KR101988668B1 - Cleaning composition for removing color resist and organic insulating layer - Google Patents

Abstract

(상기 식에서, R₁ 및 R₂는 각각 독립적으로 탄소수 1~10의 알킬기, 탄소수 2~10의 알케닐기, 탄소수 1~10의 히드록시알킬기, 카르복실기, 히드록시기로 치환 또는 비치환된 탄소수 1~10의 알콕시기로 치환된 탄소수 1~10의 알킬기, 페닐기 또는 벤질기이다.)The present invention relates to a process for the preparation of a cured product, characterized in that it comprises quaternary ammonium hydroxide, dimethylsulfoxide, glycol ether organic solvent, alkylhydroxylamine, alkylamine, alkanolamine salt and water, A color resist, and a cleaning agent composition for removing an organic insulating film.
[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, a carboxyl group, a substituted or unsubstituted C1- An alkyl group having 1 to 10 carbon atoms substituted with an alkoxy group of 1 to 10 carbon atoms, a phenyl group or a benzyl group)

Description

[0001] The present invention relates to a cleaning composition for removing color resist and organic insulating film,

The present invention relates to a color resist stripper composition for a flat panel display for removing a cured color resist of a color filter to reuse the color filter.

A color filter can be embedded in a color imaging device of an image sensor, such as a complementary metal oxide semiconductor (CMOS) or a charge coupled device (CCD), and can be used to actually obtain a color image (PDP), a liquid crystal display (LCD), a field emission display (FEL), and a light emitting display (LED), and the application range thereof is rapidly expanding. Particularly, in recent years, the use of LCDs has been further expanded, and accordingly, color filters have been recognized as one of the most important components in reproducing color tones of LCDs.

The color filter substrate includes a black matrix that blocks red (R), green (G), and blue (B) patterns and leakage light between the pixels and improves contrast, and a common electrode .

The color filter is manufactured by applying a black matrix material selected according to the application to a glass substrate, forming a black mask pattern, and then forming an RGB color resist pattern by a photolithography process.

In such a color filter manufacturing process, a defective color filter may inevitably occur, and a composition for removing a cured color resist for reuse of such a defective color filter has been developed.

For example, Korea Patent No. 10-0779037 includes 1-50 wt% of an inorganic alkali hydroxide, 5-35 wt% of an alkylene glycol ether, 5-25 wt% of a water-soluble amine compound, and 4-49 wt% of water A color resist stripping liquid composition for a TFT-LCD is disclosed. However, the alkali base of the inorganic alkali hydroxide of the above composition has a problem that precipitation of inorganic alkali occurs due to volatilization of the stripping liquid at a high temperature.

Korean Patent No. 10-1043397 discloses a coloring filter for reusing a color filter containing an inorganic alkali hydroxide or alkyl ammonium hydroxide, dimethyl sulfoxide, a dialkylene glycol ether, a water-soluble amine, an inorganic alkali acetate and water But the inorganic alkali acetate as a salt precipitates into powder due to the evaporation of water during the high temperature process, which may cause defects.

In addition, in the present flat panel display device manufacturing process, when an organic insulating film is used for coating a color filter and coating defects of RGB of the color filter occur or coating failure of the organic insulating film occurs, instead of discarding the color filter, There is a need for a cleaning composition capable of simultaneously removing the RGB color resist and the organic insulating film for reuse of the color filter because the yield of the process is improved and the cost is reduced.

KR 10-0779037 B KR 10-1043397 B

In order to solve the above-mentioned problems of the prior art by precipitation of water by volatilization in a high-temperature process and insufficient removal power of RGB or organic insulating film, the present invention provides a method of removing a cured RGB color resist and an organic insulating film for reuse of a color filter It is an object of the present invention to provide a detergent composition.

In order to attain the above object, the present invention provides a composition comprising 1 to 10% by weight of quaternary ammonium hydroxide, 30 to 80% by weight of dimethyl sulfoxide, 1 to 20% by weight of a glycol ether organic solvent, 1 to 20% by weight of an alkylhydroxylamine represented by 1, 1 to 20% by weight of an alkylamine, 0.01 to 2% by weight of an alkanolamine salt and 1 to 40% by weight of water, and A cleaning agent composition for removing an organic insulating film is provided.

In this formula,

R ₁ and R ₂ are each independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, a carboxyl group, an alkoxy group having 1 to 10 carbon atoms which is substituted or unsubstituted with a hydroxy group An alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group.

The composition of the present invention is used to remove a cured RGB color resist pattern of a color filter of a flat panel display device and removes the color resist in such a manner that the color resist is dissolved without lifting off the substrate from the substrate, Can be sufficiently removed, the filter clogging in the equipment can be minimized, and the productivity of the color filter rework can be improved.

In addition, the composition of the present invention can be used to remove the organic insulating film used for the coating of the color filter.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a composition comprising 1 to 10% by weight of quaternary ammonium hydroxide, 30 to 80% by weight of dimethyl sulfoxide, 1 to 20% by weight of a glycol ether organic solvent, an alkylhydroxyl group represented by the following formula A cleaning agent composition for removing a cured color resist and an organic insulating film, which comprises 1 to 20% by weight of an amine, 1 to 20% by weight of an alkylamine, 0.01 to 2% by weight of an alkanolamine salt and 1 to 40% to provide.

[Chemical Formula 1]

In this formula,

R ₁ and R ₂ are each independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, a carboxyl group, an alkoxy group having 1 to 10 carbon atoms which is substituted or unsubstituted with a hydroxy group An alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group.

The organic insulating layer is formed of an acrylic polymer resin, a polyimide resin, a polyether sulfone resin, or the like, which is laminated on a color filter to protect the color filter. The composition of the present invention can remove the organic insulating film as well as the cured color resist for reuse of the color filter.

The quaternary ammonium hydroxide's hydroxyl ions penetrate into the color polymer resist and promote the dissolution of the polymer resist.

Wherein the quaternary ammonium hydroxide is selected from the group consisting of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH) and tetrabutylammonium hydroxide (TBAH) , But the present invention is not limited thereto.

The quaternary ammonium hydroxide is preferably contained in an amount of 1 to 10% by weight based on the total weight of the composition. If it is less than 1% by weight, the penetration ability of the hydroxide ion color resist polymer is decreased. If it is more than 10% by weight, the content of water is increased, and the content of dimethyl sulfoxide is decreased to decrease the solubility of the polymer resist.

The dimethylsulfoxide penetrates the swollen polymer resist and dissolves the resist.

The dimethylsulfoxide is preferably contained in an amount of 30 to 80% by weight based on the total weight of the composition. When the amount is less than 30% by weight, the resist solubility decreases. When the amount exceeds 80% by weight, the penetration of the hydroxide ion into the resist decreases due to the decrease of the quaternary ammonium hydroxide.

The glycol ether organic solvent permeates the polymer resist to increase the swelling property, thereby increasing the peeling force from the substrate surface. In addition, the glycol ether organic solvent can improve the solubility and rinsing power of the detergent composition of the present invention in water.

Specific examples thereof include ethylene glycol monomethyl ether (MG), diethylene glycol monomethyl ether (MDG), diethylene glycol monoethyl ether (EDG), carbitol, Ethylene glycol monoethyl ether (EG), triethylene glycol monoethyl ether (ETG), triethylene glycol monomethyl ether (MTG), diethylene glycol methyl ethyl ether (MFG) selected from the group consisting of ethylene glycol monomethyl ether (MDG), diethylene glycol monoethyl ether (MDG), dipropylene glycol monomethyl ether (MFDG), and propylene glycol monomethyl ether Mixtures thereof, but are not limited thereto.

The glycol ether organic solvent is preferably contained in an amount of 1-20% by weight based on the total weight of the composition. If it is less than 1% by weight, the peelability of the detergent composition due to the addition of glycol ether to the polymeric resist can not be increased, and if it exceeds 20% by weight, the solubility decreases due to reduction of dimethylsulfoxide, which is uneconomical.

The alkylhydroxylamine is a compound represented by the following formula (1).

[Chemical Formula 1]

In this formula,

R ₁ and R ₂ are each independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, a carboxyl group, an alkoxy group having 1 to 10 carbon atoms which is substituted or unsubstituted with a hydroxy group An alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group.

Representative alkylhydroxylamines represented by Formula 1 include dimethylhydroxylamine, diethylhydroxylamine, dibutylhydroxylamine, and the like.

The alkylhydroxylamine is preferably included in an amount of 1-20% by weight based on the total weight of the composition. When the above range is satisfied, the alkylhydroxylamine penetrates into the crosslinked structure of the color resist to increase the swelling power of the polymer, thereby increasing the peeling force of the composition to the color resist. When the amount of the alkylhydroxylamine is less than 1% by weight, the solubility of the color resist decreases. When the amount of the alkyl hydroxylamine is more than 20% by weight, the effect of increasing the amount of the alkyl hydroxylamine is not increased.

The alkylamine serves to dissolve the dye component of the color resist.

Examples of the alkylamine include, but are not limited to, primary amines such as methylamine, ethylamine and monoisopropylamine; Secondary amines such as diethylamine, diisopropylamine and dibutylamine; Tertiary amines such as trimethylamine, triethylamine, triisopropylamine and tributylamine; Diamines such as ethylenediamine, 1,3-propanediamine, and 1,2-propylenediamine; And triamine such as diethyl triamine, dioctylenetriamine, and the like.

The alkylamine is preferably contained in an amount of 1 to 20% by weight based on the total weight of the composition. If it is contained in an amount of less than 1% by weight, it is difficult to dissolve the dye component of the color resist, and if it exceeds 20% by weight, the effect due to the increase is not increased, The solubility of the resist decreases.

The alkanolamine salt improves the peeling force against the organic insulating film. The alkanolamine salt used in the present invention is preferably selected from the group consisting of alkanolamines in which the alkyl moiety is usually lower alkyl, i.e., C1 to C5 alkyl. Other lower alkanolamine salts such as dimethylmethanolamine salts are also suitable, as one or more hydroxyl groups may remain in the alkanolamine salt, since other substituents may be present in the amine group.

Specific examples of the alkanolamine salt include alkanolamine salts such as monoethanolamine salt, diethanolamine salt, triethanolamine salt, monoisopropanolamine salt, diisopropanolamine salt and triisopropanolamine salt.

As the alkanolamine salts, commercially available products such as AB RUST CM (product of LABEMA Co.), AB RUST A4 (product of LABEMA Co.), EMADOX-NA (product of LABEMA Co.), EMADOX-NB EMADOX-103 (manufactured by LABEMA Co.), EMADOX-D520 (manufactured by LABEMA Co.), AB Rust at (manufactured by LABEMA Co.), EMADOX- . Products) may be used as appropriate.

The alkanolamine salt is preferably contained in an amount of 0.01 to 2.0% by weight based on the total weight of the composition. If it is less than 0.01% by weight, the peeling force against the organic insulating film is poor. If the amount is more than 2.0% by weight, It is not economical.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples.

Preparation of detergent composition

The cleaning agent compositions of Examples 1 to 9 and Comparative Examples 1 to 4 were prepared by mixing the ingredients shown in the following Table 1 according to the specified composition ratios.

Color resist Removability  evaluation

(RGB) color resist on a glass substrate, pre-baked at 90 DEG C for 120 seconds, exposed and developed to form a pattern, and the substrate was hardbaked in an oven at 220 DEG C to form a color filter substrate .

The color filter substrate was immersed in the cleaning agent composition solutions of Examples 1 to 9 and Comparative Examples 1 to 4 at 70 ° C for 3 minutes, 5 minutes and 10 minutes, respectively, and then the resist remained by optical microscope.

◎: 100% resist removal

○: Resist 80% or more removed

?: Less than 80% resist removal

X: No resist removal

Organic  Insulating film Removability  evaluation

The organic insulation film substrate was immersed in a cleaning agent composition solution of Examples 1 to 9 and Comparative Examples 1 to 4 at 70 DEG C for 3 minutes, 5 minutes, and 10 minutes, respectively, and then the organic insulating film was removed by an optical microscope. The results are shown in Table 2 below.

◎: 100% removal of organic insulating film

○: Removal of organic insulating film more than 80%

DELTA: Less than 80% removal of organic insulating film

X: No organic insulating film removed

Unit: wt% Quaternary ammonium hydroxide DMSO Alkylene glycol Alkylhydroxylamine Alkylamine Alkanolamine salt water Example 1 TMAH 8 45 EDG 3 Dimethylhydroxylamine 7 Ethylenediamine 5 One) 0.1 Balance Example 2 TMAH 4 60 MDG 10 Dimethylhydroxylamine 5 Diethylamine 5 2) 0.5 Balance Example 3 TMAH 6 50 MG 5 Diethylhydroxylamine 7 Ethylenediamine 8 3) One Balance Example 4 TEAH 3 65 MFG 5 Diethylhydroxylamine 12 Diethyl triamine 8 4) 0.05 Balance Example 5 TEAH 3 70 MEDG 5 Dimethylhydroxylamine 2 Diisopropylamine 13 5) 0.1 Balance Example 6 TEAH 6 50 MTG 12 Dibutylhydroxylamine 7 Triethylamine 11 One) 0.5 Balance Example 7 TMAH 2 70 MTG 8 Diethylhydroxylamine 5 Ethylenediamine 7 3) One Balance Example 8 TMAH 4 60 EDG 10 Dibutylhydroxylamine 5 Diethylamine 5 5) 1.5 Balance Example 9 TMAH 2 45 MDG 15 Dimethylhydroxylamine 15 Ethylenediamine 15 2) 0.2 Balance Comparative Example 1 TMAH 5 50 MFG 10 Dimethylhydroxylamine 15 - - 3) 0.1 Balance Comparative Example 2 TMAH 2 25 EDG 40 - - Diisopropylamine 30 4) 0.5 Balance Comparative Example 3 TEAH 3 65 - - Dimethylhydroxylamine 10 Triethylamine 10 - - Balance Comparative Example 4 TEAH 15 30 MDG 10 Diethylhydroxylamine 5 Diethyl triamine 5 - - Balance

* 1): EMADOX-NA (manufactured by LABEMA Co.)

* 2): EMADOX-NB (manufactured by LABEMA Co.)

* 3): AB-RUST-CM (manufactured by LABEMA Co.)

* 4): AB RUST A4 (manufactured by LABEMA Co.)

* 5): EMADOX-102 (manufactured by LABEMA Co.)

Board RGB substrate Organic insulating film substrate Rework time 3 minutes 5 minutes 10 minutes 3 minutes 5 minutes 10 minutes Example 1 ○ ○ ◎ ○ ○ ◎ Example 2 ○ ◎ ◎ ○ ◎ ◎ Example 3 ○ ○ ◎ ○ ◎ ◎ Example 4 ○ ◎ ◎ ○ ○ ◎ Example 5 ○ ◎ ◎ ○ ○ ◎ Example 6 ○ ○ ◎ ○ ◎ ◎ Example 7 ○ ◎ ◎ ○ ◎ ◎ Example 8 ○ ◎ ◎ ○ ◎ ◎ Example 9 ○ ○ ◎ ○ ○ ◎ Comparative Example 1 X X △ X △ △ Comparative Example 2 X X △ X △ △ Comparative Example 3 X △ △ X X △ Comparative Example 4 X △ △ X X X

As shown in Table 2, the cleaning compositions of Examples 1 to 9 exhibit a cleaning effect in a short period of time because of their excellent ability to remove not only RGB but also organic insulating films.

On the other hand, the cleaning compositions of Comparative Examples 1 to 4 required a long time to remove not only the RGB but also the organic insulating film, and the cleaning effect thereof was also insufficient.

Therefore, the color resist of the present invention and the detergent composition for removing the organic insulation film can sufficiently remove the color resist of the color filter, sufficiently remove the organic insulation film, and improve the productivity of the color filter reuse.

Claims (7)

1 to 10% by weight of quaternary ammonium hydroxide, 30 to 80% by weight of dimethyl sulfoxide, 1 to 20% by weight of a glycol ether organic solvent, 1 to 20% by weight of an alkylhydroxylamine represented by the following general formula (1) Characterized in that the cleaning agent composition comprises 20 to 20% by weight of alkylamines, 1 to 20% by weight of alkylamines, 0.01 to 2% by weight of alkanolamine salts and 1 to 40% by weight of water.
[Chemical Formula 1]

In this formula,
R ₁ and R ₂ are each independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, a carboxyl group, an alkoxy group having 1 to 10 carbon atoms which is substituted or unsubstituted with a hydroxy group An alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group. The process of claim 1, wherein the quaternary ammonium hydroxide is selected from the group consisting of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), and tetrabutylammonium hydroxide And TBAH). ≪ / RTI > The method of claim 1, wherein the glycol ether organic solvent is selected from the group consisting of ethylene glycol monomethyl ether (MG), diethylene glycol monomethyl ether (MDG), diethylene glycol monoethyl ether Ethylene glycol monoethyl ether (EG), triethylene glycol monoethyl ether (ETG), triethylene glycol monomethyl ether (MTG) ), Diethylene glycol methyl ethyl ether (MEDG), dipropylene glycol monomethyl ether (MFDG), and propylene glycol monomethyl ether (MFG). Characterized in that it is a mixture of one kind or two or more kinds of materials selected for the purpose of removing the cured color resist Detergent composition. The cleaning agent composition of claim 1, wherein the alkylhydroxylamine represented by Formula 1 is dimethylhydroxylamine, diethylhydroxylamine, or dibutylhydroxylamine. The method of claim 1, wherein the alkylamine is selected from the group consisting of methylamine, ethylamine, monoisopropylamine, diethylamine, diisopropylamine, dibutylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, ethylene Wherein the detergent composition is at least one selected from the group consisting of diamine, 1,3-propanediamine, 1,2-propylenediamine, diethyltriamine, and dioctylenetriamine. The method according to claim 1, wherein the alkanolamine salt is a monoethanolamine salt, a diethanolamine salt, a triethanolamine salt, a monoisopropanolamine salt, a diisopropanolamine salt or a triisopropanolamine salt. / RTI > The cleaning composition for removing a cured color resist according to claim 1, wherein the detergent composition is capable of simultaneously removing an organic insulating film.