KR20170076090A - Liquid composition for stripping a color resist - Google Patents

Abstract

A) an inorganic base or a salt thereof; B) quaternary ammonium salt compounds; C) alkoxyalkylamines of formula (1); D) alkylene glycol alkyl ethers; E) a solvent comprising DMSO and sulfolane; F) anticorrosives; G) Sulfur compound stabilizer; And H) water.

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.

Korean Patent Publication No. 2007-0075277 discloses a color resist stripper composition containing a sulfur compound as a solvent, but it can not sufficiently improve the peelability of a color resist, and in the case of some sulfur compounds, Thereby causing a discoloration of the ink.

Korean Patent Publication No. 2007-0075277

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and it is an object of the present invention to provide a color filter which not only minimizes discoloration of a composition but also exhibits remarkably excellent peelability without causing corrosion of a lower film, It is an object of the present invention to provide a color resist stripper composition which removes resin to enable reuse of a color filter.

In order to accomplish the above object, the present invention provides a process for producing a polyurethane foam comprising: A) an inorganic base or a salt thereof; B) quaternary ammonium salt compounds; C) alkoxyalkylamines of formula (1); D) alkylene glycol alkyl ethers; E) a solvent comprising DMSO and sulfolane; F) anticorrosives; G) Sulfur compound remover; And H) water, wherein the content of DMSO is equal to or greater than the content of sulfolane.

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 minimizes discoloration but also removes the cured color resist, the organic insulating film and the transparent resin of the color filter with remarkably excellent peeling property without causing corrosion of the lower film, Enables reuse.

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

The present invention provides a color resist stripper composition comprising: A) an inorganic base or a salt thereof; B) quaternary ammonium salt compounds; C) alkoxyalkylamines; D) alkylene glycol alkyl ethers; E) a solvent comprising DMSO and sulfolane; F) anticorrosives; G) Sulfur compound stabilizer; And H) water, wherein the content of DMSO is equal to or greater than the content of sulfolane. The color resist stripper composition of the present invention exhibits fast and strong peeling performance against cured color resist. In particular, when the solvent and the sulfur compound stabilizer which simultaneously contain DMSO and sulfolane are included in the color resist stripper composition, discoloration of the stripper composition is minimized, and peeling resistance It was confirmed that the improvement was remarkable experimentally.

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  compound

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) Alkoxyalkylamine

The alkoxyalkylamine of the present invention functions to dissolve the polymer by penetrating into the cured resin to break the bond

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

[Chemical Formula 1]

Wherein R ₁ is a C ₁ to C ₆ chained or cyclic alkoxy group, and 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 -C ₆ chain or cyclic alkyl group, and n 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. If the alkoxyalkylamine is contained in the detergent composition of the present invention in an amount of less than 1% by weight, the force to break the bond due to penetration into the cured resin is lowered. If the alkoxyalkylamine is more than 20% by weight, the quaternary ammonium salt compound and the solvent The solubility of the polymer resist decreases.

D) Alkylene glycol alkyl ether

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

Examples of the alkylene glycol dialkyl ether include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl butyl ether, propylene glycol dimethyl ether And dipropylene glycol dimethyl ether.

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) DMSO and Sulfolane  At the same time,

The DMSO and sulfolane of the present invention penetrate the resist to increase the swelling property and increase 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 solvent containing DMSO and sulfolane of the present invention is preferably contained in an amount of 20-70% by weight based on the total weight of the composition. If the polar solvent is included in the detergent composition of the present invention, the solubility of the polymer resin is lowered. If the polar solvent is contained in an amount of more than 70% by weight, the activity of the ammonium salt compound is deteriorated.

Also, it is preferable that the content of DMSO is equal to or greater than the content of sulfolane. In this case, it is possible to increase the peeling force from the substrate surface by increasing the swelling property by penetrating the resist. If the DMSO content is less than the sulfolane content, the swellability of the resist is lowered and the peeling force is lowered.

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) Sulfur compound stabilizer

The sulfur compound stabilizer of the present invention may be a compound having a structure represented by the following formula (2).

(2)

In Formula 2,

R ₄ and R ₅ are respectively independently, C ₁ ~ C ₁₀ an alkyl group, a phenyl group or a benzyl group, a C ₁ ~ C ₁₀ alkyl group, phenyl group or benzyl group is C ₁ ~ C ₁₀ alkyl group, C ₂ ~ C of _A C ₁ to C ₁₀ hydroxyalkyl group, a carboxyl group, a hydroxy group, or a C ₁ to C ₁₀ alkoxy group.

The sulfur compound stabilizer may be contained in an amount of 0.1 to 5% by weight based on the total weight of the resist stripper composition. When the content 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. If the content is more than 5% by weight, secondary contamination and peeling If less than 0.1 wt%, the stability of the sulfur compound is not improved. If it is more than 5 wt%, secondary contamination due to adsorption of the surface and deterioration of the peeling force may occur.

H) water

The resist stripper composition of the present invention may be appropriately selected according to the specific needs of the above components, and then water may be added 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  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 compound C)
The alkoxyalkylamines of formula (I) D)
Alkylene glycol alkyl ether Le E)
DMSO and Solvent containing sulfolane F)
Anti-corrosion agent G)
Sulfur compound stabilizer ingredient weight ingredient weight ingredient weight ingredient weight ingredient weight ingredient weight ingredient weight ingredient weight Example 1 KOH 0.4 TMAH 7 A1 15 G1 20 S1 20 S3 10 BTA 0.1 H1 3 Example 2 KOH 0.1 TMAH 5 A1 15 G1 10 S1 35 S3 15 BTA One H2 One Example 3 KOH One TMAH 10 A1 15 G1 15 S1 25 S3 25 BTA 0.3 H1 0.1 Example 4 KOH 0.1 TMAH 5 A2 15 G1 10 S1 35 S3 15 BTA One H1 One Example 5 KOH 0.1 TMAH 5 A2 15 G2 10 S1 35 S3 15 BTA One H2 One Comparative Example 1 KOH 0.5 TMAH 7 A1 10 G1 20 S1 15 S3 30 BTA 1.5 Comparative Example 2 KOH 0.3 TMAH 8 A1 20 G1 15 S3 40 BTA 2 H2 5 Comparative Example 3 KOH 0.7 TMAH 9 A1 15 G1 20 S1 45 BTA 0.5 H1 2 Comparative Example 4 KOH 0.4 TMAH 10 A1 10 G1 10 S1 30 S3 25 BTA One HA One Comparative Example 5 KOH 0.4 TMAH 7 A1 15 G2 20 S1 20 S2 10 BTA 0.1 H1 3

KOH: Potassium hydroxide

TMAH: tetramethylammonium hydroxide

A1: 3-methoxypropylamine

A2: 3-ethoxypropylamine

G1: Diethylene glycol dimethyl ether

G2: triethylene glycol dimethyl ether

S1: dimethyl sulfoxide

S2: dipropyl sulfoxide

S3: Sulforan

H1: Diethylhydroxylamine

H2: dimethylhydroxylamine

HA: Hydroxylamine

BTA: benzotriazole

EXPERIMENTAL EXAMPLE 1 Evaluation of Peelability of Peeling Solution

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. < tb > < TABLE >

◎: 100% resist removal

○: Resist 80% or more removed

?: Less than 80% resist removal

X: No resist removal

EXPERIMENTAL EXAMPLE 2 Evaluation of discoloration of peeling liquid

Changes in color were observed while the compositions of the above Examples and Comparative Examples were left at 75 占 폚. The results are shown in Table 2. < tb > < TABLE >

◎; No discoloration was observed after 12 hours.

○; Discoloration was confirmed after 9 hours.

?; Discoloration was confirmed after 6 hours.

×; Discoloration was confirmed after 3 hours.

≪ Experimental Example 3 > Evaluation of corrosion of the lower film of the peeling liquid

The substrate was immersed in the 75 ° composition of the above Examples and Comparative Examples, and copper corrosion was observed with an optical microscope. The results are shown in Table 2. < tb > < TABLE >

◎; Corrosion of the lower film after 3 hours is not confirmed.

○; Corrosion of the lower film was confirmed after 2 hours.

?; Corrosion of the lower film was confirmed after 1 hour.

×; Corrosion of the lower film was confirmed after 0.5 hours.

Peelability Discoloration Lower membrane corrosion Example 1 ◎ ◎ ◎ Example 2 ◎ ◎ ◎ Example 3 ◎ ◎ ◎ Example 4 ◎ ◎ ◎ Example 5 ◎ ◎ ◎ Comparative Example 1 △ × △ Comparative Example 2 △ ◎ ◎ Comparative Example 3 △ ◎ ◎ Comparative Example 4 △ × △ Comparative Example 5 △ ◎ ◎ Comparative Example 6 △ ◎ ◎

As shown in Table 2, when the photoresist peeling solution of the example was used, the peeling property, the discoloring property, and the lower film corrosion evaluation were both excellent as compared with the case of using the photoresist peeling solution composition of the comparative example Respectively.

Claims (9)

A) an inorganic base or a salt thereof; B) quaternary ammonium salt compounds; C) alkoxyalkylamines of formula (1); D) alkylene glycol alkyl ethers; E) a solvent comprising DMSO and sulfolane; F) anticorrosives; G) Sulfur compound stabilizer; And H) water, wherein the content of DMSO is equal to or greater than the content of sulfolane.
[Chemical Formula 1]

Wherein R ₁ is a C ₁ to C ₆ chained or cyclic alkoxy group, and 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 -C ₆ chain or cyclic alkyl group, and n is an integer of 1 to 4.
The composition according to claim 1,
A) 0.01-2% by weight of an inorganic base or salt thereof;
B) 1 to 10% by weight of a quaternary ammonium salt compound;
C) 1-20% by weight of an alkoxyalkylamine of formula (1);
D) 1-20% by weight of an alkylene glycol alkyl ether;
E) 20-70% by weight of a solvent comprising DMSO and sulfolane;
F) antiseptics 0.1-5% by weight;
G) 0.1-5% by weight of a sulfur compound stabilizer; And
H) remaining amount of water.
The color resist stripping composition according to claim 1, wherein the G) sulfur compound stabilizer has a structure represented by the following formula (2):
(2)

In Formula 2,
R ₄ and R ₅ are, each independently, C ₁ ~ C ₁₀ an alkyl group, a phenyl group or a benzyl group, a C ₁ ~ C ₁₀ alkyl group, phenyl group or benzyl group is C ₁ ~ C ₁₀ alkyl group, C ₂ ~ C of _A C ₁ to C ₁₀ hydroxyalkyl group, a carboxyl group, a hydroxy group, or a C ₁ to C ₁₀ alkoxy group.
The method of claim 1, wherein the inorganic base or salt thereof 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, Resist stripper composition.
The method according to claim 1, wherein the B) quaternary ammonium salt compound is at least one selected from the group consisting of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH) and tetrabutylammonium hydroxide TBAH). ≪ / RTI >
The method of claim 1, wherein the alkoxyalkylamine of the formula (1) is selected from the group consisting of methoxyethylamine, methoxypropylamine, ethoxypropylamine, propoxyethylamine, isopropoxypropylamine, methoxyethoxypropyl Amine and at least one selected from the group consisting of oxolan-2-yl-methanamine, (oxolan-2-yl-methyl) butan- 1 -amine and methyloxolan-2-yl-methanamine.
The process according to claim 1, wherein the D) alkylene glycol alkyl ether is selected from the group consisting of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl butyl Ether, propylene glycol dimethyl ether, and dipropylene glycol dimethyl ether.
The method according to claim 1, 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 photoresist stripping liquid composition of any one of claims 1 to 8.