KR20150026584A - Liquid composition for stripping a color resist and an organic insulating layer - Google Patents

Abstract

The present invention relates to a liquid composition for peeling a color resist and an organic insulating layer not including akylene glycoleether, which is characterized by including A) 1-10 wt% of a quaternary ammonium salt compound; B) 40-80 wt% of dimethyl sulfoxide; C) 1-20 wt% of alkyl amine; D) 0.005-0.5 wt% of an inorganic alkali compound; E) 0.005-1 wt% of a surfactant; and F) a remaining amount of water based on the total weight of the composition.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color resist and an organic insulating film,

The present invention relates to a color resist and an organic insulation film peeling liquid composition for reusing a color filter by removing a cured color resist and an organic insulation film of a color filter.

An OLED panel is formed by overcoating a flat film on a TFT formed substrate, forming a bank pattern for forming a boundary of the pixel region thereon, and then forming red, green, and blue color resists on each pixel region. In the manufacturing process of such an OLED panel, the overcoat, the bank or the color resist pattern defect may occur inevitably. When the resin constituting such a material is once cured, it is almost impossible to repair only the erroneous portion and repair it. Since there is almost no solvent, there is a problem that the panel with poor coating is mostly discarded without being subjected to rework such as repair, and the productivity is lowered.

On the other hand, the resist can be largely divided into a positive type resist and a negative type resist. Unlike the positive type resist, which is easily removed and removed by a stripping agent based on an organic solvent at a temperature of 40 to 50 캜 within 1 minute, Resists have properties of a negative type resist which has a high degree of curing and is hardened by heat treatment and is difficult to peel off. Accordingly, in order to remove the color resist, a time of not less than 5 minutes is required under the temperature condition of 70 ° C or more, so that stronger peeling performance is required. In addition, the bank is classified into benzocyclobutene (BCB) based resin, acrylic based resin, polyimide based resin and the like. It is preferable that the pattern is formed by a spraying method, a spin coating method or an inkjet coating method which is a general wet process. It has a high hardness and a thickness of about 2 microns and has a characteristic of being difficult to peel off because a material having excellent heat resistance and chemical resistance is used. The overcoat is formed to have a thickness of about 2 microns or so to cover a plurality of TFTs and a plurality of contact holes, and has excellent heat resistance and chemical resistance due to strong heat treatment, and is difficult to peel off.

In order to solve this problem, there is a demand for development of a release liquid composition having quick and strong release performance against both cured color resist, bank and overcoat.

Korean Patent Laid-Open Publication No. 2003-0026664 discloses a color resist stripping liquid composition comprising an inorganic alkali hydroxide, an alkylene glycol ether, a water-soluble amine compound and water. However, in the case of a bank or an overcoat, There is an issue that does not show.

Korea Patent Publication No. 2003-0026664

In order to solve the problems of the prior art, the present invention provides a color resist and an organic insulating film peeling liquid composition which simultaneously removes a cured color resist and an organic insulating film of a color filter at a high speed to enable reuse of a color filter .

In order to achieve the above object, the present invention provides a color resist and organic insulation film peeling liquid composition which does not contain an alkylenecarboxylic ether, which comprises A) 1-10% by weight of a quaternary ammonium salt compound; B) 40-80 wt% dimethylsulfoxide; C) 1-20% by weight alkylamine; D) 0.005-0.5% by weight of an inorganic alkali compound; E) 0.005-1% by weight of a surfactant; And F) residual water. The present invention provides a color resist and an organic insulation film peeling liquid composition.

The release liquid composition of the present invention exhibits rapid and strong peeling performance against both the cured color resist, the bank and the overcoat, and can improve the productivity of the color filter reuse.

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

The present invention relates to a color resist and an organic insulating film peeling liquid composition which does not contain an alkylene glycol ether, comprising: A) a quaternary ammonium salt compound; B) dimethylsulfoxide; C) alkylamines; D) an inorganic alkali compound; E) Surfactants; And F) water. The present invention also relates to a color resist and an organic insulation film peeling liquid composition. The color resist and organic insulation film peeling liquid composition of the present invention shows rapid and strong peeling performance against both the cured color resist, the bank and the overcoat, and the present invention is characterized in that the alkylene glycol ether is included in the color resist and organic insulation film peeling liquid composition , The peelability is lowered and the peeling performance against the cured color resist, the bank and the overcoat is improved by the addition of the surfactant.

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

A) Quaternary ammonium salt compound

The quaternary ammonium salt compound penetrates into the color polymer resist to promote the dissolution of the polymer resist.

The quaternary ammonium salt compound of the present invention is a compound of the group consisting of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH) and tetrabutylammonium hydroxide (TBAH) , But is not limited thereto.

The quaternary ammonium salt of the present invention is preferably contained in an amount of 1-10% by weight based on the total weight of the composition, and if it is less than 1% by weight, penetration into the color resist polymer of the hydroxide ion is reduced, The content of water is increased and the solubility to the polymer resist is reduced.

B) Dimethyl sulfoxide

The dimethylsulfoxide penetrates the swollen resist and dissolves the resist.

The dimethylsulfoxide of the present invention is preferably contained in an amount of 40-80% by weight, more preferably 40-70% by weight, based on the total weight of the composition. If the content of dimethyl sulfoxide is less than 40% by weight, the solubility of the resist may be decreased. If the content of dimethyl sulfoxide is more than 80% by weight, the content of quaternary ammonium hydroxide and other components may be decreased, Can be lowered.

C) alkylamine

The alkylamine may be a primary amine such as methylamine, ethylamine, isopropylamine or monoisopropylamine; Secondary amines such as diethylamine, diisopropylamine and dibutylamine; Tertiary amines such as trimethylamine, triethylamine, triisopropyramine and tributylamine; Diamines such as ethylenediamine, propylenediamine, 1,3-propanediamine, and 1,2-propylenediamine; And triamines such as diethyltriamine and dioctylenetriamine, but the present invention is not limited thereto.

More preferably, the alkylamine is selected from the group consisting of methylamine, ethylamine, isopropylamine, monoisopropylamine, diethylamine, diisopropylamine, dibutylamine, trimethylamine, triethylamine, triisopropyramine, 1, 2, 3, 4, 5 or 6 members selected from the group consisting of tributylamine, ethylenediamine, diethyltriamine, triethyltetramine, propylenediamine, 1,3-propanediamine, 1,2-propylenediamine, diethylenetriamine and dioctylenetriamine It can be more than a species.

The alkylamine of the present invention is preferably contained in an amount of 1-20 wt% based on the total weight of the composition. When the amount is less than 1 wt%, the dye component of the color resist is difficult to dissolve. There is no increase in the effect, which is not economical, and the solubility of the polymer resist due to the relative reduction of the quaternary alkylammonium compound and dimethylsulfoxide is lowered.

D) Inorganic alkali compound

The inorganic alkaline compound serves to improve the peeling force against the organic insulating film. The inorganic alkaline compound of the present invention may be at least one member 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. But is not limited thereto.

The content of the inorganic alkaline compound is preferably 0.005 to 0.5% by weight based on the total weight of the composition. When the content is less than 0.005% by weight, the peeling force against the organic insulating film is poor. When the content is more than 0.5% by weight, Is insignificant and not economical.

E) Surfactants

The surfactant of the present invention serves to speed up the desorption of the polymer resist from the substrate.

Examples of the surfactant include nonionic surfactants, cationic surfactants and anionic surfactants which are generally used, and these surfactants may be used alone or in combination. Specifically, Rhodoclean MSC (Ethoxy-propoxyl terpene, Rhodia Co., Ltd), Rhodoclean EFC (Ethoxy-propoxyl terpene, Rhodia Co., Ltd), TD- S-505LF (Linear alcohol alkylate, BASF Co., Ltd) or SL92 (Ethoxylated propoxylated, BASF Co., Ltd.), CS-10 (Polycarboxylated anionic surfactant, Ltd., Ltd., and the like can be used, but the present invention is not limited thereto.

The surfactant is preferably contained in an amount of 0.005 to 1 wt% based on the total weight of the composition. If the surfactant is less than 0.005 wt%, there is a problem with the desorption ability of the resist. If the surfactant is more than 1 wt% there is a problem.

F) Water

The water of the present invention serves to improve the solubility of the inorganic alkali and plays a role of preventing precipitation in the solution.

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

Example  And Comparative Example : Peeling liquid  Preparation of composition

The components shown in the following Table 1 were mixed according to the determined composition ratios to prepare color resist stripping liquid compositions of Examples 1 to 10 and Comparative Examples 1 to 5.

A. Quaternary ammonium hydroxides B. Dimethyl sulfoxide C. alkylamine D. Inorganic alkali E. Surfactants F. Water Glycol ether Kinds weight% Kinds Kinds weight% Kinds weight% Kinds weight% Kinds Example 1 TMAH 5 40 Diethylamine 10 Sodium hydroxide 0.1 MSC 0.01 Balance - Example 2 TMAH 3 50 Isopropylamine 15 Potassium hydroxide 0.1 S-505LF 0.01 Balance - Example 3 TMAH 2 60 Ethylenediamine 10 Potassium carbonate 0.2 TD-730 0.05 Balance - Example 4 TMAH 7 40 Diethyl triamine 15 Potassium hydroxide 0.05 EFC 0.02 Balance - Example 5 TEAH 7 50 Diethyl triamine 10 Potassium hydroxide 0.01 TD-2007 0.05 Balance - Example 6 TEAH 3 65 Isopropylamine 10 Sodium hydroxide 0.02 CS-10 0.1 Balance - Example 7 TEAH 5 55 Diethylamine 5 Potassium hydroxide 0.1 SL92 0.01 Balance - Example 8 TMAH 4 50 Diethyl triamine 3 Sodium carbonate 0.1 EFC 0.05 Balance - Example 9 TMAH 6 45 Ethylenediamine 15 Potassium nitrate 0.2 PEG 0.005 Balance - Example 10 TMAH 8 40 Triethyltetramine 5 Potassium hydroxide 0.2 CS-10 0.01 Balance - Comparative Example 1 TMAH 4 40 Diethylamine 10 Potassium hydroxide 0.5 S-505LF 0.03 Balance MDG 15 Comparative Example 2 TMAH 2 - Diethyl triamine 20 Potassium carbonate 0.2 TD-730 0.05 Balance BDG 50 Comparative Example 3 TMAH 0.5 55 Ethylenediamine 10 - - S-505LF 0.005 Balance - Comparative Example 4 TEAH 15 Propylene diamine 5 - - TD-2007 0.2 Balance EDG 12 Comparative Example 5 TEAH 6 50 - - Sodium hydroxide 0.3 SL92 0.03 Balance - Comparative Example 6 TEAH 5 55 Diethylamine 5 Potassium hydroxide 0.1 - - Balance - Comparative Example 7 PRS-2000 Comparative Example 8 EKC-922

SL-92: Ethoxylated propoxylated, BASF Co., Ltd

EFC: Ethoxy-propoxy terpene, Rhodia Co., Ltd

MSC: Ethoxy-propoxy terpene, Rhodia Co., Ltd

CS-10: Polycarboxylated anionic surfactant BASF Co., Ltd

S-505LF: Linear alcohol alkylate, BASF Co., Ltd

TD-730: Monool block type, Lion Co., Ltd

TD-2007: Monool block type, Lion Co., Ltd

PEG: Polyethyleneglycol

MDG: Diethylene Glycol Monomethyl Ether

BDG: Diethylene Glycol Monobuthyl Ether

EDG: Diethylene Glycol Monoethyl Ether

PRS-2000: Posi-type photoresist stripper, Mallinckrodt Baker, Inc

EKC922: Negative-type photoresist stripper, Dupont, Inc

Experimental Example : Peeling liquid  Of the composition Color resist , Banks and overcoats Peel force  evaluation

Using the release liquid compositions of the examples and comparative examples prepared above, the peel force on the color resist, the bank and the overcoat was evaluated by the following method.

First, a color filter substrate on which red, green, and blue (hereinafter referred to as RGB) were respectively applied was used for evaluation of removal of the color resist. The color resist was applied after being prebaked at 90 ° C for 120 seconds after exposure, developed, and then hard baked in a 220 ° C oven to form a patterned substrate in an oven.

The removal evaluation of the bank was performed by applying a polyimide resin on a glass substrate by a spin process, prebaking at 80 ° C for 120 seconds, hard baking in an oven at 220 ° C, and forming a film having a thickness of about 2 micrometers.

The removal of the overcoat was evaluated by coating the organic insulating film of the acrylic resin by a spin process, prebaking at 80 ° C for 120 seconds, hard baking in an oven at 220 ° C, and forming a film having a thickness of about 2 micrometers.

To confirm the removability of the color resist, the resist was dipped in a solution at 70 ° C for 10 minutes, 20 minutes, and 30 minutes, and the resist remained by an optical microscope. To confirm the removability of the bank, the resist was dipped in a solution at 70 ° C for 3 minutes, 5 minutes, and 10 minutes, and the resist remained by an optical microscope. In order to confirm the removability of the overcoat, the resist was dipped in a solution at 70 ° C for 10 minutes, 20 minutes and 30 minutes, and the presence or absence of the resist was confirmed by an optical microscope. The results are shown in Table 2 below.

◎: 100% resist removal

○: Resist 80% or more removed

?: Less than 80% resist removal

X: No resist removal

RGB substrate Banks Overcoat Rework time 10 minutes 20 minutes 30 minutes 3 minutes 5 minutes 10 minutes 10 minutes 20 minutes 30 minutes Example 1 ○ ○ ◎ ○ ◎ ◎ ○ ○ ◎ Example 2 ○ ○ ◎ ○ ◎ ◎ ○ ○ ◎ Example 3 ○ ○ ◎ ◎ ◎ ◎ ○ ○ ◎ Example 4 ○ ◎ ◎ ○ ◎ ◎ ○ ○ ◎ Example 5 ○ ◎ ◎ ◎ ◎ ◎ ○ ○ ◎ Example 6 ○ ○ ◎ ○ ◎ ◎ ○ ◎ ◎ Example 7 ○ ◎ ◎ ○ ◎ ◎ ○ ◎ ◎ Example 8 ○ ○ ◎ ◎ ◎ ◎ ○ ◎ ◎ Example 9 ○ ◎ ◎ ◎ ◎ ◎ ○ ◎ ◎ Comparative Example 1 ○ ○ ◎ X △ ○ X △ △ Comparative Example 2 X X X X △ △ X X X Comparative Example 3 X X △ X △ △ X △ △ Comparative Example 4 X X X X X X X X X Comparative Example 5 X X X X △ △ X X X Comparative Example 6 △ △ ○ △ △ ○ X X △ Comparative Example 7 X X X X △ △ X X X Comparative Example 8 X X △ X △ △ X X X

The results of the experiments show that, in particular, the peeling effect is extremely low in all RGB substrates, banks, and overcoats of PRS-2000 or EKC-922 (Comparative Example 7 or 8) It was confirmed that the liquid compositions (Examples 1 to 9) exhibited excellent peeling effects in both RGB substrates, banks, and overcoats.

On the other hand, in Comparative Examples 1, 2 and 4, which are compositions containing glycol ether, and Comparative Examples 3 to 6, which are compositions containing no alkylamine, inorganic alkali or surfactant, And it was confirmed that the constitution of the alkylamine, the inorganic alkali and the surfactant etc. of the peeling liquid composition of the present invention is an essential constitution.

Accordingly, it can be seen that the release liquid composition of the present invention has the effect of simultaneously removing the cured color resist of the color filter and the organic insulating film at a high speed, and enabling the reuse of the color filter.

Claims (5)

A color resist and an organic insulation film peeling liquid composition which does not contain an alkylene glycol ether,
A) 1-10 wt% quaternary ammonium salt compound;
B) 40-80 wt% dimethylsulfoxide;
C) 1-20% by weight alkylamine;
D) 0.005-0.5% by weight of an inorganic alkali compound;
E) 0.005-1% by weight of a surfactant; And
F) residual water. The color resist and the organic insulation film peeling liquid composition according to claim 1,
The method according to claim 1,
The quaternary ammonium salt compound (A) is a compound composed of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH) and tetrabutylammonium hydroxide And the organic insulating film removing liquid composition.
The method according to claim 1,
The C) alkylamine is preferably selected from the group consisting of methylamine, ethylamine, isopropylamine, monoisopropylamine, diethylamine, diisopropylamine, dibutylamine, trimethylamine, triethylamine, triisopropyramine, tributylamine , At least one member selected from the group consisting of ethylenediamine, diethyltriamine, triethyltetramine, propylenediamine, 1,3-propanediamine, 1,2-propylenediamine, diethylenetriamine and dioctylenetriamine Wherein the color resist and the organic insulation film peeling liquid composition are characterized by:
The method according to claim 1,
The inorganic alkaline compound (D) 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 and potassium silicate Color resist and organic insulation film peeling liquid composition.
The method according to claim 1,
A color resist and an organic insulating film peeling liquid composition for peeling a cured color resist, a bank and an overcoat.