KR20230103515A - Stripper composition for removing color resist and insulating layer - Google Patents

Abstract

The present invention relates to a stripper composition for removing a color resist and an insulating film, and more particularly, a first aprotic polar solvent containing a nitrogen atom (N) and a second aprotic polar solvent having a molecular weight different from that of the first aprotic polar solvent. Solvents including solvents, glycol ether compounds, inorganic bases or their salt compounds, chain-type amine compounds and alkylammonium compounds, as well as color resists, negative and positive organic insulating films, inorganic insulating films as underlying materials, and various metal wires It relates to a stripper composition that can be removed in a short time without damaging the skin.

Description

Stripper composition for removing color resist and insulating film {STRIPPER COMPOSITION FOR REMOVING COLOR RESIST AND INSULATING LAYER}

The present invention relates to a stripper composition capable of removing color resists and insulating films in order to reuse defective substrates generated in TFT-LCD and OLED processes.

TFT-LCD and OLED require color filter layers with red, green, and blue patterns to realize the color of each pixel.

A process of manufacturing the color filter on the upper substrate is as follows. Taking a TFT-LCD as an example, a color resist is coated on the TFT structure and exposed to light, and the color resist is cured by a photopolymerization reaction. After the exposure is finished, the unexposed portion of the color resist is removed by development and subjected to a firing process. When a defect occurs in the color filter during this process, in the related art, the defective substrate is mostly discarded without being reused. Accordingly, there is an increasing demand for a stripper composition for reusing a substrate by removing a defective color filter.

Korean Patent Registration No. 10-1488265 regarding a stripper composition for stripping a color filter or organic insulating film includes a hydroxide-based compound, an alkylene glycol alkyl ether-based compound, an alkanolamine-based compound, an inorganic salt compound, and a residual amount of water Discloses a stripper composition for removing a color resist, but there is a problem of deterioration in removability when used for a long time due to volatilization during a high-temperature process, and a problem of not showing the effect of rapidly removing the color resist and organic insulating film. there is.

An object of the present invention is to provide a stripper composition capable of easily removing a color resist and an organic insulating film at a high speed without damaging the underlying film, and particularly having excellent organic insulating film removability.

Another object of the present invention is to provide a stripper composition that does not damage silicon nitride (SiN _x ), silicon oxide (SiO _x ), etc., which are silicon-based lower films, in the process of removing the color resist and the organic insulating film.

In order to achieve the above object, a stripper composition according to an embodiment of the present invention includes a first aprotic polar solvent containing a nitrogen atom (N) and a solvent containing a second aprotic polar solvent; glycol ether compounds; inorganic bases or salt compounds thereof; chain amine compounds; and an alkylammonium compound, wherein the first aprotic polar solvent and the second aprotic polar solvent have different molecular weights, and the weight ratio of the first aprotic polar solvent to the second aprotic polar solvent is 1:1 to 1 : 40.

A difference in molecular weight between the first aprotic polar solvent and the second aprotic polar solvent may be 5 to 65 g/mol.

The first aprotic polar solvent is N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethylform It may contain at least one selected from amide (N-Ethylformamide), N-methylformamide (N-Methylformamide) and pyrrolidone (pyrrolidone).

The second aprotic polar solvent may have a molecular weight of 70 to 140 g/mol.

The second aprotic polar solvent may include at least one selected from dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide and sulfolane.

The first aprotic polar solvent may be N-ethyl-2-pyrrolidone.

The stripper composition may include 10 to 100 parts by weight of the glycol ether compound based on 100 parts by weight of the solvent.

The glycol ether compound is ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether , diethylene glycol butyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol butyl ether, diethylene glycol dimethyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, ethylene glycol dimethyl ether, dipropylene It may include at least one selected from glycol dimethyl ether, triethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether.

Also, the stripper composition may include 0.001 to 0.05 parts by weight of the inorganic base or a salt compound thereof based on 100 parts by weight of the solvent.

The inorganic base or its salt compound includes potassium acetate, potassium nitrate, potassium carbonate, potassium pyrophosphate, potassium oleate, potassium benzoate, potassium laurate, potassium tert-butoxide, potassium sulfate, potassium sorbate, Potassium Amino Benzoate, Potassium Disulfate, Potassium Cyanate, Potassium Sulfide, Potassium Xyrene Sulfonate, Sodium Xyrene Sulfonate, Lithium Hydroxide, Sodium Hydroxide, Potassium Hydroxide, Sodium Carbonate, Sodium Hydrogen It may include at least one selected from carbonate, potassium hydrogen carbonate, sodium nitrate, sodium sulfate, sodium acetate, sodium silicate, and potassium silicate.

The stripper composition may include 20 to 145 parts by weight of the chain amine compound and the alkylammonium compound based on 100 parts by weight of the solvent.

Also, the stripper composition may include 15 to 29% by weight of the alkylammonium compound based on the total weight of the stripper composition.

The stripper composition may include the inorganic base or its salt compound and the alkylammonium compound in a weight ratio of 1:1,000 to 1:20,000.

The chain amine compound is aminoethanol, diethanolamine, N-methylethanolamine, triethanolamine, glycolamine, diglycolamine, hydroxylamine, methylamine, ethylamine, isopropylamine, monoisopropylamine, diethyl Amine, diisopropylamine, dibutylamine, ethylenediamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, monoisopropanolamine, aminoethoxyethanol, propoxyethylamine, isopropoxypropylamine, Methoxyethoxypropylamine, aminoethylethanol, methoxyethylamine, methoxypropylamine, ethoxypropylamine, 3-methoxypropylamine, 3-ethoxypropylamine, n-methylmethanolamine, monomethanolamine, Monoethanolamine, diethylamino propylamine, bis-2-methoxyethylamine, propylenediamine, 1,3-propanediamine, 1,2-propylenediamine, diethylenetriamine, dihexylenetriamine, triethylenetetramine, It may contain at least one selected from tetraethylenepentamine, oxolan-2-yl-methanamine, (oxolan-2-yl-methyl)butan-1-amine and methyloxolan-2-yl-methanamine. there is.

The alkylammonium compound may include at least one selected from tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.

The stripper composition may further include a corrosion inhibitor, and may include 0.2 to 25 parts by weight of the corrosion inhibitor based on 100 parts by weight of the solvent. In this case, the corrosion inhibitor may include at least one selected from tolytriazole, benzotriazole, mercaptomethylimidazole, catechol-based compounds, and alkyl gallate-based compounds.

A stripper composition for a silicon oxide film according to another embodiment of the present invention includes a glycol ether compound; inorganic bases or salt compounds thereof; chain amine compounds; It includes an alkylammonium compound and an aprotic solvent, and contains 0.001 to 0.05 parts by weight of the inorganic base or its salt compound based on 100 parts by weight of the solvent.

The stripper composition of the present invention removes not only color resist, but also negative and positive organic insulating films in a short period of time without damaging inorganic insulating films and various metal wirings, which are the underlying film, to form color filter substrates and thin film transistors (TFTs). Make the substrate reusable.

The peeling solution composition of the present invention has an effect of hardly causing damage due to corrosion during the peeling process for an inorganic insulating film made of SiO _x as well as an inorganic insulating film made of SiN _x .

The stripper composition of the present invention can easily remove color resist and organic insulating film materials in a short time, and can rinse only with water without using organic solvents such as isopropyl alcohol and dimethyl sulfoxide in a subsequent rinse process. There is an advantage, in particular, the color filter substrate can be reused because the resist pattern can be removed.

1 is a photograph taken with a scanning electron microscope (SEM) of a TFT substrate on which a color resist (Color Layer) and an organic insulating film layer (Over Coat, OC) are formed before peeling.
FIG. 2 is an enlarged SEM picture (a) of FIG. 1 and a SEM picture (b) after peeling according to the stripper composition of Example 1. FIG.
3 is a SEM photograph of a substrate on which metal wiring and a lower film layer (inorganic insulating film, SiO _x ) are formed before a color resist (Color Layer) and an organic insulating film layer (Over Coat, OC) are formed, and the thickness of the lower film layer it is shown
Figure 4 is a metal wiring and a lower film layer (inorganic insulating film, SiO _x ) are formed after stripping a color resist (Color Layer) and an organic insulating film layer (OC) using a stripper composition according to embodiments of the present invention. It shows the SEM picture of the substrate and the thickness of each lower film layer.

The terms or words used in this specification and claims should not be construed as being limited to ordinary or dictionary meanings, and the inventors may appropriately define the concept of terms in order to explain their invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

Therefore, the configurations shown in the embodiments and manufacturing examples described in this specification are only one of the most preferred embodiments of the present invention, and do not represent all the technical ideas of the present invention, so they can be replaced at the time of the present application. It should be understood that there may be many equivalents and variations.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention can be implemented in many different forms and is not limited to the manufacturing examples and examples described herein.

The present invention is a stripper composition that can easily remove color resist (CR) and organic insulating film (Over Coat, OC) without damaging the lower film layer such as inorganic insulating film and metal wiring on a substrate. It is about.

The stripper composition according to one aspect of the present invention can easily peel the color resist and organic insulating film by increasing the solvency of the color resist and organic insulating film on the substrate using two or more polar solvents having different molecular weights. Specifically, the polar solvent includes a first aprotic polar solvent containing a nitrogen atom (N) and a second aprotic polar solvent having a molecular weight different from that of the first aprotic polar solvent. That is, the stripper composition according to one aspect of the present invention includes a glycol ether compound in a solvent having excellent solubility for the color resist and organic insulating film; inorganic bases or salt compounds thereof; A chain amine compound and an alkylammonium compound are mixed. And at this time, when the weight ratio of the first aprotic polar solvent and the second aprotic polar solvent containing nitrogen atoms (N) is 1: 1 to 1: 40, the color resist and organic insulating film solvency of the stripper is more excellent. If it is out of the range, the organic insulating film solvency may be lowered, and the aging performance (time for which performance is maintained) of the stripper composition is reduced.

Among the first aprotic solvent and the second aprotic solvent having a molecular weight difference, the solvent having a small molecular weight first penetrates into the cured overcoating layer and the color resist layer in the process of dissolving the overcoating layer and the color resist layer, thereby polymerizing the polymer. The gap between them is widened (first step), and a solvent with a high molecular weight penetrates secondarily to break intermolecular bonds, and the bonded overcoating layer and color resist layer particles are surrounded by the solvent and dissolved in a stable state (second step). step). Due to the peeling process of the first step and the second step, the solvency of the solvent for the overcoating layer and the color resist layer may be excellent.

When the molecular weight difference between the molecular weight of the first aprotic polar solvent containing the nitrogen atom (N) and the molecular weight of the second aprotic polar solvent in the solvent is within a specific range, primary separation of the organic insulating film layer (overcoating layer) in the peeling process may occur more easily, specifically, there may be a difference of 5 to 65 g / mol, and more specifically, there may be a difference of 5 to 55 g / mol. In the solvent, the difference in molecular weight between the first aprotic polar solvent and the second aprotic polar solvent containing nitrogen atoms (N) must be 5 or more, so that the effect of increasing the solvency through the two-step peeling process can be expressed, In the solvent, when the difference in molecular weight between the first aprotic polar solvent and the second aprotic polar solvent containing nitrogen atoms (N) is higher than 65 g/mol, a problem in which the cleaning ability is lowered in the cleaning step after the peeling step may occur. there is. The molecular weight of the first aprotic polar solvent containing a nitrogen atom (N) may be greater than the molecular weight of the second aprotic polar solvent, conversely, the molecular weight of the second aprotic polar solvent containing a nitrogen atom (N) It may be greater than the molecular weight of the first aprotic polar solvent. In addition, a case in which the molecular weight difference between the molecular weight of the first aprotic polar solvent and the second aprotic polar solvent including the nitrogen atom (N) is 5 to 55 g/mol may be preferred for effective separation.

The first aprotic polar solvent containing a nitrogen atom (N) may specifically have a molecular weight of 50 to 120 g/mol, for example, N-ethyl-2-pyrrolidone (N-ethyl-2- pyrrolidone), N-Methyl-2-Pyrrolidinone, N-Ethylformamide, N-Methylformamide and pyrrolidone It may include any one or more selected from among.

In addition, the second aprotic polar solvent is not particularly limited as long as it is an aprotic polar solvent having a molecular weight difference from the first aprotic polar solvent, but may include a nitrogen atom (N) or a sulfur atom (S) in consideration of compatibility. And, the molecular weight may be specifically 70 to 140 g / mol. The second aprotic polar solvent satisfying the above conditions may include, for example, at least one selected from dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, and sulfolane. The second aprotic polar solvent is used together with the first aprotic polar solvent containing the nitrogen atom (N), and when using an aprotic polar solvent having a molecular weight of 70 to 140 g/mol, it is applied to a color resist and an organic insulating film. The swelling effect is excellently expressed, the peeling force is increased due to excellent dissolution performance, and the residue removal effect may also be excellent.

As the first aprotic polar solvent containing a nitrogen atom (N), N-ethyl-2-pyrrolidone has a high molecular weight of 113.16 g/mol and has a cyclic structure, so it has a high solute solubility. In addition to being suitable as a solvent, the solvency of the overcoating layer can be particularly excellent through the relatively large molecular structure of the ring type, so that the first aprotic polar solvent containing nitrogen atoms (N) is N-ethyl- 2-pyrrolidone can be used.

In the stripper composition of the present invention, the glycol ether compound serves as a buffer so that various components included in the stripper can be evenly dissolved in the solvent, and the stripper remaining on the substrate when washed with ultrapure water in the cleaning step after the stripping step It serves to allow the composition to be smoothly washed without being adsorbed to foreign substances. When the glycol ether compound is included in the stripper composition in an amount of 10 to 100 parts by weight based on 100 parts by weight of the solvent, the buffering role may occur, particularly when the glycol ether compound is included in 12 to 50 parts by weight based on 100 parts by weight of the solvent. The buffering role can be better expressed. When the glycol ether compound is included in less than the above parts by weight in the stripper composition, the inorganic base or its salt compound, amine compound, alkylammonium compound, etc. contained in the solvent are not evenly mixed, and the state of the substrate after stripping may be uneven There may be a problem, and when the glycol ether compound is included in the stripper composition in excess of the above weight part, the specific gravity of the material without stripping performance may be too high, resulting in a decrease in the stripping effect.

The glycol ether compound is, for example, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol Ethyl ether, diethylene glycol butyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol butyl ether, diethylene glycol dimethyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, ethylene glycol dimethyl ether, It may include at least one selected from dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether.

In the stripping solution composition of the present invention, the inorganic base or its salt compound is included in the stripping solution together with an alkylammonium compound so that the overcoating layer and the color resist layer dissolved by the solvent can be quickly peeled off. ) to enhance the ability of In addition, the inorganic base or its salt compound can improve the corrosion resistance of the lower layer even if it is included in a small amount in the stripper composition, and can realize an excellent stripping effect through interaction with other components of the stripper composition. Specifically, the above effect can be exhibited even when the inorganic base or its salt compound is included in a small amount of 0.001 to 0.05 part by weight based on 100 parts by weight of the solvent in the stripper composition, and the amount of the inorganic base or its salt compound must be 0.001 part by weight or more. Although the effect of enhancing the peeling ability may be significantly expressed, when it is included in an amount exceeding 0.05 parts by weight, corrosion of the inorganic insulating film under the color resist may occur due to the excessive peeling effect. In particular, when the inorganic base or its salt compound is included in an amount of 0.002 to 0.04 parts by weight based on 100 parts by weight of the solvent, the color resist and organic insulating film removal ability of the stripping solution can be more excellently expressed.

The inorganic base or its salt compound may be, for example, an alkali salt compound, specifically potassium acetate, potassium nitrate, potassium carbonate, potassium pyrophosphate, potassium oleate, potassium benzoate, potassium laurate, potassium tert ( tert)-butoxide, potassium sulfate, potassium sorbate, potassium amino benzoate, potassium disulfate, potassium cyanate, potassium sulfide, potassium xyrene sulfonate, sodium xyrene sulfonate, lithium hydroxide, sodium hydroxide side, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium nitrate, sodium sulfate, sodium acetate, sodium silicate, and potassium silicate, and may include at least one selected from, in particular, an inorganic base Alternatively, when potassium acetate is used as a salt compound thereof, the peeling effect of the stripper composition is more excellently expressed, and the anti-corrosion effect on the lower inorganic insulating film can be further enhanced.

The first aprotic polar solvent containing nitrogen atoms (N) contained in the solvent of the stripper composition improves the solubility of the overcoating layer, but apart from this, the chain-type amine compound and the alkylammonium compound dissolved in the solvent directly act as solutes. It serves to separate the photoresist and the overcoating layer. When the weight sum of the chain-type amine compound and the alkylammonium compound is 20 to 145 parts by weight with respect to 100 parts by weight of the solvent in the stripper composition, the overcoat layer and the color resist show swelling easily. Stripping may be more likely to occur. In particular, the swelling and peeling can occur more easily when the weight sum of the chain-type amine compound and the alkylammonium compound is 30 to 80 parts by weight based on 100 parts by weight of the solvent.

The stripper composition contains an alkylammonium compound to improve color resist and organic insulating film removal performance, and specifically, when the alkylammonium compound is included in an amount of 15% by weight or more based on the total weight of the stripper composition, the color resist and organic insulating film of the stripper composition are included. Removal performance can be greatly improved. However, when the alkylammonium compound is included in an amount of more than 29% by weight based on the total weight of the stripper composition, corrosiveness of the lower film may be caused, so it is avoided. When the alkylammonium compound is included in an amount of 15 to 20% by weight based on the total weight of the stripper composition, the color resist and organic insulating layer removal ability of the stripper may be more excellently expressed.

The alkylammonium compound serves to efficiently cause stripping through swelling and peeling of the overcoating layer and the color resist, and therefore, an inorganic base or a salt compound thereof imparting peeling characteristics and It is good to adjust the content in relation to the weight of Considering that a small amount of an inorganic base or its salt compound is included in the stripper composition, it is preferable to include the inorganic base or its salt compound and the alkylammonium compound in a weight ratio of 1:1,000 to 1:20,000 in the stripper composition for excellent stripping properties. helps to give In the stripper composition, the removal performance of the color resist and organic insulating film (overcoating layer) can be maintained excellently in the ratio of the inorganic base or its salt compound and the alkylammonium compound in the above weight ratio range, and corrosion on the inorganic insulating film including SiO _x The inhibitory effect may also be excellent, but if the weight ratio is out of the above range, even if the stripper composition is volatilized, residual precipitates may remain, which may impair the performance of the substrate.

The chain amine compound is, for example, aminoethanol, diethanolamine, N-methylethanolamine, triethanolamine, glycolamine, diglycolamine, hydroxylamine, methylamine, ethylamine, isopropylamine, monoisopropylamine , diethylamine, diisopropylamine, dibutylamine, ethylenediamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, monoisopropanolamine, aminoethoxyethanol, propoxyethylamine, isopropoxy Propylamine, methoxyethoxypropylamine, aminoethylethanol, methoxyethylamine, methoxypropylamine, ethoxypropylamine, 3-methoxypropylamine, 3-ethoxypropylamine, n-methylmethanolamine, mono Methanolamine, monoethanolamine, diethylamino propylamine, bis-2-methoxyethylamine, propylenediamine, 1,3-propanediamine, 1,2-propylenediamine, diethylenetriamine, dihexylenetriamine, triethylene At least one selected from tetramine, tetraethylenepentamine, oxolan-2-yl-methanamine, (oxolan-2-yl-methyl)butan-1-amine and methyloxolan-2-yl-methanamine In particular, when monoethanolamine, 3-ethoxypropylamine, N-methylethanolamine, hydroxylamine, monoisopropanolamine or 3-methoxypropylamine is used, the peeling effect can be more excellently expressed. there is.

The alkylammonium compound may include, for example, at least one selected from tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide, and particularly tetramethylammonium. In the case of using hydroxide, swelling and pilling effects can be more excellently expressed.

The stripping solution composition of the present invention may further contain a corrosion inhibitor in order to prevent corrosion of a lower layer such as an inorganic insulating layer and a metal wiring under a color resist layer during a stripping process.

In the case of including a corrosion inhibitor, 0.2 parts by weight or more with respect to 100 parts by weight of the solvent may be included to have a significant corrosion effect of the lower film layer, and if it is included in an amount exceeding 25 parts by weight, peeling properties may be impaired, and When included in the composition in an amount of 0.3 to 15 parts by weight based on 100 parts by weight of the solvent, the effect of preventing corrosion of the lower film layer may be particularly excellent.

Corrosion inhibitors include, for example, azole-based compounds such as tolytriazole, benzotriazole, and mercaptomethylimidazole; catechol-based compounds; and alkyl gallate compounds; In particular, when tolytriazole is used, the effect of preventing corrosion of the lower film layer can be more excellently expressed.

In addition to the above composition, the stripper composition of the present invention may include water, specifically distilled water, to activate the ammonium chloride compound, and the water content is the remaining amount of the composition and is 30 to 35% by weight based on the total weight of the stripper composition. It may be advantageous to include as much as possible to ensure that exfoliation occurs effectively.

A stripper composition for a silicon oxide film according to an aspect of the present invention includes at least one aprotic solvent, a glycol ether compound, an inorganic base or a salt compound thereof, a chain amine compound, and an alkylammonium compound, 100 parts by weight of the solvent 0.001 to 0.05 parts by weight of the inorganic base or its salt compound, even after completely removing the overcoating layer, which is the color resist and organic insulating film, with the stripper composition, the lower part such as the inorganic insulating film and metal wiring under the color resist It is a stripper composition for a silicon oxide film that can keep the film layer intact, especially when the lower film material includes a silicon oxide film (SiO _x ), which is easily corroded in the peeling process, and can be maintained intact. . At this time, the aprotic solvent of the stripper composition for the silicon oxide film may include at least one of the first aprotic solvent and the second aprotic solvent, and may include a glycol ether compound, an inorganic base or a salt compound thereof, and a chain amine compound And the alkylammonium compound may use the composition of each specific example described above.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

[Production Example: Preparation of stripper composition]

A stripper composition according to an embodiment of the present invention and a comparative example for effect comparison were prepared by mixing each component according to the composition shown in Table 1 below. The content of each component was described in parts by weight based on 100 parts by weight of the total amount of the first and second solvents.

first solvent second solvent glycol
ether inorganic base
or
his chloride chain
amine alkyl
ammonium corrosion
inhibitor water Example 1 NEP 14.5 DMSO 85.5 EDG 25 PA 0.0005 MEA 25 TMAH 45 TT 0.25 balance Example 2 NEP 14.5 DMSO 85.5 EDG 25 PA 0.001 MEA 25 TMAH 45 TT 0.25 balance Example 3 NEP 14.5 DMSO 85.5 EDG 25 PA 0.013 MEA 25 TMAH 45 TT 0.25 balance Example 4 NEP 40.0 DMSO 60.0 EDG 25 PA 0.013 MEA 25 TMAH 45 TT 0.25 balance Example 5 NEP 5.0 DMSO 95.0 EDG 25 PA 0.013 MEA 25 TMAH 45 TT 0.25 balance Example 6 NEP 14.5 DMSO 85.5 EDG 25 PA 0.04 MEA 25 TMAH 45 TT 0.25 balance Example 7 NEP 14.5 DMSO 85.5 EDG 25 PA 0.06 MEA 25 TMAH 45 TT 0.25 balance Example 8 NEF 14.5 DMSO 85.5 EDG 25 PA 0.013 MEA 25 TMAH 45 TT 0.25 balance Example 9 NEP 14.5 Sulfolane 85.5 EDG 25 PA 0.013 MEA 25 TMAH 45 TT 0.25 balance Example
10 NEP 14.5 DMSO 85.5 MDG 25 PA 0.013 MEA 25 TMAH 45 TT 0.25 balance Example
11 NEP 14.5 DMSO 85.5 EDG 25 PA 0.013 MEA 25 TMAH 37.5 TT 0.25 balance Example
12 NEP 14.5 DMSO 85.5 EDG 25 PA 0.013 MEA 25 TMAH 32.5 TT 0.25 balance Example
13 NEP 14.5 DMSO 85.5 EDG 25 PA 0.013 MEA 25 TMAH 25 TT 0.25 balance Example
14 NEP 14.5 DMSO 85.5 EDG 25 PA 0.013 MEA 25 TMAH 55 TT 0.25 balance Example
15 NEP 14.5 DMSO 85.5 EDG 25 KOH 0.013 MEA 25 TMAH 45 TT 0.25 balance Comparative Example 1 - - DMSO 100 EDG 25 PA 0.0005 MEA 25 TMAH 45 TT 0.25 balance Comparative Example 2 NEP 14.5 DMSO 85.5 EDG 25 - - MEA 25 TMAH 45 TT 0.25 balance Comparative Example 3 NEP 14.5 DMSO 85.5 EDG 25 PA 0.0005 MEA 25 - - TT 0.25 balance Comparative Example 4 NEP 55.0 DMSO 45.0 EDG 25 PA 0.0005 MEA 25 TMAH 45 TT 0.25 balance Comparative Example 5 NEP 80.0 DMSO 20.0 EDG 25 PA 0.0005 MEA 25 TMAH 45 TT 0.25 balance Comparative Example 6 NEP 2.3 DMSO 97.7 EDG 25 PA 0.0005 MEA 25 TMAH 45 TT 0.25 balance Comparative Example 7 NEP 2.0 DMSO 98.0 EDG 25 PA 0.0005 MEA 25 TMAH 45 TT 0.25 balance

(unit: parts by weight)

- NEP: N-ethyl-2-pyrrolidone; - NEF : N-Ethylformamide

- DMSO: Dimethyl sulfoxide; - EDG : Diethylene glycol ethyl ether

- MDG : Diethylene glycol methyl ether; - PA : Potassium acetate

- MEA : Mono ethanol amine; - TMAH : Tetra Methyl Ammonium Hydroxide

- TT: Tolyl triazole; - Water: DI water

[Experimental Example: Evaluation of Physical Properties of Stripper Composition]

Removal evaluation of the color resist and the insulating film used a substrate on which a red color resist, a green color resist, a blue color resist, and an organic insulating film were all formed.

<Experimental Example 1: Evaluation of removal performance>

In order to confirm the removal performance of the color resist and the organic insulating film, the temperature of the stripper composition prepared in Examples and Comparative Examples was raised to 75° C., and then the substrate was immersed to measure the complete stripping time. Subsequently, after taking the substrate out of the stripper composition, washing with ultrapure water and drying with nitrogen gas, it was confirmed with an optical microscope whether or not the color resist and organic insulating film remained in the pattern. It was evaluated based on the following criteria and the results are shown in Table 2 below.

◎: Completely removed within 2 minutes

○: When completely removed within 4 minutes

△: Completely removed within 6 minutes

X: If not removed within 6 minutes

<Experimental Example 2: Lower membrane damage evaluation 1-SEM>

While the removal performance evaluation proceeded, the damage (degree of corrosion) of the lower film (inorganic insulating film) was confirmed by SEM. It was evaluated based on the following criteria, and the results are shown in Table 2 and FIGS. 2 and 4 below.

○: no change in thickness up to 60 minutes

△: change in thickness within 30 minutes

X: thickness change within 5 minutes

<Experimental Example 3: Lower membrane damage evaluation 2-E/R>

The substrate was immersed for 60 minutes in the stripper compositions of Examples and Comparative Examples, the temperature of which was raised to 75°C. After the substrate was taken out of the stripper composition, washed with ultrapure water and dried with nitrogen gas, the thickness of the lower film (SiO _X ) was measured using an SEM. E / R (etch rate) was calculated using the formula below, and the results are shown in Table 2 below.

- E/R (etch rate) = (thickness of lower film before immersion - thickness of lower film after immersion) / 60min

<Experimental Example 4: Lower film damage evaluation 3-Si elution amount>

The substrate was immersed for 60 minutes in the stripper compositions of Examples and Comparative Examples, the temperature of which was raised to 75°C. After removing the substrate, the amount of Si eluted in the stripper composition was measured with a dissolution evaluation measuring instrument (ICP-OES, Thermo Scientific Co.), and the results are shown in Table 2 below.

Removal performance evaluation
(Experimental Example 1) Lower membrane damage assessment 1
(SEM, Experimental Example 2) E/R (nm/min)
(Experimental Example 3) Si elution amount (ppm)
(Experimental Example 4) Example 1 ○ ○ 0 0.10 Example 2 ◎ ○ 0 0.16 Example 3 ◎ ○ 0 0.30 Example 4 ◎ ○ 0 0.30 Example 5 ◎ ○ 0 0.30 Example 6 ◎ △ 1.15 0.79 Example 7 ◎ △ 1.90 0.94 Example 8 ○ ○ 0 0.28 Example 9 ○ ○ 0 0.30 Example 10 ◎ ○ 0 0.30 Example 11 ◎ ○ 0 0.30 Example 12 ○ ○ 0 0.30 Example 13 ○ ○ 0 0.30 Example 14 ◎ ○ 0 0.30 Example 15 ◎ △ 0.9 0.71 Comparative Example 1 △ ○ 0 0.30 Comparative Example 2 X ○ 0 0.30 Comparative Example 3 X ○ 0 0.30 Comparative Example 4 △ ○ 0 0.30 Comparative Example 5 △ ○ 0 0.30 Comparative Example 6 △ ○ 0 0.30 Comparative Example 7 △ ○ 0 0.30

Through Table 2, Examples 1 to 15 and Comparative Examples 1 to 7 all showed good results in the lower film damage evaluation (Experimental Examples 2 to 4), but in the removal performance of the color resist and organic insulating film, Comparative Examples and Example It can be seen that there is a large difference between examples. Examples 1 to 15 of the present invention showed excellent color resist and organic insulating film removal performance, but Comparative Examples 1 to 7 showed poor color resist and organic insulating film removal performance to the extent that it was difficult to use as a stripper composition. can In particular, Examples 2 to 5, 10, 11, and 14 have excellent removal performance of color resist and organic insulating film as well as excellent results of evaluation of damage to the lower layer. It can be seen that the organic insulating film removability is excellent and the lower film quality is not damaged. In addition, it can be seen that Examples 10, 11, and 14 containing 15% by weight or more of an alkylammonium compound relative to the total stripper composition have better removal performance than Examples 12 and 13 containing less than 15% by weight of an alkylammonium compound. .

1 is a photograph taken by SEM of a TFT substrate on which a color layer and an organic insulating film (Over Coat, OC) are formed before exfoliation. 2(a) is an enlarged SEM photograph of a portion in which metal wiring (Cu), an inorganic insulating film (SiO _x ), and a color resist (color layer) are stacked in FIG. 1, and FIG. After stripping the stripper composition of Example 1 prepared in Preparation Example by the above method, the color resist and organic insulating film (OC) are completely peeled off, and the inorganic insulating film (SiO _x ) is a photograph taken by SEM.

In the same way, the substrate was peeled off with the stripper composition prepared according to the embodiment of the present invention and taken by SEM is shown in FIG. 4, and the thickness of the remaining inorganic insulating film (SiO _x ) is also indicated. 3 is a substrate before forming a color resist (Color Layer) and an organic insulating film layer (OC), and is an enlarged SEM photograph of a portion where a metal wiring (Cu) and an inorganic insulating film (SiO _x ) are formed. It can be seen that the insulating film (SiO _x ) is formed to be 522 nm. Referring to FIGS. 3 and 4, when the stripper composition of the embodiment of the present invention is used (FIG. 4), even though both the color resist (Color Layer) and the organic insulating film layer (OC) are removed, the inorganic insulating film (SiO _x ) It can be confirmed that the thickness of is maintained well, and in the case of Examples 1 to 3, the thickness of the inorganic insulating film (SiO _x ) is 522 nm, and it can be seen that no damage to the inorganic insulating film has occurred even after the peeling evaluation.

Although the embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and variations are possible without departing from the technical spirit of the present invention described in the claims. It will be obvious to those skilled in the art.

Claims (19)

a solvent comprising a first aprotic polar solvent containing a nitrogen atom (N) and a second aprotic polar solvent;
glycol ether compounds;
inorganic bases or salt compounds thereof;
chain amine compounds; and
Alkyl ammonium compounds; including,
The first aprotic polar solvent and the second aprotic polar solvent have different molecular weights,
Wherein the weight ratio of the first aprotic polar solvent and the second aprotic polar solvent is 1: 1 to 1: 40, the stripper composition.
According to claim 1,
The peeling solution composition of claim 1, wherein the molecular weight difference between the first aprotic polar solvent and the second aprotic polar solvent is 5 to 65 g/mol.
According to claim 1,
The first aprotic polar solvent is N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethylform A stripper composition comprising at least one selected from amide (N-Ethylformamide), N-methylformamide (N-Methylformamide) and pyrrolidone (pyrrolidone).
According to claim 1,
The second aprotic polar solvent has a molecular weight of 70 to 140 g / mol, the stripper composition.
According to claim 1,
Wherein the second aprotic polar solvent includes at least one selected from dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide and sulfolane.
According to claim 1,
The first aprotic polar solvent is N-ethyl-2-pyrrolidone, the stripper composition.
According to claim 1,
A stripper composition comprising 10 to 100 parts by weight of the glycol ether compound based on 100 parts by weight of the solvent.
According to claim 1,
The glycol ether compound is ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether , diethylene glycol butyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol butyl ether, diethylene glycol dimethyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, ethylene glycol dimethyl ether, dipropylene A peeling solution composition comprising at least one selected from glycol dimethyl ether, triethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether and diethylene glycol methyl ethyl ether.
According to claim 1,
A stripper composition comprising 0.001 to 0.05 parts by weight of the inorganic base or its salt compound based on 100 parts by weight of the solvent.
According to claim 1,
The inorganic base or its salt compound includes potassium acetate, potassium nitrate, potassium carbonate, potassium pyrophosphate, potassium oleate, potassium benzoate, potassium laurate, potassium tert-butoxide, potassium sulfate, potassium sorbate, Potassium Amino Benzoate, Potassium Disulfate, Potassium Cyanate, Potassium Sulfide, Potassium Xyrene Sulfonate, Sodium Xyrene Sulfonate, Lithium Hydroxide, Sodium Hydroxide, Potassium Hydroxide, Sodium Carbonate, Sodium Hydrogen A stripper composition comprising at least one selected from carbonate, potassium hydrogen carbonate, sodium nitrate, sodium sulfate, sodium acetate, sodium silicate and potassium silicate.
According to claim 1,
A stripper composition comprising 20 to 145 parts by weight of the chain-type amine compound and the alkylammonium compound based on 100 parts by weight of the solvent.
According to claim 1,
A stripper composition comprising 15 to 29% by weight of the alkylammonium compound based on the total weight of the stripper composition.
According to claim 1,
A stripper composition comprising the inorganic base or its salt compound and the alkylammonium compound in a weight ratio of 1:1,000 to 1:20,000.
According to claim 1,
The chain amine compound is aminoethanol, diethanolamine, N-methylethanolamine, triethanolamine, glycolamine, diglycolamine, hydroxylamine, methylamine, ethylamine, isopropylamine, monoisopropylamine, diethyl Amine, diisopropylamine, dibutylamine, ethylenediamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, monoisopropanolamine, aminoethoxyethanol, propoxyethylamine, isopropoxypropylamine, Methoxyethoxypropylamine, aminoethylethanol, methoxyethylamine, methoxypropylamine, ethoxypropylamine, 3-methoxypropylamine, 3-ethoxypropylamine, n-methylmethanolamine, monomethanolamine, Monoethanolamine, diethylamino propylamine, bis-2-methoxyethylamine, propylenediamine, 1,3-propanediamine, 1,2-propylenediamine, diethylenetriamine, dihexylenetriamine, triethylenetetramine, containing at least one selected from tetraethylenepentaamine, oxolan-2-yl-methanamine, (oxolan-2-yl-methyl)butan-1-amine and methyloxolan-2-yl-methanamine, stripper composition.
According to claim 1,
Wherein the alkylammonium compound includes at least one selected from tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.
According to claim 1,
A stripper composition further comprising a corrosion inhibitor.
According to claim 16,
A stripper composition comprising 0.2 to 25 parts by weight of the corrosion inhibitor based on 100 parts by weight of the solvent.
According to claim 16,
Wherein the corrosion inhibitor includes at least one selected from tolytriazole, benzotriazole, mercaptomethylimidazole, catechol-based compounds, and alkyl gallate-based compounds.
glycol ether compounds;
inorganic bases or salt compounds thereof;
chain amine compounds;
alkylammonium compounds; and
Including; an aprotic solvent;
A stripper composition for a silicon oxide film comprising 0.001 to 0.05 parts by weight of the inorganic base or a salt thereof based on 100 parts by weight of the solvent.

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