KR20100033006A - Remover composition for removing thermosetting resin of tft-lcd - Google Patents

Abstract

PURPOSE: A stripper composition is provided to reuse a color filter base material and a TFT substrate by removing a color resist and negative and positive organic insulating films in a short time. CONSTITUTION: A stripper composition comprises 0.5 ~ 15 parts by weight of alkylammonium hydroxide compound with ammonium hydroxide or C1-4 alkyl group, 9 ~ 89 parts by weight of alkyleneglycolether with C1-4 alkyl group, 10 ~ 40 parts by weight of glycol ether compound, 10 ~ 40 parts by weight of glycol ether compound, 0.01 ~ 5 parts by weight of corrosion inhibitor, and 0.1 ~ 5 parts by weight of water.

Description

Thermosetting resin peeling liquid composition for TF LCD [Remover composition for removing Thermosetting resin of TFT-LCD}

The present invention relates to a thermosetting resin stripper composition for TFT-LCD, and more particularly, to remove a dielectric layer, an organic protective layer, an insulating layer, an alignment layer, a color filter, and the like of a defective substrate generated during a thermosetting resin process. The present invention relates to a stripping liquid composition for color resist, negative and positive organic insulating films of TFC LCD which is excellent in effect and can reuse a lower film layer.

In the case of a defective substrate generated in a process in which an inorganic insulating film and a metal are present as the lower layer of the organic protective layer, it is known that it is difficult to remove the organic insulating layer without damaging the lower layer.

Existing processes are generally negative resists, which makes them difficult to peel compared to the positive ones. In order to obtain such a strong peeling performance, an organic or inorganic peeling liquid has been proposed to have a high pH. For example, it is disclosed in Korean Patent Laid-Open Publication No. 2005-0006980, Japanese Patent Laid-Open Publication No. 51-72503 and European Patent Publication No. 0119337 as an organic stripping solution.

However, in the case of the organic stripping solution, the high pH may cause serious damage to the lower inorganic insulating film and the metal wiring. When a weak alkali compound is applied to lower the pH, the organic insulating film is not damaged but the organic insulating film is not removed. There is a problem.

In addition, in the case of the positive and negative organic insulating film, there is a resist stripping solution for LCDs which is generally used and disclosed in Korean Patent Laid-Open Publication No. 1998-0003889. G, however, the residual film was present even after long-term treatment, and the phenomenon of floating in the liquid without melting was observed.

As described above, it is difficult to remove a large amount of color resist and polyimide or organic insulating film stably with a conventional method of removing color resist and polyimide or organic insulating film, or damage of lower film quality is impossible, and thus the substrate cannot be reused. Or there is a problem that the yield falls.

Therefore, there is a need for a method of removing a large amount of color resist and polyimide or organic insulating film through a safe method.

An object of the present invention is to provide a peeling liquid composition for safely removing a large amount of color resist and polyimide or organic insulating film used during the manufacturing process of TF.

In order to achieve the above object, the present invention

(a) 0.5 to 15 parts by weight of an alkyl ammonium hydroxide compound having an ammonium hydroxide or an alkyl group having 1 to 4 carbon atoms; (b) 9 to 89 parts by weight of alkylene glycol ether having an alkyl group having 1 to 4 carbon atoms; (c) 10 to 40 parts by weight of a glycol ether compound; (d) 0.01 to 5 parts by weight of a corrosion inhibitor; And (e) 0.1 to 5 parts by weight of water.

The stripper composition may further comprise 1 to 50 parts by weight of a polar solvent.

Hereinafter, the present invention will be described in detail.

According to the present invention, as a result of repetitive studies for reusing color resist and polyimide or organic insulating film, using a stripper composition having a specific composition, the color resist and polyimide or organic insulating film can be easily removed without damaging the underlying film quality. It has been found that the present invention can be removed, and the present invention has been completed.

Such stripper composition of the present invention comprises (a) an ammonium hydroxide or an alkyl ammonium hydroxide compound having an alkyl group having 1 to 4 carbon atoms; (b) alkylene glycol ethers having an alkyl group having 1 to 4 carbon atoms; (c) glycol ether compounds; (d) corrosion inhibitors; And (e) water. In particular, the composition of the present invention can exhibit an excellent removal effect even using a minimum amount of water than conventional.

As the hydroxide compound used in the stripper composition of the present invention, an ammonium hydroxide or an alkyl ammonium hydroxide having an alkyl group having 1 to 4 carbon atoms may be used, preferably an alkyl ammonium having an alkyl group having 1 to 4 carbon atoms Hydroxide is used. The amount of the hydroxide compound is preferably used in an amount of 0.5 to 15 parts by weight based on the total composition. When the content is less than 0.5 parts by weight, the penetrating ability to penetrate into the polymer component constituting the polyimide is insufficient to completely remove the polyimide. If the amount is more than 15 parts by weight, the component ratio of the other solvents is lowered, which may adversely affect the removal time.

The alkyl ammonium hydroxide having an alkyl group having 1 to 4 carbon atoms may be tetraethyl ammonium hydroxide, tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, or tetrabutyl ammonium hydroxide. , And mixtures thereof.

In addition, the alkylene glycol ether (alkyleneglycol ether) having an alkyl group having 1 to 4 carbon atoms is excellent in the ability to lower the surface tension and the dissolving ability to the color resist or organic insulating film to reduce the surface tension acting between the floating polymer and the glass surface To easily peel off the thermosetting resin. In addition, the alkylene glycol ether functions to dissolve the exfoliated thermosetting resin binder or polymer. The amount of the alkylene glycol ether used is included in the remainder relative to the total composition, preferably 9 to 89 parts by weight may be used. At this time, if the content is less than 9 parts by weight, it is difficult to completely remove the floating polyimide. If the content is more than 89 parts by weight, the polarity of the stripping solution is decreased, so that the acrylic resin or polyimide resin, which is a polymer material of the color resist or organic insulating film, is dissolved. There is a disadvantage in that the membrane is suspended in the liquid. Alkylene glycol ether used in the present invention is ethylene glycol monobutyl ether (ethyleneglycol monobutylether), diethylene glycol monobutyl ether (diethylene glycol monobutylether), triethyleneglycol monobutylether (triethyleneglycol monobutylether), ethylene glycol monomethyl ether (ethyleneglycol It is preferable to use one selected from the group consisting of monomethylether, diethyleneglycol monomethylether, triethyleneglycol monomethylether, ethyleneglycol monoethylether and mixtures thereof. .

In addition, the glycol ether compound serves to improve the rinse ability of the stripper. The glycol ether compound may be used in an amount of 10 to 40 parts by weight based on the total composition, and when the content is less than 10 parts by weight, there is a problem of lowering the rinse ability. All. As the glycol ether compound, one or more selected from the group consisting of ethylene glycol, methylene glycol, butylene glycol, and tetraethylene glycol may be used.

In addition, the corrosion inhibitor in the present invention serves to inhibit the corrosion of the substrate metal layer (Substrate metal layer). The amount of the corrosion inhibitor is used in an amount of 0.01 to 5 parts by weight based on the total composition, when the content is less than 0.01 parts by weight, there is a problem of lowering the corrosion inhibitory effect, and when it exceeds 5 parts by weight, there is a problem of lowering the rinse ability. For example, the corrosion inhibitor may be selected from the group consisting of ascorbic acid, benzyl triazole, catechol, tolyl triazole, and mixtures thereof.

In addition, the present invention can reduce the amount of water used to minimize the role of water previously used. That is, although the amount of water is generally used in the related art, the present invention can maximize the effect of removing the resin and preventing corrosion even with a minimum amount of water by using a specific amount of hydroxide and a corrosion inhibitor. Therefore, in the present invention, the amount of water may be used in 1 to 5 parts by weight of the total composition. When the water content is less than 1 part by weight, the activity of the hydroxide is lowered, and the process time and the peeling time are longer, and when the content of the water is more than 5 parts by weight, the effect of corrosion protection may not be seen, and the lower film process may be reused. In addition, the water used by this invention generally uses that whose specific resistance is 18 (M (ohm)) or more.

In addition, the composition of the present invention may further comprise a polar solvent. The polar solvent is excellent in the penetration and dissolving power to the polyimide penetrates between the polymer of the polyimide to cause swelling phenomenon. The amount of the polar solvent is preferably 1 to 50 parts by weight based on the total composition, wherein if the content is less than 1 part by weight, the time is greatly increased to completely remove the polyimide, and if the amount is greater than 50 parts by weight, the inorganic alkali hydroxide compound and It is not expected to improve the performance by decreasing the solubility. Polar solvents used in the present invention dimethylsulfoxide (dimethylsulfoxide), diethylsulfoxide (diethylsulfoxide), dipropylsulfoxide (dipropylsulfoxide), sulfolane (sulfolane), n-methylpyrrolidone ( N -Methyl-2- Preference is given to using those selected from the group consisting of pyrrolidone, pyrrolidone, n-ethyl pyrrolidone and mixtures thereof.

In addition, the manufacturing method of the peeling liquid composition of this invention can be manufactured by those skilled in the art, and the method is not specifically limited. In addition, the peeling liquid composition of the present invention can be used in the removal process of the color resist and polyimide or organic insulating film which are thermosetting resins of a typical TFT manufacturing process.

As described above, the peeling liquid composition of the present invention can easily remove the color resist and the organic insulating film in a short time by the synergistic effect of the respective components and can reuse the polyimide substrate, there is an economic advantage.

Hereinafter, the present invention will be described in more detail with reference to the following examples. These examples are only for illustrating the present invention, of course, the scope of the present invention is not limited to the following examples. In the following examples, unless stated otherwise, percentages and mixing ratios are by weight.

[Example 1-13 and Comparative Example 1-4]

Each component was mixed at the ratio shown to the following Tables 1 and 2, and the color resist stripper composition of the Example and the comparative example was produced, respectively. (Unit: weight part)

TABLE 1

Example (a) (b) (c) (d) (e) (f) One TMAH 2.5 MDG 80 EG 14.7 ASA 0.3 2.5 2 TMAH 2.5 MDG 60 EG 34.7 ASA 0.3 2.5 3 TMAH 2.5 MDG 80 EG 16.2 ASA 0.3 One 4 TMAH 2.5 MDG 80 EG 14.9 ASA 0.1 2.5 5 TMAH One MDG 80 EG 16.7 ASA 0.3 2 6 TMAH 3 MDG 77 EG 14.7 ASA 0.3 2 7 TMAH 2.5 MDG 70 EG 24 ASA One 2.5 8 TMAH 2.5 MDG 60 EG 24 ASA One 2.5 Sulfolane 10 9 TMAH 2.5 MDG 60 EG 24 ASA One 2 NMP 10 10 TMAH 2.5 MDG 60 EG 24 ASA One 2 DMSO 10 11 TMAH 2.5 MDG 80 EG 15.2 Catechol 0.3 2 12 TMAH 2.5 MDG 80 EG 15.2 BT 0.3 2 13 TMAH 2.5 MDG 80 EG 15.2 TT 0.3 2

TABLE 2

Comparative example (a) (b) (c) (d) (e) (g) One TMAH 35 MDG 52 EG 10 ASA One 2 2 MDG 80 EG 17 ASA One 2 3 TMAH 2.5 MDG 80 EG 15.5 2 4 TMAH 2.5 MDG 50 EG 15.5 ASA 2 20 MEA 10

Note) In Tables 1 and 2 above,

(a): hydroxide compound, (b): alkylene glycol ether, (c): glycol ether

(d): corrosion inhibitor, (e): water, (f): polar solvent, (g) amines

TMAH: tetramethylammonium hydroxide

MDG: Diethylene Glycol Methyl Ether

EG: ethylene glycol MEA: monoethanolamine

ASA: Ascorbic acid

BT: Benzyl Triazole TT: Tolyl Triazole

[Experimental Example]

In order to evaluate the performance of the color resist stripper composition prepared in Examples 1-13 and Comparative Examples 1-4, a thermosetting resin removal experiment was performed as follows using the color filter substrate.

1. Specimen Manufacturing

(1) Psalm 1

Polyimide (PI) is made on the glass on which Mo / Al / Mo multilayers are deposited and pattern is made on the bottom, and spin coating is performed on a color resist composition (trade name: DCR-725S manufactured by Dongjin Semichem Co., Ltd.). The film thickness was applied so as to be 1.7 mu m. Subsequently, the resist film was pre-baked at 90 ° C. for 120 seconds on a hot plate. Subsequently, after exposure and development at room temperature for 60 seconds with 1% potassium hydroxide (KOH) developer, the specimen with the pattern was hard-baked in an oven at 220 ° C. for 20 minutes to prepare specimen 1.

(2) Psalm 2

In addition, in order to make a polyimide-coated specimen, an organic insulating film composition (trade name SOJN-091 manufactured by Dongjin Semichem Co., Ltd., product name: SOJN-091) is spin-coated on a glass on which a Mo / Al / Mo multilayer is deposited and a pattern is formed on the bottom to obtain a final film thickness. Was applied so as to be 4.0 탆. The polyimide was then soft-baked at 90 ° C. for 120 seconds on a hot plate. Subsequently, after exposing for 70 seconds at room temperature with 2.38% TMAH developing solution, the whole surface exposure was performed, it hard-baked at 130 degreeC for 3 minutes, and the specimen 2 was produced.

2. Removal test

(1) Removal time comparison test

The specimens 1 and 2 prepared above were immersed in a stripper composition for removing color resist and removing polyimide material at a temperature of 70 ° C., and the time for completely removing the color resist or organic insulating film from the substrate was measured. Subsequently, after removing the specimen 1 from the color resist stripper composition, it was washed with ultrapure water, dried with nitrogen gas, and inspected whether the color resist remained in the pattern by 100 times magnification with an Olympus microscope, and the color resist remained in the substrate. Whether or not.

(2) Al film quality damage degree comparison test

In order to observe the damage of the lower film quality, the specimens coated with the color resist were immersed for 30 minutes in each peeling liquid composition and observed for damage by SEM.

Table 3 below shows the results obtained by measuring the time when the organic insulating film material and the color resist were completely peeled off and no residue was found.

[Table 3]

number Al film damage Removal time Psalm 1 (Polyimide) Psalm 2 (Organic Insulation) Example One ◎ 2 minutes 1 minute 2 ◎ 2 minutes 1 minute 3 ◎ 2 minutes 1 minute 4 ◎ 2 minutes 1 minute 5 ◎ 2 minutes 1 minute 6 ◎ 2 minutes 1 minute 7 ◎ 2 minutes 1 minute 8 ◎ 2 minutes 1 minute 9 ◎ 2 minutes 1 minute 10 ◎ 2 minutes 1 minute 11 ◎ 2 minutes 1 minute 12 ◎ 2 minutes 1 minute 13 ◎ 2 minutes 1 minute Comparative example One X 2 minutes 1 minute 2 ◎ 20 minutes or more More than 10 minutes 3 X 2 minutes 2 minutes 4 △ 2 minutes 1 minute

Note) In Table 3, <X: wiring disappears completely, △: serious damage of Al, ○: surface fitting occurs, ◎: no damage>

As can be seen in Table 3, the embodiment of the present application is not only excellent in the color resist removal performance and the organic insulating film removal performance, it can be seen that there is no damage to the lower film quality. In addition, it can be seen that the present invention has excellent color resist removal performance and corrosion prevention performance as compared to the comparative example without major components such as corrosion inhibitor and hydroxylamine.

The stripper composition according to the present invention can easily remove the color resist and the organic insulating film in a short time, and can be rinsed with water only in the subsequent rinsing process without using organic solvents such as isopropyl alcohol and dimethyl sulfoxide. There is an advantage, and in particular the removal of the resist pattern is possible so that the substrate can be reused.

Claims (8)

(a) 0.5 to 15 parts by weight of an alkyl ammonium hydroxide compound having an ammonium hydroxide or an alkyl group having 1 to 4 carbon atoms; (b) 9 to 89 parts by weight of alkylene glycol ether having an alkyl group having 1 to 4 carbon atoms; (c) 10 to 40 parts by weight of a glycol ether compound; (d) 0.01 to 5 parts by weight of a corrosion inhibitor; And (e) 0.1 to 5 parts by weight of water Characterized in that it comprises a peeling liquid composition. The method of claim 1, wherein the alkyl ammonium hydroxide having an alkyl group having 1 to 4 carbon atoms is tetraethyl ammonium hydroxide, tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, trimethylbenzyl ammonium hydroxide, and A peeling liquid composition, characterized in that it is selected from the group consisting of these. The alkylene glycol ether having an alkyl group having 1 to 4 carbon atoms is ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monomethyl ether, diethylene glycol mono A stripper composition, which is selected from the group consisting of methyl ether, triethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and mixtures thereof. The stripper composition according to claim 1, wherein the glycol ether compound is at least one member selected from the group consisting of ethylene glycol, methylene glycol, butylene glycol, and tetraethylene glycol. The stripper composition according to claim 1, wherein the preservative is selected from the group consisting of ascorbic acid, benzyl triazole, catechol, tolyl triazole, and mixtures thereof. The composition according to claim 1, wherein the composition further comprises 1 to 50 parts by weight of a polar solvent based on the total composition. 7. The polar solvent of claim 6, wherein the polar solvent comprises dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, sulfolane, n-methylpyrrolidone, pyrrolidone, n-ethylpyrrolidone and mixtures thereof. A peeling liquid composition, characterized in that it is selected from the group. The stripper composition according to claim 1, wherein the composition is used for removal of color resist of TFT LCD and negative or positive organic insulating film.