weight, the pH of the composition may be lowered, and thus the ability to remove particles may be lowered, and the viscosity of the cleaning liquid may increase without deteriorating the cleaning power.

The alkanolamine salt contained in the cleaning liquid composition according to the present invention prevents corrosion of the metal and excessive etching of the oxide layer when cleaning the substrate having the metal pattern and the oxide layer, and imparts inhibition of pH change of the cleaning liquid. pH buffering effect. The salt used for the preparation of the alkanolamine salt can be maintained at a temperature of 90 ° C or lower.

The alkanolamine salt can be prepared from an alkanolamine comprising a lower alkyl group (e.g., a C1 to C5 alkyl group). Further, in the case where the amine group has one or two hydroxyalkyl groups, other substituents may be bonded to the amine group, and other lower alkanolamine salts such as dimethylmethanolamine salts may be used. Specific examples of the alkanolamine salt include monoethanolamine salt, diethanolamine salt, triethanolamine salt, monoisopropanolamine salt, diisopropanolamine salt, and triisopropanolamine salt, either alone or in Use of a mixture of two or more.

The alkanolamine salt may include commercially available products such as AB RUST CM (available from LABEMA Co.), AB RUST A4 (available from LABEMA Co.), EMADOX-NA (available from LABEMA Co.), EMADOX-NB (obtained) From LABEMA Co.), EMADOX-NCAL (from LABEMA Co.), EMADOX-102 (from LABEMA Co.), EMADOX-103 (from LABEMA Co.), EMADOX-D520 (from LABEMA Co.), And AB RUST AT (available from LABEMA Co.).

The alkanolamine salt may be used in an amount of 0.001 to 10% by weight, and preferably 0.01 to 3% by weight, based on the total mass of the composition. If the amount of the alkanolamine salt is less than 0.001% by weight, the pH buffering effect and the ability to prevent corrosion of the metal wiring may be poor. Conversely, if the amount exceeds 10% by weight, the pH may be lowered, thus the cleaning power is lowered, and the corrosion resistance is not linearly increased in proportion to the amount thereof.

The pyrrole compound contained in the cleaning liquid composition according to the present invention can be represented by the following formula 2.

In Formula 2, R ₄ , R ₅ and R ₆ are independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an allyl group, an aryl group, an amine group, an alkylamino group, a nitro group, a cyano group, A mercapto group, an alkyl group, a hydroxyl group, a hydroxyalkyl group, a carboxyl group, a carboxyalkyl group, a decyl group, an alkoxy group, or a monovalent group having a heterocyclic ring.

Wherein the alkyl group has 1 to 10 carbon atoms, the aryl group has 5 to 12 carbon atoms, the alkoxy group has 1 to 10 carbon atoms, and the heterocyclic ring has 4 to 12 carbon atoms. .

Specific examples of the pyrrole-based compound include 2,2'-[[[benzotriazol-1-yl]methyl]imino]oxime ethanol, 2,2'-[[[methyl-1H- Benzotriazol-1-yl]methyl]imino]indole methanol, 2,2'-[[[ethyl-1H-benzotriazol-1-yl]methyl]imino]indoleethanol , 2,2'-[[[methyl-1H-benzotriazol-1-yl]methyl]imino]indoleethanol, 2,2'-[[[methyl-1H-benzotriazole] -1-yl]methyl]imino]anthracenecarboxylic acid, 2,2'-[[[methyl-1H-benzotriazol-1-yl]methyl]imino]]methylamine, and 2,2'-[[[Amine-1H-benzotriazol-1-yl]methyl]imino]oximeethanol, which may be used singly or in a mixture of two or more thereof.

The azole compound can be used in an amount of 0.001 to 10% by weight, and preferably 0.01 to 3% by weight, based on the total weight of the composition. When the amount of the component is within the above range, the metal layer can be minimized and economic benefits can be ensured.

Further, the water contained in the cleaning liquid composition according to the present invention is not particularly limited, but may include deionized water having a resistivity (which is a degree to which ions are removed from water) of at least 18 MΩ/cm.

Substrate cleaning using the cleaning fluid composition in accordance with the present invention can be carried out by methods generally known in the art. The cleaning method can include, for example, spraying, spinning, soaking, and using ultrasonic soaking. The temperature at which the cleaning liquid composition according to the present invention exhibits the maximum cleaning effect is set to be 20 to 80 ° C, and preferably 20 to 50 ° C. Further, substrate cleaning using the cleaning liquid composition according to the present invention can be carried out for a period of 30 seconds to 10 minutes.

The invention is best understood by the following examples, which are not to be construed as limiting. The following embodiments are appropriately modified within the scope of the invention by those skilled in the art.

Examples 1 to 20 and Comparative Examples 1 to 3: Preparation of cleaning liquid composition

A predetermined amount of the components shown in Table 1 below were mixed and stirred to prepare a cleaning liquid composition.

A-1: tetramethylammonium hydroxide (TMAH)

A-2: Tetraethylammonium hydroxide (TEAH)

A-3: monoisopropylamine (MIPA)

A-4: monoethanolamine (MEA)

B-1: N-methylpyrrolidone (NMP)

B-2: 1,3-dimethyl-2-tetrahydroimidazolidone (DMI)

C-1:1-hydroxyethylidene-1,1-diphosphonic acid

C-2: amine ginseng (methylene phosphonic acid)

D-1: Polyacrylic acid-maleic acid copolymer (PAMA)

D-2: Poly(methyl) methacrylate-maleic acid copolymer (PMAMA)

E-1: EMADOX-NB (available from LABEMA Co.)

E-2: EMADOX-D520 (available from LABEMA Co.)

F-1: 2,2'-[[[Ethyl-1H-benzotriazol-1-yl]methyl]imino]indoleethanol

Test case: Evaluation of the properties of the cleaning liquid composition

1) Evaluation of Al and Cu etch rates

A glass substrate having an Al layer of 2000 angstroms and a glass substrate having a Cu layer of 2,500 angstroms were immersed in the cleaning liquid compositions of Examples 1 to 9, 13, 17, and Comparative Examples 1 to 3 for 30 minutes. . The temperature of the cleaning liquid is 40 ° C, and the thicknesses of the Al layer and the Cu layer are measured before and after the immersion, and the dissolution rates of the Al layer and the Cu layer are calculated from the thickness changes. The results are shown in Table 2 below.

2) Assessment of the ability to remove organic pollutants-1

In order to evaluate the ability of organic contaminants, the surface of a glass substrate having a size of 5 cm x 5 cm was contaminated with a human fingerprint or with an organic felt tip pen, and the surface to be contaminated was treated with a spray type glass substrate cleaning device as in Examples 3, 4. , 4~20 of 40 ° C cleaning solution composition cleaned for 2 minutes. The substrate was then washed with ultrapure water for 30 seconds and then dried using nitrogen. It is indicated by ○ when it is judged that the organic pollutant has been removed, and is represented by X when it is judged that the organic pollutant has not been removed. The results are shown in Table 2 below.

Further, the results of removing the organic contaminant using the cleaning liquid composition of Example 4 are shown in Figs. 1 is a photograph showing a glass substrate contaminated with organic contaminants marked with an organic felt tip before cleaning, and FIG. 2 is a photograph showing the glass substrate contaminated with an organic felt tip pen after cleaning. 3 is a photograph showing a glass substrate contaminated with organic pollutants of a human fingerprint before cleaning, and FIG. 4 is a photograph showing a glass substrate contaminated with fingerprints after cleaning.

3) Assessment of the ability to remove organic pollutants-2

The glass substrate was allowed to stand in the air for 24 hours, so as to be contaminated with various organic substances, inorganic substances, and particles in the air, and then cleaned with the spray type glass substrate cleaning device at 40 ° C of the cleaning liquid composition of Examples 3, 4, and 7-20. 2 minutes. The substrate was then washed with ultrapure water for 30 seconds and then dried using nitrogen. Then, 0.5 μl of ultrapure water was dropped on the glass substrate, and the contact angle after cleaning was measured. The results are shown in Table 2 below.

4) Assessment of the ability to remove organic pollutants-3

The glass substrate contaminated with the organic particle solution was cleaned with the cleaning liquid compositions of Examples 3, 9, 13, and 17. Specifically, the glass substrate was contaminated with an organic particle solution having an average particle size of 0.8 μm, spun at 3000 rpm for 1 minute, and then cleaned with a spray type glass substrate cleaning device at a temperature of 40 ° C or more for 2 minutes. The substrate was then washed with ultrapure water for 30 seconds and then dried using nitrogen. The number of particles having a size of 0.1 μm or more before and after cleaning was calculated using a surface particle counter (Topcon WM-1500). The results are shown in Table 2 below.

As is apparent from the results of Table 2 and Figs. 1 to 4, the cleaning liquid composition according to the present invention has high corrosion resistance to Al or Cu, and the ability to remove organic contaminants and particles is very high.

As described above, the present invention provides a cleaning liquid composition for a semiconductor device. According to the present invention, the cleaning liquid composition has high ability to remove organic contaminants from the surface of the FPD glass substrate or the metal layer, and prevents metal lines such as Al, Al alloy, Cu, Cu alloy formed on the substrate from being The ability to corrode is also high. Further, the cleaning liquid composition contains a large amount of water, and thus is easy to handle and environmentally friendly.

While the invention has been described with respect to the embodiments of the present invention, it will be understood that Scope and spirit.

The features and advantages of the present invention are more clearly understood from the following detailed description in conjunction with the accompanying drawings in which: FIG. 1 is a photograph showing a glass substrate contaminated with organic contaminants marked by an organic felt tip before cleaning; FIG. 2 is a view Photograph of the glass substrate contaminated by the organic felt tip pen after cleaning using the cleaning liquid composition of Example 4; FIG. 3 is a photograph showing the glass substrate contaminated by organic fingerprints of the human fingerprint before cleaning; and FIG. A photograph of the glass substrate contaminated with the fingerprint after cleaning using the cleaning liquid composition of Example 4 is displayed.

Claims (9)

A cleaning liquid composition comprising 0.05 to 20% by weight of a basic compound, 0.1 to 40% by weight of a water-soluble polar organic solvent, 0.01 to 10% by weight of an organic phosphoric acid compound, 0.01~, based on the total weight of the composition 10% by weight of a polycarboxylic acid copolymer, 0.001 to 10% by weight of an alkanolamine salt, 0.001 to 10% by weight of a pyrrole compound, and the balance being water, wherein the pyrrole compound is represented by the following formula 2: Wherein R ₄ , R ₅ and R ₆ are independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an allyl group, an aryl group, an amine group, an alkylamino group, a nitro group, a cyano group, a decyl group or an alkyl fluorenyl group. a hydroxy group, a hydroxyalkyl group, a carboxyl group, a carboxyalkyl group, a decyl group, an alkoxy group, or a monovalent group having a heterocyclic ring, wherein the alkyl group has 1 to 10 carbon atoms, and the aryl group has 5 to 12 The carbon atom has 1 to 10 carbon atoms, and the heterocyclic ring has 4 to 12 carbon atoms. The cleaning liquid composition of claim 1, wherein the basic compound is selected from the group consisting of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), and hydroxide. Tetrabutylammonium (TBAH), methylamine, ethylamine, monoisopropylamine, diethylamine, diisopropylamine, dibutylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, choline, monoethanolamine, Diethanolamine, 2-aminoethanol, 2-(ethylamino)ethanol, 2-(methylamino)ethanol, N-methyldiethanolamine, dimethylaminoethanol, diethylaminoethanol, nitrogen triethanol , 2-(2-Aminoethoxy)ethanol, 1-Amino-2-propanol, three One or more of the group consisting of ethanolamine, monopropanolamine, and dibutanolamine. The cleaning liquid composition of claim 1, wherein the water-soluble polar organic solvent is selected from the group consisting of N-methylpyrrolidone (NMP) and 1,3-dimethyl-2-tetrahydroimidazolidone (DMI). ), dimethyl hydrazine (DMSO), dimethyl acetamide (DMAc), dimethylformamide (DMF), tetrahydrofurfuryl alcohol, isophorone, diethyl adipate, glutaric acid One or more of the group consisting of methyl ester, cyclobutyl hydrazine, and γ-butyrolactone (GBL). The cleaning liquid composition of claim 1, wherein the organic phosphoric acid compound is selected from the group consisting of an amine group (methylene phosphonic acid), ethylene diphosphonic acid, 1-hydroxyethylidene-1, 1- Diphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, 1-hydroxybutylidene-1,1-diphosphonic acid, ethylaminopurine (methylenephosphonic acid), 1,2-propane Diamine tetra (methylene phosphonic acid), dodecylamine hydrazine (methylene phosphonic acid), nitrosyl (methylene phosphonic acid), ethylenediamine oxime (methylene phosphonic acid), ethylene Amine tetra (methylene phosphonic acid), hexamethylene diamine tetra (methylene phosphonic acid), diethylene triamine penta (methylene phosphonic acid), cyclohexane diamine tetra (methylene phosphonic acid), One or more of the group consisting of hydroxyphosphinic acid and 2-phosphono-butane-1,2,4-tricarboxylic acid. The cleaning liquid composition of claim 1, wherein the polycarboxylic acid copolymer comprises a monomer of the following formula 1: Wherein R ₁ to R ₃ are independently a hydrogen atom, a methyl group, an ethyl group, or a -(CH ₂ )m ₂ COOM ₂ , and the M ₁ and M ₂ systems are independently a hydrogen atom, an alkali metal, an alkaline earth metal, or an ammonium salt. The base, and m ₁ and m ₂ are independently an integer of 0 to 2. The cleaning liquid composition of claim 5, wherein the polycarboxylic acid copolymer is selected from the group consisting of polyacrylic acid polymer (PAA), poly(methyl) methacrylate copolymer (PMAA), polyacrylic acid-cis. Butene acid copolymer (PAMA), polyacrylic acid-poly(methyl) methacrylate copolymer (PAMAA), polymaleic acid copolymer (PMA), poly(methyl) methacrylate-cis-butyl One or more of the group consisting of olefinic acid copolymer (PMAMA) and its salts. The cleaning liquid composition of claim 1, wherein the alkanolamine salt is selected from the group consisting of monoethanolamine salt, diethanolamine salt, triethanolamine salt, monoisopropanolamine salt, diisopropanolamine salt, and One or more of the groups consisting of isopropanolamine salts. The cleaning liquid composition according to claim 1, wherein the pyrrole compound is selected from the group consisting of 2,2'-[[[benzotriazol-1-yl]methyl]imino] oxime ethanol, 2, 2'-[[[methyl-1H-benzotriazol-1-yl]methyl]imino]indole methanol, 2,2'-[[[ethyl-1H-benzotriazole-1- Methyl]imido]oxime ethanol, 2,2'-[[[methyl-1H-benzotriazol-1-yl]methyl]imino]oxime ethanol, 2,2'-[ [[Methyl-1H-benzotriazol-1-yl]methyl]imino]indolecarboxylic acid, 2,2'-[[[methyl-1H-benzotriazol-1-yl]- One of the groups consisting of 2,2'-[[[amine-1H-benzotriazol-1-yl]methyl]imino]indoleethanol or the above. A method of manufacturing a matrix substrate for a liquid crystal display, which comprises cleaning the substrate using a cleaning liquid composition as in the first aspect of the patent application.