KR20170076087A - Liquid composition for stripping a color resist - Google Patents

Abstract

The present invention relates to a color resist stripping composition comprising an alkylene glycol alkyl ether of formula (2).

Description

LIQUID COMPOSITION FOR STRIPPING A COLOR RESIST

The present invention relates to a color resist stripper composition for reusing a color filter by removing a cured color resist of a 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, a color filter has been recognized as one of the most important components in reproducing color tone of an LCD.

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 a color resist pattern by a photolithography process.

If the color resist is cured once, it is almost impossible to repair only a wrong part, and since there is almost no solvent capable of removing the color resist, a poor There is a problem that the color filter is mostly disposed of immediately without being reworked, such as repair, and the productivity is lowered. To solve this problem, a composition for removing a cured color resist has been developed.

Resists can be largely divided into positive resists and negative resists, which, unlike positive resists, which are easier to remove and are removed by organic solvent-based exfoliants within one minute at a temperature of 40 to 50, And is hardened by heat treatment to make it difficult to remove the resist. Accordingly, in order to remove the color resist, it takes more than 5 minutes at a temperature of 70 or more, and therefore stronger peeling performance is required.

In addition, in order to realize a high resolution of a display, the number of pixels of the panel is increased. In the case of the RGBW transparent resist having a four-pixel structure for increasing the light efficiency of such a panel, thermal stability and chemical stability There is a problem that removal is more difficult by using a high resin. In this regard, the color resist stripper composition containing an alkylene glycol alkyl ether has been disclosed in Japanese Patent Laid-Open No. 10-2007-0075277. However, there is a problem in that the peelability of the color resist over time can not be sufficiently increased.

Korean Patent Publication No. 10-2007-0075277

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a color filter which eliminates a cured color resist, an organic insulating film and a transparent resin of a color filter with remarkably excellent peeling property, It is an object of the present invention to provide a color resist stripper composition which enables reuse of a color resist stripper composition.

In order to accomplish the above object, the present invention provides a color resist, an organic insulating film and a detergent composition for removing a transparent resin, which comprises an alkylene glycol alkyl ether of the formula (2).

In addition, the present invention provides a method of manufacturing a flat panel display substrate including a step of cleaning the flat panel display substrate using the color resist stripping liquid composition.

The color resist stripper composition according to the present invention not only exhibits excellent effects in terms of volatilization and aging but also removes the cured color resist of the color filter with remarkably excellent peeling property and enables the reuse of the color filter.

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

The present invention is a color resist stripping liquid composition comprising a specific alkylene glycol alkyl ether. The present invention relates to the above-mentioned alkylenecarboxylic alkyl ether, which contains a compound having a specific structure represented by the following general formula (2), and exhibits excellent effects in terms of volatilization and aging. In addition, the present invention provides a cured color resist, And thus the present invention has been completed.

The present invention relates to a color photoresist stripping liquid composition comprising an alkylene glycol alkyl ether represented by the general formula (2), and more specifically, (A) an inorganic base or a salt thereof; B) Quaternary ammonium salts; D) an alkylene glycol alkyl ether of Formula 2 ; And E) a polar solvent. Also, more specifically, A) an inorganic base or a salt thereof; B) Quaternary ammonium salts; C) alkoxyalkylamines; D) an alkylene glycol alkyl ether of Formula 2; E) polar solvent; F) anticorrosives; And G) water.

Hereinafter, each configuration of the present invention will be described in detail.

A) an inorganic base or a salt thereof

The inorganic base or salt thereof of the present invention has a role of improving the peeling force against the organic insulating film.

The inorganic base or its salt may be at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium nitrate, potassium nitrate, sodium sulfate, potassium sulfate, sodium silicate and potassium silicate.

The inorganic base or salt thereof of the present invention is preferably contained in an amount of 0.01 to 2% by weight based on the total weight of the composition. If the content of the inorganic base or its salt in the detergent composition of the present invention is less than 0.01% by weight, the peeling force against the organic insulating film is poor. If the amount is more than 2% by weight, the effect of increasing the amount is insignificant and not economical.

B) Quaternary ammonium salt

The quaternary ammonium salt compound of the present invention releases hydroxide ions, which penetrate into the resist and promote the dissolution of the polymer resist.

The quaternary ammonium salt compound is selected from the group consisting of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH) and tetrabutylammonium hydroxide (TBAH) Or more.

The quaternary ammonium salt compound of the present invention is preferably contained in an amount of 1-10% by weight based on the total weight of the composition. When the quaternary ammonium salt compound is contained in the detergent composition of the present invention in an amount of less than 1% by weight, penetration ability into the color resist polymer of the hydroxide ion is decreased. When the quaternary ammonium salt compound is contained in an amount of more than 10% by weight, There is a problem of being reduced.

C) Alkoxyalkylamines

The alkoxyalkylamine of the present invention penetrates into the cured resin and breaks bonds to dissolve the polymer.

In the present invention, the alkoxyalkylamine is a compound represented by the following formula (1).

(Formula 1)

Wherein R ₁ is a C ₁ to C ₆ chained or cyclic alkoxy group, the alkoxy group is a C ₁ to C ₆ chained or cyclic alkyl group, or a C ₁ to C ₃ alkoxy group And R ₂ and R ₃ are each independently hydrogen or a C ₁ to C ₆ chain or cyclic alkyl group, and m is an integer of 1 to 4.

Specifically, the alkoxyalkylamine represented by the above-mentioned general formula (1) is preferably selected from the group consisting of methoxyethylamine, methoxypropylamine, ethoxypropylamine, propoxyethylamine, isopropoxypropylamine, methoxyethoxypropylamine, oxolane- -Methanamine, (oxolan-2-yl-methyl) butan-l-amine and methyloxolan-2-yl-methanamine.

The alkoxyalkylamine of the present invention is preferably contained in an amount of 1-20% by weight based on the total weight of the composition. When the alkoxyalkylamine is contained in the detergent composition of the present invention in an amount of less than 1% by weight, the strength of breaking the bond by penetration into the cured resin is lowered. When the alkoxyalkylamine is more than 20% by weight, The solubility of the polymer resist is lowered.

D) Alkylene glycol alkyl ether

The alkylenecrylic alkyl ether of the present invention has the structure of the following formula (2).

(2)

In Formula 2, n is an integer of 0 to 4; And R ₄ are independently hydrogen, a C ₁ to C ₆ chained or cyclic alkyl group, or a C ₁ to C ₆ chained or cyclic alkoxy group.

Specifically, the compound of Formula 2 may have the structure of Formula 2-1.

(Formula 2-1)

In Formula 2-1, R ₅ is a C ₁ to C ₄ aliphatic hydrocarbon.

More specifically, the compound of Formula 2 may have a structure of any one of the following Formulas 2-2 to 2-4:

(2-2)

(Formula 2-3)

(2-4)

By including the alkylene glycol alkyl ether having the specific structure described above, it has been experimentally confirmed that the composition of the present invention not only exhibits excellent effects in terms of volatilization and aging but also shows rapid and strong peeling performance against a cured color resist.

The alkylene glycol alkyl ether of formula (2) of the present invention penetrates into the organic insulating film and swells to facilitate desorption on the substrate.

Specifically, the alkylene glycol alkyl ether of the formula (2) of the present invention may be Ethyltetrahydrofurfurylether, 2- (2-methoxyethoxymethyl) oxolane, Bistetrahydrofurfuryl-ether, and the like.

The alkylene glycol dialkyl ether of the present invention is preferably contained in an amount of 1-20% by weight based on the total weight of the composition. If the content of the alkylene glycol dialkyl ether is less than 1% by weight in the detergent composition of the present invention, the swelling effect of the resist polymer is reduced to decrease penetration into the resist of the hydroxide ion, and if it exceeds 20% by weight, There is no further effect and the solubility of the inorganic salt is reduced.

E) polar solvent

The polar solvent of the present invention penetrates the resist and increases the swelling property, thereby increasing the peeling force from the substrate surface. Further, the dissolution ability of the resist stripper composition of the present invention in water is improved, and the residue can be easily removed in the subsequent water washing step.

The polar solvent according to the present invention is not particularly limited and includes, for example, dimethylsulfoxide, diethylsulfoxide, dipropylsulfoxide, sulfolane, n-methylpyrrolidone, pyrrolidone, n-ethylpyrrolidone . These may be used alone or in combination of two or more.

The polar solvent may be included in an amount of 20 to 70% by weight, preferably 25 to 65% by weight based on the total weight of the resist stripper composition. When the content of the polar solvent is less than 20% by weight, the solubility of the resist may be decreased. When the content of the polar solvent is more than 70% by weight, the content of quaternary ammonium hydroxide and other components may be decreased, Can be degraded.

F) Corrective agent

The antifoaming agent of the present invention is not particularly limited and includes, for example, benzotriazole, tolythriazole, methyltolytriazole, 2,2 '- [[[benzotriazole] methyl] imino] Methyl] imino] bist methanol, 2,2 '- [[[ethyl-1-hydrogen benzotriazol- 1 -yl] methyl] Imino] bisethanol, 2,2 '- [[[methyl-1-hydrogen-benzotriazole- Benzimidazol-1-yl] methyl] imino] bismethylamine, 2,2 '- [[ An azole-based compound comprising [[amine-1-hydrogen-benzotriazol-1-yl] methyl] imino] bisethanol; Quinone compounds including 1,2-benzoquinone, 1,4-benzoquinone, 1,4-naphthoquinone, and anthraquinone; Catechol; Alkyl gallate compounds including pyrogallol, methyl gallate, propyl gallate, dodecyl galatate, octyl galatate and gallic acid. These may be used alone or in combination of two or more.

The anticorrosive agent may be contained in an amount of 0.1 to 5% by weight based on the total weight of the resist stripper composition. If the content of the anticorrosive agent is less than 0.1% by weight, corrosion may occur in a metal wiring made of aluminum or an aluminum alloy and a copper or copper alloy in a peeling or deionized water rinsing process, and if it exceeds 5% by weight, Contamination and degradation of the peeling force may occur.

G) Water

The water of the present invention may be prepared by appropriately adopting the above-mentioned components according to the specific needs of the resist stripper composition, and then adding water to adjust the total composition so that the remaining amount of the entire composition is occupied by water. Preferably, the components are adjusted to have the aforementioned content ranges.

The kind of water is not particularly limited, but it is preferably deionized distilled water, more preferably deionized distilled water for semiconductor processing, and has a specific resistance value of 18 M OMEGA. Or more.

The present invention provides a method for manufacturing a flat panel display substrate including a step of cleaning a flat panel display substrate including a bottom film and various metal wirings using the color resist stripping liquid composition described above. The underlying film may include, but is not limited to, one or more of Cu, Mo, and Al.

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. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Example

Example  And Comparative Example : Resist  Preparation of release liquid composition

A residual amount of water was added to the composition and the content (% by weight) described below to prepare a resist stripping liquid composition.

A) an inorganic base or a salt thereof B) Quaternary ammonium salt C) Alkoxyalkylamines D) Alkylene glycol alkyl ether E) polar solvent F) Corrective agent ingredient weight ingredient weight ingredient weight ingredient weight ingredient weight ingredient weight Example 1 KOH 0.4 TMAH 8 A1 10 C 15 DMSO 30 BTA 0.1 Example 2 KOH 0.2 TMAH 10 A2 13 C1 18 DMSO 40 BTA One Example 3 KOH 0.3 TMAH 10 A1 13 C2 17 DMSO 35 BTA One Example 4 KOH 0.7 TMAH 8 A2 17 C2 17 DMSO 33 BTA One Example 5 KOH 0.1 TMAH 7 C2 20 DMSO 50 BTA One Example 6 KOH 0.1 TMAH 8 C1 18 DMSO 52 BTA Comparative Example 1 KOH 0.5 TMAH 10 A2 17 DMSO 50 BTA 1.5 Comparative Example 2 KOH 0.2 TMAH 10 A2 17 DMDG 20 DMSO 30 BTA 1.5 Comparative Example 3 KOH 0.2 TMAH 10 A2 17 DMG 17 DMSO 30 BTA 1.5

KOH: Potassium hydroxide

TMAH: tetramethylammonium hydroxide

C: Ethyl tetrahydrofurfuryl ether (ethyl tetrahydrofurfuryl ether)

C1: 2- (2-methoxyethoxymethyl) oxolane

C2: Bistetrahydrofurfuryl-ether

DMDG: Diethylene glycol dimethyl ether

DMG: ethylene glycol dimethyl ether

DMSO: dimethylsulfoxide

BTA: benzotriazole

A1: 3-methoxypropylamine

A2: 3-ethoxypropylamine

< Experimental Example 1 > Peel force  evaluation

A color filter substrate on which Red, Green, and Blue (hereinafter referred to as RGB) were respectively applied was used for the removal evaluation of the color resist.

The color resist was applied, pre-baked at 90 캜 for 120 seconds, exposed, and then developed. Thereafter, the substrate having the pattern formed in the oven was hard baked in an oven at 220 캜.

 In order to confirm the removability of the color resist, the resist was immersed in a 75 ° C solution for 3 minutes, 5 minutes, and 10 minutes, and the presence or absence of the resist was confirmed by an optical microscope. The results are shown in Table 2. &lt; tb &gt; &lt; TABLE &gt;

◎: 100% resist removal

○: Resist 80% or more removed

?: Less than 80% resist removal

X: No resist removal

< Experimental Example 2>  Timed Assessment

The compositions of the Examples and Comparative Examples were immersed in the solution for 10 minutes while being left at 75 DEG C, and the presence or absence of the resist remained over time with an optical microscope. The results are shown in Table 2. &lt; tb &gt; &lt; TABLE &gt;

◎; 100% resist removal after 12 hours.

○; 100% resist removal after 9 hours.

?; After 6 hours, 100% of the resist was removed.

×; 100% resist removal after 3 hours

Peelability depreciation Example 1 ◎ ◎ Example 2 ◎ ◎ Example 3 ◎ ◎ Example 4 ◎ ◎ Example 5 ○ ◎ Example 6 ○ ◎ Comparative Example 1 x × Comparative Example 2 △ × Comparative Example 3 △ ×

As shown in Table 2, when the color resist stripping solution of the example was used, it was confirmed that the color resist stripping solution composition of the comparative example exhibited excellent effects in both the peelability and the evaluation of the aging time.

Claims (12)

A color resist stripping liquid composition comprising an alkylene glycol alkyl ether of formula (2):
(2)

In Formula 2, n is an integer of 0 to 4; And R ₄ are independently hydrogen, a C ₁ to C ₆ chained or cyclic alkyl group, or a C ₁ to C ₆ chained or cyclic alkoxy group.
The method according to claim 1,
A) an inorganic base or a salt thereof; B) Quaternary ammonium salts; D) an alkylene glycol alkyl ether of Formula 2; And E) a polar solvent.
The method according to claim 1,
A) an inorganic base or a salt thereof; B) Quaternary ammonium salts; C) alkoxyalkylamines; D) an alkylene glycol alkyl ether of Formula 2; E) polar solvent; F) anticorrosives; And G) water.
4. The composition according to claim 3,
A) 0.01-2% by weight of an inorganic base or salt thereof; B) 1-10% by weight of quaternary ammonium salt; C) 1-20% by weight of alkoxyalkylamines; D) 1-20% by weight of an alkylene glycol alkyl ether; E) 20-70% by weight polar solvent; F) antiseptics 0.1-5% by weight; And G) a residual amount of water.
The color resist stripping composition according to any one of claims 1 to 3, wherein the compound of formula (2) has the following formula (2-1):
(Formula 2-1)

In Formula 2-1, R ₅ is a C ₁ to C ₄ aliphatic hydrocarbon.
4. The method according to any one of claims 1 to 3,
Wherein the compound of formula (2) has a structure of any one of the following formulas (2-2) to (2-4):
(2-2)

(Formula 2-3)

(2-4)

.
The method of claim 2 or 3, wherein the inorganic salt or salt A) is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium nitrate, potassium nitrate, sodium sulfate, potassium sulfate, sodium silicate, Color resist stripping liquid composition.
The method according to claim 2 or 3, wherein the B) quaternary ammonium salt is at least one selected from the group consisting of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH) and tetrabutylammonium hydroxide (TBAH). &Lt; / RTI &gt;
The method of claim 3, wherein the C) alkoxyalkylamine is selected from the group consisting of methoxyethylamine, methoxypropylamine, ethoxypropylamine, propoxyethylamine, isopropoxypropylamine, methoxyethoxypropylamine, 1-amine and methyloxolan-2-yl-methanamine, wherein at least one selected from the group consisting of mono-methane amine, (oxolan-2-yl-methyl) butan-
4. The method of claim 3, wherein the E) polar solvent is selected from the group consisting of dimethylsulfoxide, diethylsulfoxide, dipropylsulfoxide, sulfolane, n-methylpyrrolidone, pyrrolidone, Or more.
[4] The method of claim 3, wherein the F) anticorrosion agent is selected from the group consisting of benzotriazole, tolythriazole, methyltolytriazole, 2,2 '- [[[benzotriazole] methyl] imino] - [[ethyl-1-hydrogen benzotriazol-1-yl] methyl] imino] Dihydrobenzotriazol-1-yl] methyl] imino] bisethanol, 2,2 '- [[[methyl- - [[methyl-1-hydrogen-benzotriazol-1-yl] methyl] imino] bismethylamine, 2,2 '- [[[ -1 hydrogen-benzotriazol-1-yl] methyl] imino] bisethanol; Quinone compounds including 1,2-benzoquinone, 1,4-benzoquinone, 1,4-naphthoquinone, and anthraquinone; Catechol; And alkyl gallate compounds including pyrogallol, methyl gallate, propyl gallate, dodecyl gale, octyl galeate, and gallic acid.
A method for manufacturing a flat panel display substrate comprising the step of cleaning a flat panel display substrate using the color resist stripping composition according to any one of claims 1 to 3.