KR102040064B1

KR102040064B1 - color resist stripper composition

Info

Publication number: KR102040064B1
Application number: KR1020120152360A
Authority: KR
Inventors: 윤효중; 김우일; 방순홍
Original assignee: 동우 화인켐 주식회사
Priority date: 2012-12-24
Filing date: 2012-12-24
Publication date: 2019-11-04
Also published as: KR20140082418A

Abstract

The present invention relates to a color resist stripper composition containing no alkylene glycol ether, comprising a quaternary ammonium salt compound, dimethyl sulfoxide, an alkylhydroxylamine represented by the following general formula (1), an alkylamine, an alkali salt compound, and water. It relates to a resist stripper composition. The color resist stripper composition of the present invention can not only sufficiently remove the color resist of the color filter, but also minimize the change over time of the removal force.

Description

Color resist stripper composition

The present invention relates to a color resist stripper composition, and more particularly to a color resist stripper composition for removing the cured color resist of the color filter to reuse the color filter.

The color filter is 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 may be used to actually obtain a color image. In addition, it is widely used in photographing devices, plasma display panels (PDPs), liquid crystal displays (LCDs), field emission displays (FELs), and light emitting displays (LEDs), and its application range is rapidly expanding. In particular, in recent years, the use of LCDs has been further expanded. Accordingly, color filters have been recognized as one of the most important components in reproducing the color tone of LCDs.

The color filter substrate is composed of a red matrix, a green matrix, a blue matrix, and a black matrix, which serves to block leakage light and improve contrast between pixels, and a common electrode for applying a voltage to the liquid crystal cell. It consists of.

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.

While a bad color filter may inevitably occur during the manufacturing process of such a color filter, a composition for removing the cured color resist has been developed for reuse of the bad color filter.

For example, JP 1995-028254 A discloses a composition comprising sugar alcohols, DMSO, alcohol amines, quaternary ammonium salt compounds and water for the removal of cured resist resulting from dry etching of wiring material by halogen gas. The composition can be used to remove the resist using a quaternary ammonium salt compound, dimethyl sulfoxide, alcohol amine, water, but there is a disadvantage in that it does not exhibit sufficient removal power for the heat-cured color resist.

In addition, Republic of Korea 10-2005-0006980 discloses a stripper composition for color filter reuse containing inorganic alkali hydroxide or alkyl ammonium hydroxide, dimethyl sulfoxide, alkylene glycol ether and water. The composition can remove the color resist pattern using alkylammonium hydroxide, dimethylsulfoxide and water, but the disadvantage is that the solution does not last long due to the low boiling point of the hydroxyl amine by including hydroxyl amine. have.

Therefore, there is a need for a color resist stripper composition capable of sufficiently removing the cured color resist and maintaining the removal force for a long time for reuse of the color filter.

JP 1995-028254 A KR 2005-0006980 A

In order to solve the problems of the prior art, an object of the present invention is to provide a color resist stripper composition that can sufficiently remove the cured color resist for reuse of the color filter, and can maintain a long time removal force.

In order to achieve the above object,

The present invention is a color resist stripper composition containing no alkylene glycol ether, 1 to 10% by weight of the quaternary ammonium salt compound, 30 to 80% by weight of dimethyl sulfoxide, based on the total weight of the composition, alkyl represented by the following general formula (1) It relates to a color resist stripper composition comprising 1 to 20% by weight of hydroxylamine, 1 to 20% by weight of alkylamine, 0.001 to 1% by weight of alkali salt compound and 1-40% by weight of water.

Where

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

The color resist stripper composition of the present invention is used to remove the cured RGB color resist pattern of the LCD color filter to remove color resist in such a way that the color resist is dissolved without lifting off the substrate. The resist can be sufficiently removed, the filter clogging in the equipment can be minimized, and the removal force can be maintained for a long time, thereby improving the productivity of color filter reuse.

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

[Formula 1]

Where

The quaternary ammonium salt compound serves to promote the dissolution of the polymer resist by the penetration of hydroxide ions into the color polymer resist.

The quaternary ammonium salt compound is preferably included in an amount of 1 to 10% by weight based on the total weight of the composition. When the quaternary ammonium salt compound is less than 1% by weight, the penetration force of the hydroxide ions into the color resist polymer is reduced. The content is increased to decrease the dissolving power for 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). Although it is preferable that it is 1 or more types chosen, it is not necessarily limited to this.

The dimethyl sulfoxide penetrates into the swollen polymer resist and serves to dissolve the resist.

The dimethyl sulfoxide is preferably contained in 30 to 80% by weight based on the total weight of the composition, less than 30% by weight of the resist solubility is reduced, and more than 80% by weight of the hydroxide ions due to the reduction of the quaternary ammonium salt compound Reduces the penetration into the resist.

The alkylhydroxylamine penetrates into the crosslinked structure of the color resist and increases the swelling force of the polymer to increase the peel force from the substrate.

As the alkyl hydroxyl amine represented by Formula 1, one or more selected from the group consisting of dimethyl hydroxyl amine, diethyl hydroxyl amine, dibutyl hydroxyl amine, and dipropyl hydroxyl amine may be used, but is not limited thereto. It doesn't work.

The alkylhydroxylamine is preferably included in an amount of 1 to 20% by weight based on the total weight of the composition, and when included in less than 1% by weight, the dissolving power of the color resist is reduced, and when it exceeds 20% by weight, the effect of the increase is increased. It is not economical because there is no increase, and the number of treatments may decrease.

The alkyl amine serves to dissolve the dye component of the color resist.

The alkyl amine is not particularly limited, but may be a primary amine such as methyl amine, ethyl amine, isopropyl amine, or monoisopropyl amine; Secondary amines such as diethyl amine, diisopropyl amine and dibutylamine; Tertiary amines such as trimethylamine, triethylamine, triisopropylamine and tributylamine; Diamines such as ethylenediamine, propylenediamine, 1,3-propanediamine and 1,2-propylenediamine; And triamines such as diethylenetriamine and dihexylenetriamine.

The alkylamine is preferably included in an amount of 1 to 20% by weight based on the total weight of the composition. When the alkylamine is included in an amount of less than 1% by weight, it is difficult to dissolve the dye component of the color resist. It is not economical because there is no increase, and the solubility of the polymer resist is lowered due to the relative decrease of the content of the quaternary ammonium compound and dimethyl sulfoxide.

The alkali salt compound serves to maintain the peeling performance of the color resist for a long time, and if less than 0.001% by weight can not be expected to improve the life of the peeling solution, if it exceeds 1% by weight secondary pollution due to the generation of precipitates in the process equipment Generates.

The alkali salt compound is not particularly limited but is preferably at least one selected from the group consisting of potassium acetate, potassium nitrate, potassium sulfate, potassium silicate, monopotassium phosphate, dipotassium phosphate, and tripotassium phosphate.

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

Example

Color resist Stripper Preparation of the composition

The components shown in Table 1 were mixed according to a predetermined composition ratio to prepare the color resist stripper compositions of Examples 1 to 9 and Comparative Examples 1 to 4.

Color resist Peel force evaluation

Evaluation of color resist peeling force used the color filter board | substrate which red, green, and blue (hereafter RGB) apply | coated, respectively. The color resist was prepared by prebaking at 90 ° C. for 120 seconds after application and then exposing and developing the substrate to which the patterned substrate was hard baked in a 220 ° C. oven. The prepared color resist substrate was immersed for 5 minutes in the color resist stripping solution of Examples 1 to 9 and Comparative Examples 1 to 4 after 1 day, 10 days, and 2 weeks, respectively, and then subjected to a resist under an optical microscope. After confirming whether or not, the results are shown in Table 2 below.

Quaternary Ammonium Hydroxide DMSO Alkylhydroxylamine Alkylamine Alkaline salt compounds Hydroxylamine water Kinds weight% weight% Kinds weight% Kinds weight% Kinds weight% weight% Example 1 TMAH 2 50 Dimethylhydroxylamine 10 Ethylenediamine 10 Potassium acetate 0.1 - Remaining amount Example 2 TMAH 4 50 Dimethylhydroxylamine 15 Diethyl amine 5 Potassium Nitrate 0.1 - Remaining amount Example 3 TMAH 6 50 Diethylhydroxylamine 10 Ethylenediamine 10 Potassium sulfate 0.1 - Remaining amount Example 4 TEAH 3 40 Diethylhydroxylamine 15 Diethylenetriamine 10 Dipotassium Phosphate 0.05 - Remaining amount Example 5 TEAH 3 60 Dimethylhydroxylamine 5 Diisopropyl amine 15 Potassium acetate 0.1 - Remaining amount Example 6 TEAH 6 40 Dibutylhydroxylamine 15 Triethylamine 15 Potassium Nitrate 0.05 - Remaining amount Example 7 TMAH 2 70 Diethylhydroxylamine 5 Ethylenediamine 15 Potassium sulfate 0.5 - Remaining amount Example 8 TMAH 2 60 Dibutylhydroxylamine 10 Diethyl amine 5 Dipotassium Phosphate 0.05 - Remaining amount Example 9 TMAH 2 70 Dimethylhydroxylamine 10 Ethylenediamine 5 Potassium acetate 0.2 - Remaining amount Comparative Example 1 - - 80 Dimethylhydroxylamine 5 Diethylenetriamine 5 Potassium Nitrate 0.1 0.5 Remaining amount Comparative Example 2 TMAH 2 60 - - Diisopropyl amine 15 - - 15 Remaining amount Comparative Example 3 TEAH 5 35 - - Triethylamine 30 - - 5 Remaining amount Comparative Example 4 TEAH 15 20 - - - - Potassium acetate One 19 Remaining amount

TMAH: Tetramethylammonium Hydroxide

TEAH: tetraethylammonium hydroxide

DMSO: Dimethylsulfoxide

Resist Remaining 1 day 10 days 2 weeks 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 Comparative Example 3 Ⅹ Ⅹ Ⅹ Comparative Example 4 Ⅹ Ⅹ Ⅹ

As shown in Table 2, the color resist stripper composition of Examples 1 to 9 had little change over time in the resist removal ability even after a time after manufacture, whereas Comparative Examples 1 to 4 containing hydroxylamine It can be seen that the resist removal ability of the color resist stripping liquid composition is significantly lowered over time. This is because the boiling point of hydroxylamine is low and the life of the stripping solution does not last long.

Therefore, the color resist stripper composition of the present invention can not only sufficiently remove the color resist of the color filter, but also can minimize the change of the removal force over time, thereby improving the productivity of color filter reuse.

Claims

A color resist stripper composition that does not contain alkylene glycol ether and hydroxyl amine, which is 1 to 10% by weight of quaternary ammonium salt compound, 30 to 80% by weight of dimethyl sulfoxide, and 1 to 1% of alkylhydroxylamine based on the total weight of the composition. 20 wt%, 1-20 wt% of alkylamine, 0.001-1 wt% of alkali salt compound and 1-40 wt% of water,
The alkyl hydroxyl amine is at least one selected from the group consisting of dimethyl hydroxyl amine, diethyl hydroxyl amine, dibutyl hydroxyl amine and dipropyl hydroxyl amine,
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) Characterized in that it is at least one
The alkylamine is to dissolve the dye component of the color resist, color resist stripping liquid composition.

delete

The method of claim 1, wherein the alkyl amine is methyl amine, ethylamine, isopropyl amine, monoisopropylamine, diethyl amine, diisopropyl amine, dibutylamine, trimethylamine, triethylamine, triisopropylamine, tri Color resist stripping liquid composition, characterized in that at least one selected from the group consisting of butylamine, ethylenediamine, propylenediamine, 1,3-propanediamine, 1,2-propylenediamine, diethylenetriamine and dihexylenetriamine .

The method according to claim 1, wherein the alkali salt is a color resist stripping, characterized in that at least one selected from the group consisting of potassium acetate, potassium nitrate, potassium sulfate, potassium silicate, monopotassium phosphate, dipotassium phosphate and tripotassium phosphate Liquid composition.