Stripper composition for removing color resist and insulating layer

Abstract

The present invention relates to a stripping solution composition for removing color resist and insulating films, and more specifically, to a stripping solution composition comprising a first non-protic polar solvent containing a nitrogen atom (N), a second non-protic polar solvent having a different molecular weight from the first non-protic polar solvent, a glycol ether compound, an inorganic base or its salt compound, a chain-type amine compound, and an alkylammonium compound, which can remove not only color resist but also negative and positive organic insulating films in a short time without damaging the underlying inorganic insulating film and various metal wirings.

Description

Technology Field

[0001] The present invention relates to a stripping solution composition capable of removing color resist and insulating film in order to reuse defective substrates generated in TFT-LCD, OLED, etc. processes. Background Technology

[0002] TFT-LCDs and OLEDs require color filter layers with red, green, and blue patterns to implement the color of each pixel.

[0003] The process for manufacturing a color filter on an upper substrate is as follows. Taking a TFT-LCD as an example, a color resist is applied over a TFT structure and exposed to light to cure the color resist through a photopolymerization reaction. After the exposure is complete, unexposed areas of the color resist are removed by development, and the material undergoes a sintering process. In the event that a defect occurs in the color filter during this process, conventionally, the defective substrate was not reused and was mostly disposed of. Consequently, there is an increasing demand for stripping solution compositions that allow for the removal of defective color filters and the reuse of the substrate.

[0004] Korean Registered Patent No. 10-1488265, regarding a stripping solution composition for stripping a color filter or an organic insulating film, discloses a stripping solution composition for removing a color resist comprising a hydroxide-based compound, an alkylene glycol alkyl ether-based compound, an alkanolamine-based compound, an inorganic salt compound, and a remainder of water. However, there is a problem in that the removal performance deteriorates when used for a long period due to volatilization during a high-temperature process, and there is also a problem in that it does not exhibit the effect of removing the color resist and the organic insulating film at a rapid speed. The problem to be solved

[0005] The objective of the present invention is to provide a stripping solution composition that can easily remove a color resist and an organic insulating film at a high speed without damaging the underlying film, and in particular has excellent removal properties for the organic insulating film.

[0006] Another objective of the present invention is that, in the process of removing color resist and organic insulating film, silicon nitride (SiN), which is a silicon-based underlying film, x ), silicon oxide (SiO x The purpose is to provide a stripping solution composition that does not cause damage to the ) etc. means of solving the problem

[0007] To achieve the above objective, a stripping solution composition according to one embodiment of the present invention comprises a solvent comprising a first nonprotic polar solvent containing a nitrogen atom (N) and a second nonprotic polar solvent; a glycol ether compound; an inorganic base or a salt compound thereof; a chain-type amine compound; and an alkylammonium compound, wherein the molecular weights of the first nonprotic polar solvent and the second nonprotic polar solvent are different, and the weight ratio of the first nonprotic polar solvent and the second nonprotic polar solvent is 1:1 to 1:40.

[0008] The difference in molecular weight between the first aprotic polar solvent and the second aprotic polar solvent may be 5 to 65 g / mol.

[0009] The above-mentioned first non-protic polar solvent may include one or more selected from N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethylformamide, N-methylformamide, and pyrrolidone.

[0010] The above second aprotic polar solvent may have a molecular weight of 70 to 140 g / mol.

[0011] The above second non-protic polar solvent may include one or more selected from dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, and sulfolane.

[0012] The first aprotic polar solvent may be N-ethyl-2-pyrrolidone.

[0013] The above stripping solution composition may contain 10 to 100 parts by weight of the glycol ether compound per 100 parts by weight of solvent.

[0014] The glycol ether compound may include one or more selected from 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 glycol dimethyl ether, triethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether.

[0015] In addition, the above stripping solution composition may contain 0.001 to 0.05 parts by weight of the inorganic base or its salt compound with respect to 100 parts by weight of the solvent.

[0016] The above inorganic base or its salt compound may include one or more selected from potassium acetate, potassium nitrate, potassium carbonate, potassium pyrophosphate, potassium oleate, potassium benzoate, potassium laurate, potassium tert-butoxide, potassium sulfate, potassium sorbate, potassium aminobenzoate, potassium disulfate, potassium cyanate, potassium sulfide, potassium xylene sulfonate, sodium xylene sulfonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium nitrate, sodium sulfate, sodium acetate, sodium silicate, and potassium silicate.

[0017] The above stripping solution composition may contain 20 to 145 parts by weight of the chain-type amine compound and the alkylammonium compound per 100 parts by weight of the solvent.

[0018] In addition, the stripping solution composition may contain 15 to 29 weight percent of the alkylammonium compound based on the total weight of the stripping solution composition.

[0019] The above stripping solution composition may contain the inorganic base or its chloride compound and the alkylammonium compound in a weight ratio of 1:1,000 to 1:20,000.

[0020] The above chain-type amine compound is aminoethanol, diethanolamine, N-methylethanolamine, triethanolamine, glycolamine, diglycolamine, hydroxylamine, methylamine, ethylamine, isopropylamine, monoisopropylamine, diethylamine, diisopropylamine, dibutylamine, ethylenediamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, monoisopropanolamine, aminoethoxyethanol, propoxyethylamine, isopropoxypropylamine, methoxyethoxypropylamine, aminoethylethanol, methoxyethylamine, methoxypropylamine, ethoxypropylamine, 3-methoxypropylamine, 3-ethoxypropylamine, n-methylmethanolamine, monomethanolamine, monoethanolamine, diethylaminopropylamine, bis-2-methoxyethylamine, propylenediamine, 1,3-propanediamine, It may include one or more selected from 1,2-propylenediamine, diethylenetriamine, dihexyllentriaamine, triethylenetetramine, tetraethylenepentaamine, oxolan-2-yl-methaneamine, (oxolan-2-yl-methyl)butan-1-amine and methyloxolan-2-yl-methaneamine.

[0021] The above alkylammonium compound may include one or more selected from tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.

[0022] The stripping solution composition may further include a corrosion inhibitor, and may include 0.2 to 25 parts by weight of the corrosion inhibitor per 100 parts by weight of the solvent. In this case, the corrosion inhibitor may include one or more selected from tolytriazole, benzotriazole, mercaptomailimidazole, catechol-based compounds, and alkyl gallate compounds.

[0023] A stripping solution composition for a silicon oxide film according to another embodiment of the present invention comprises a glycol ether compound; an inorganic base or its salt compound; a chain-type amine compound; an alkylammonium compound and an aprotic solvent, wherein the inorganic base or its salt compound is contained in an amount of 0.001 to 0.05 parts by weight per 100 parts by weight of the solvent. Effects of the invention

[0024] The stripping solution composition of the present invention enables the reuse of color filter substrates and TFT (Thin Film Transistor) substrates by removing not only the color resist but also negative and positive organic insulating films in a short time without damaging the underlying inorganic insulating film and various metal wirings.

[0025] The stripping solution composition of the present invention is SiN x In addition to inorganic insulating films composed of, SiO x Even for inorganic insulating films made of [material], there is an effect of causing almost no damage due to corrosion during the peeling process.

[0026] The stripping solution composition of the present invention can easily remove color resist and organic insulating film materials within a short period of time, and has the advantage of being able to rinse with only water without the need to use organic solvents such as isopropyl alcohol or dimethyl sulfoxide in a subsequent rinsing process, and in particular, the color filter substrate can be reused by enabling the removal of the resist pattern. Brief explanation of the drawing

[0027] Figure 1 is a scanning electron microscope (SEM) image of a TFT substrate with a color resist (Color Layer) and an organic insulating film layer (Over Coat, OC) formed before peeling. Figure 2 is an enlarged SEM image of Figure 1 (a) and an SEM image after peeling according to the peeling solution composition of Example 1 (b). FIG. 3 shows metal wiring and an underlying film layer (inorganic insulating film, SiO₂) before the formation of the color resist (Color Layer) and organic insulating film layer (Over Coat, OC). x This shows an SEM image of a substrate on which ) is formed and the thickness of the underlying film layer. FIG. 4 shows the metal wiring and the underlying film layer (inorganic insulating film, SiO₂) after peeling off the color resist (Color Layer) and the organic insulating film layer (OC) using a peeling solution composition according to embodiments of the present invention. x This shows an SEM image of a substrate on which ) is formed and the thickness of each underlying film layer. Specific details for implementing the invention

[0028] Terms and words used in this specification and claims should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted in a meaning and concept consistent with the technical spirit of the invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0029] Therefore, the configurations illustrated in the embodiments and manufacturing examples described in this specification are merely one preferred embodiment of the present invention and do not represent all of the technical ideas of the present invention; thus, it should be understood that various equivalents and modifications that can replace them may exist at the time of filing this application.

[0030] Hereinafter, embodiments of the present invention are described in detail so that those skilled in the art can easily implement the invention. However, the present invention may be embodied in various different forms and is not limited to the manufacturing examples and embodiments described herein.

[0031] The present invention relates to a stripping solution composition that can easily remove a color resist (CR) and an organic insulating film (Over Coat, OC), etc., without causing damage to an underlying film layer such as an inorganic insulating film and metal wiring on a substrate.

[0032] A stripping solution composition according to one aspect of the present invention is a composition that can easily strip a color resist and an organic insulating film by increasing the dissolving power for the color resist and the organic insulating film on a substrate using two or more polar solvents having different molecular weights. Specifically, the polar solvents include a first non-protic polar solvent containing a nitrogen atom (N) and a second non-protic polar solvent having a molecular weight different from that of the first non-protic polar solvent. That is, the stripping solution composition according to one aspect of the present invention is a mixture of a glycol ether compound; an inorganic base or its salt compound; a chain-type amine compound and an alkylammonium compound in a solvent having excellent dissolving power for the color resist and the organic insulating film. In addition, the weight ratio of the first non-protic polar solvent containing nitrogen atoms (N) and the second non-protic polar solvent is 1:1 to 1:40, which can further improve the dissolving power of the color resist and organic insulating film of the stripping solution. If the ratio is outside this range, the dissolving power of the organic insulating film may decrease, and there is a disadvantage that the performance over time (time during which performance is maintained) of the stripping solution composition is reduced.

[0033] Among the first aprotic solvent or the second aprotic solvent having the difference in molecular weight, the solvent with the smaller molecular weight penetrates primarily into the cured overcoating layer and color resist layer during the process of dissolving the overcoating layer and color resist layer to widen the gaps between the polymers (Step 1), and the solvent with the larger molecular weight penetrates secondarily to break the intermolecular bonds, and the overcoating layer and color resist layer particles with broken bonds are surrounded by the solvent and dissolved in a stable state (Step 2). Due to the peeling process of Step 1 and Step 2, the solvent's dissolving power for the overcoating layer and color resist layer can be excellent.

[0034] When the difference in molecular weight between the first non-protic polar solvent containing the nitrogen atom (N) and the second non-protic polar solvent in the solvent is within a specific range, the primary separation of the organic insulating film layer (overcoating layer) during the peeling process can occur more easily. Specifically, there may be a difference of 5 to 65 g / mol, and more specifically, a difference of 5 to 55 g / mol. The difference in molecular weight between the first non-protic polar solvent containing the nitrogen atom (N) and the second non-protic polar solvent in the solvent must be 5 or more so that the effect of increasing solubility through the two-step peeling process can be manifested. If the difference in molecular weight between the first non-protic polar solvent containing the nitrogen atom (N) and the second non-protic polar solvent in the solvent is higher than 65 g / mol, a problem may occur in which the cleaning ability is reduced during the cleaning step after the peeling step. The molecular weight of the first nonprotic polar solvent containing the nitrogen atom (N) may be greater than the molecular weight of the second nonprotic polar solvent, or conversely, the molecular weight of the second nonprotic polar solvent may be greater than the molecular weight of the first nonprotic polar solvent containing the nitrogen atom (N). In addition, a case where the difference between the molecular weight of the first nonprotic polar solvent containing the nitrogen atom (N) and the molecular weight of the second nonprotic polar solvent is 5 to 55 g / mol may be preferred for effective exfoliation.

[0035] The first non-protic polar solvent containing the nitrogen atom (N) may specifically have a molecular weight of 50 to 120 g / mol and may include, for example, one or more selected from N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidinone, N-ethylformamide, N-methylformamide, and pyrrolidone.

[0036] In addition, the second non-protic polar solvent is not particularly limited as long as it is a non-protic polar solvent with a molecular weight difference from the first non-protic polar solvent, but considering compatibility, it may include a nitrogen atom (N) or a sulfur atom (S), and specifically, the molecular weight may be 70 to 140 g / mol. The second non-protic polar solvent satisfying the above conditions may include, for example, one or more selected from dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, and sulfolane. The second non-protic polar solvent is used together with the first non-protic polar solvent containing the nitrogen atom (N), and when using a non-protic polar solvent with a molecular weight of 70 to 140 g / mol, an excellent swelling effect on the color resist and organic insulating film is exhibited, and the peeling power is increased due to excellent dissolution performance, as well as an excellent residue removal effect.

[0037] As a first nonprotic polar solvent containing the above nitrogen atom (N), N-ethyl-2-pyrrolidone has a high molecular weight of 113.16 g / mol and includes a cyclic structure, so it is suitable as a solvent because it has excellent solubility for solutes, and also has particularly excellent solubility for the overcoating layer through its relatively large cyclic molecular structure, so N-ethyl-2-pyrrolidone can be used as a first nonprotic polar solvent containing the nitrogen atom (N).

[0038] In the stripping solution composition of the present invention, the glycol ether compound acts as a buffer to ensure that various compositions included in the stripping solution are evenly dissolved in the solvent, and also plays a role in ensuring that the stripping solution composition remaining on the substrate is washed away smoothly without adsorbing foreign substances, etc. when cleaned with ultrapure water during the cleaning step following the stripping step. The above buffering role can be effectively achieved when the glycol ether compound is included in the stripping solution composition in an amount of 10 to 100 parts by weight per 100 parts by weight of solvent, and in particular, the above buffering role can be exhibited even more excellently when the glycol ether compound is included in an amount of 12 to 50 parts by weight per 100 parts by weight of solvent. If the glycol ether compound is included in the stripping solution composition in an amount less than the above weight part, the inorganic base or its salt compound, amine compound, alkylammonium compound, etc. included in the solvent may not be evenly mixed, and there may be a problem in that the condition of the substrate after stripping may not be uniform. If the glycol ether compound is included in the stripping solution composition in excess of the above weight part, the specific gravity of the material without stripping performance may become excessively high, and there may be a problem in that the stripping effect is reduced.

[0039] The glycol ether compound may include, for example, one or more selected from 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 glycol dimethyl ether, triethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether.

[0040] In the stripping solution composition of the present invention, an inorganic base or its salt compound is included in the stripping solution together with an alkylammonium compound to rapidly strip the overcoating layer and the color resist layer dissolved by the solvent, thereby serving to enhance the stripping ability of the stripping solution. Furthermore, even if the inorganic base or its salt compound is included in a small amount in the stripping solution composition, it can improve the corrosion resistance of the underlying film and achieve an excellent stripping effect through interaction with other components of the stripping solution composition. Specifically, the above effect can be achieved even if the inorganic base or its salt compound is included in a small amount of 0.001 to 0.05 parts by weight per 100 parts by weight of solvent in the stripping solution composition. However, for the stripping ability enhancement effect to be significantly manifested, the inorganic base or its salt compound must be at least 0.001 parts by weight; if it is included in an amount exceeding 0.05 parts by weight, corrosion of the inorganic insulating film beneath the color resist may occur due to an excessive stripping effect. In particular, when an inorganic base or its salt compound is included in an amount of 0.002 to 0.04 parts by weight per 100 parts by weight of solvent, the ability of the stripping solution to remove color resist and organic insulating film can be exhibited more excellently.

[0041] The above inorganic base or its salt compound may be, for example, an alkali salt compound, and specifically may include one or more selected from potassium acetate, potassium nitrate, potassium carbonate, potassium pyrophosphate, potassium oleate, potassium benzoate, potassium laurate, potassium tert-butoxide, potassium sulfate, potassium sorbate, potassium aminobenzoate, potassium disulfate, potassium cyanate, potassium sulfide, potassium xylene sulfonate, sodium xylene sulfonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium nitrate, sodium sulfate, sodium acetate, sodium silicate, and potassium silicate, and in particular, an inorganic base or When potassium acetate is used as its chloride compound, the stripping effect of the stripping solution composition is exhibited more excellently, and the corrosion prevention effect on the underlying inorganic insulating film can be further enhanced.

[0042] A first non-protic polar solvent containing a nitrogen atom (N) included in the solvent of the stripping solution composition improves the solubility for the overcoating layer, but separately, the chain-type amine compound and the alkylammonium compound dissolved in the solvent serve as solutes to directly strip the photoresist and the overcoating layer. When the weight sum of the chain-type amine compound and the alkylammonium compound is included in the stripping solution composition at 20 to 145 parts by weight per 100 parts by weight of the solvent, swelling of the overcoating layer and the color resist occurs easily, and stripping can occur more effectively. In particular, when the weight sum of the chain-type amine compound and the alkylammonium compound is 30 to 80 parts by weight per 100 parts by weight of the solvent, the swelling and stripping can occur even more effectively.

[0043] The stripping solution composition includes an alkylammonium compound to improve the removal performance of color resist and organic insulating films. Specifically, when the stripping solution composition contains 15% by weight or more of the alkylammonium compound relative to the total weight of the stripping solution composition, the removal performance of the color resist and organic insulating films of the stripping solution composition can be significantly improved. However, when the stripping solution composition contains more than 29% by weight of the alkylammonium compound relative to the total weight of the stripping solution composition, it is avoided as it may cause corrosiveness to the underlying film. When the alkylammonium compound is included in an amount of 15 to 20% by weight relative to the total weight of the stripping solution composition, the ability of the stripping solution to remove color resist and organic insulating films can be exhibited even more excellently.

[0044] The above-mentioned alkylammonium compound plays a role in enabling efficient stripping through swelling and peeling of the overcoating layer and color resist; therefore, it is advisable to adjust its content in relation to the weight of the inorganic base or its chloride compound that imparts stripping properties. Considering that the inorganic base or its chloride compound is included in a small amount in the stripping solution composition, including the inorganic base or its chloride compound and the alkylammonium compound in a weight ratio of 1:1,000 to 1:20,000 helps to impart excellent stripping properties. When the ratio of the inorganic base or its chloride compound and the alkylammonium compound in the stripping solution composition is within the above weight ratio range, the removal performance of the color resist and the organic insulating film (overcoating layer) can be maintained at an excellent level, and SiO x Although the corrosion inhibition effect on inorganic insulating films including [the product] may be excellent, if the weight ratio is outside the above range, residual precipitates, etc. may remain even after the stripping solution composition has evaporated, which may impair the performance of the substrate.

[0045] The above chain-type amine compounds are, 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, isopropoxypropylamine, methoxyethoxypropylamine, aminoethylethanol, methoxyethylamine, methoxypropylamine, ethoxypropylamine, 3-methoxypropylamine, 3-ethoxypropylamine, n-methylmethanolamine, monomethanolamine, monoethanolamine, diethylaminopropylamine, bis-2-methoxyethylamine, propylenediamine, 1,3-propanediamine, It may include one or more selected from 1,2-propylenediamine, diethylenetriamine, dihexyllentriaamine, triethylenetetramine, tetraethylenepentaamine, oxolan-2-yl-methaneamine, (oxolan-2-yl-methyl)butan-1-amine and methyloxolan-2-yl-methaneamine, and in particular, when monoethanolamine, 3-ethoxypropylamine, N-methylethanolamine, hydroxylamine, monoisopropanolamine or 3-methoxypropylamine is used, the peeling effect may be expressed more excellently.

[0046] The above alkylammonium compound may include one or more selected from, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide, and in particular, when tetramethylammonium hydroxide is used, swelling and peeling effects may be expressed more excellently.

[0047] The stripping solution composition of the present invention may further include a corrosion inhibitor to prevent corrosion of the underlying film layer, such as an inorganic insulating film and metal wiring, beneath the color resist layer during the stripping process.

[0048] When a corrosion inhibitor is included, it must be included in an amount of at least 0.2 parts by weight per 100 parts by weight of solvent for the corrosion effect of the lower film layer to be significant, and if included in an amount exceeding 25 parts by weight, the peeling characteristics may be impaired, and when included in an amount of 0.3 to 15 parts by weight per 100 parts by weight of solvent in the peeling solution composition, the corrosion prevention effect of the lower film layer can be particularly excellently expressed.

[0049] The corrosion inhibitor may include one or more selected from azole compounds such as tolytriazole, benzotriazole, and mercaptomethylimidazole; catechol compounds; and alkyl gallate compounds; and in particular, when tolytriazole is used, the corrosion prevention effect of the underlying film layer can be exhibited more excellently.

[0050] In addition to the above composition, the stripping solution composition of the present invention may include water, specifically distilled water, to activate the ammonium chloride compound, and it may be advantageous to include the water content as the remainder of the above composition in an amount of 30 to 35 weight percent relative to the total weight of the stripping solution composition to ensure that stripping occurs effectively.

[0051] A stripping solution composition for a silicon oxide film according to one aspect of the present invention comprises one or more aprotic solvents, a glycol ether compound, an inorganic base or a salt compound thereof, a chain-type amine compound, and an alkylammonium compound, wherein the inorganic base or its salt compound is included in a very small amount of 0.001 to 0.05 parts by weight per 100 parts by weight of the solvent, so that even after the overcoating layer, which is a color resist and an organic insulating film, is completely removed by the stripping solution composition, the underlying film layer, such as an inorganic insulating film and metal wiring beneath the color resist, can be maintained intact, and in particular, the silicon oxide film (SiO₂), which is prone to corrosion during the stripping process xThe composition is a stripping solution for a silicon oxide film having the characteristic that the underlying film can be fully maintained even when the underlying film is included as the underlying film. In this case, the aprotic solvent of the stripping solution composition for a silicon oxide film may include one or more of the first aprotic solvent or the second aprotic solvent, and the glycol ether compound, inorganic base or its salt compound, chain-type amine compound and alkylammonium compound may use the compositions of each specific example described above.

[0052] Hereinafter, embodiments of the present invention are described in detail so that those skilled in the art can easily implement the invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[0054] [Preparation Example: Preparation of a stripping solution composition]

[0055] A comparative example for comparing the peeling solution composition and effects according to the embodiment of the present invention was 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 a total amount of 100 parts by weight of the first and second solvents.

[0056] First solvent Second solvent Glycol ether Inorganic bases or their salt compounds chain amines alkylammonium Corrosion inhibitor water Example 1 NEP 14.5 DMSO 85.5 EDG 25 PA 0.0005 MEA 25 TMAH 45 TT 0.25 Remaining amount Example 2 NEP 14.5 DMSO 85.5 EDG 25 PA 0.001 MEA 25 TMAH 45 TT 0.25 Remaining amount Example 3 NEP 14.5 DMSO 85.5 EDG 25 PA 0.013 MEA 25 TMAH 45 TT 0.25 Remaining amount Example 4 NEP 40.0 DMSO 60.0 EDG 25 PA 0.013 MEA 25 TMAH 45 TT 0.25 Remaining amount Example 5 NEP 5.0 DMSO 95.0 EDG 25 PA 0.013 MEA 25 TMAH 45 TT 0.25 Remaining amount Example 6 NEP 14.5 DMSO 85.5 EDG 25 PA 0.04 MEA 25 TMAH 45 TT 0.25 Remaining amount Example 7 NEP 14.5 DMSO 85.5 EDG 25 PA 0.06 MEA 25 TMAH 45 TT 0.25 Remaining amount Example 8 NEF 14.5 DMSO 85.5 EDG 25 PA 0.013 MEA 25 TMAH 45 TT 0.25 Remaining amount Example 9 NEP 14.5 Sulfolane 85.5 EDG 25 PA 0.013 MEA 25 TMAH 45 TT 0.25 Remaining amount Example 10 NEP 14.5 DMSO 85.5 MDG 25 PA 0.013 MEA 25 TMAH 45 TT 0.25 Remaining amount Example 11 NEP 14.5 DMSO 85.5 EDG 25 PA 0.013 MEA 25 TMAH 37.5 TT 0.25 Remaining amount Example 13 NEP 14.5 DMSO 85.5 EDG 25 PA 0.013 MEA 25 TMAH 25 TT 0.25 Remaining amount Example 14 NEP 14.5 DMSO 85.5 EDG 25 PA 0.013 MEA 25 TMAH 55 TT 0.25 Remaining amount Example 15 NEP 14.5 DMSO 85.5 EDG 25 KOH 0.013 MEA 25 TMAH 45 TT 0.25 Remaining amount Comparative Example 1 - - DMSO 100 EDG 25 PA 0.0005 MEA 25 TMAH 45 TT 0.25 Remaining amount Comparative Example 2 NEP 14.5 DMSO 85.5 EDG 25 - - MEA 25 TMAH 45 TT 0.25 Remaining amount Comparative Example 3 NEP 14.5 DMSO 85.5 EDG 25 PA 0.0005 MEA 25 - - TT 0.25 Remaining amount Comparative Example 4 NEP 55.0 DMSO 45.0 EDG 25 PA 0.0005 MEA 25 TMAH 45 TT 0.25 Remaining amount Comparative Example 5 NEP 80.0 DMSO 20.0 EDG 25 PA 0.0005 MEA 25 TMAH 45 TT 0.25 Remaining amount Comparative Example 6 NEP 2.3 DMSO 97.7 EDG 25 PA 0.0005 MEA 25 TMAH 45 TT 0.25 Remaining amount Comparative Example 7 NEP 2.0 DMSO 98.0 EDG 25 PA 0.0005 MEA 25 TMAH 45 TT 0.25 Remaining amount

[0057] (Unit: parts by weight)

[0058] - NEP: N-ethyl-2-pyrrolidone; -NEF: N-Ethylformamide

[0059] - DMSO: Dimethyl sulfoxide; - EDG: Diethylene glycol ethyl ether

[0060] -MDG: Diethylene glycol methyl ether; - PA: Potassium acetate

[0061] - MEA: Mono ethanol amine; - TMAH: Tetra Methyl Ammonium Hydroxide

[0062] - TT: Tolyl triazole; - Water: DI water

[0064] [Experimental Example: Evaluation of Physical Properties of Stripping Solution Composition]

[0065] For the evaluation of the removal of color resists and insulating films, a substrate having red, green, and blue color resists and an organic insulating film formed on it was used.

[0067] <Experimental Example 1: Evaluation of Removal Performance>

[0068] To verify the removal performance of color resist and organic insulating films, the stripping solution compositions prepared in the above examples and comparative examples were heated to 75°C, and a substrate was immersed in them to measure the time required for complete stripping. Subsequently, after removing the substrate from the stripping solution composition, it was rinsed with ultrapure water and dried with nitrogen gas, and then an optical microscope was used to check whether any color resist and organic insulating film remained within the pattern. The results were evaluated based on the following criteria and are shown in Table 2 below.

[0069] ◎ : If completely removed within 2 minutes

[0070] ○ : If completely removed within 4 minutes

[0071] △ : If completely removed within 6 minutes

[0072] X: If not removed within 6 minutes

[0074] <Experimental Example 2: Sublayer Damage Evaluation 1 - SEM>

[0075] While conducting the above removal performance evaluation, the damage (degree of corrosion) of the underlying film (inorganic insulating film) was confirmed using SEM. The evaluation was conducted based on the following criteria, and the results are shown in Table 2 and Figures 2 and 4 below.

[0076] ○ : No change in thickness up to 60 minutes

[0077] △ : Thickness change within 30 minutes

[0078] X: Thickness change within 5 minutes

[0080] <Experimental Example 3: Sublayer Damage Evaluation 2 - E / R>

[0081] The substrate was immersed for 60 minutes in the stripping solution composition of the above examples and comparative examples, which was heated to a temperature of 75°C. After removing the substrate from the stripping solution composition, rinsing it with ultrapure water and drying it with nitrogen gas, the underlying film (SiO₂) was examined using SEM. X The thickness of ) was measured. The E / R (etch rate) was calculated using the formula below, and the results are shown in Table 2 below.

[0082] - E / R(etch rate) = (Substrate thickness before immersion - Substrate thickness after immersion) / 60 min

[0084] <Experimental Example 4: Substrate Damage Evaluation 3 - Si Elution Amount>

[0085] A substrate was immersed for 60 minutes in the stripping solution composition of the above examples and comparative examples, which was heated to a temperature of 75°C. After removing the substrate, the amount of Si eluted into the stripping solution composition was measured using an elution evaluation measuring instrument (ICP-OES, Thermo Scientific), and the results are shown in Table 2 below.

[0086] Removal Performance Evaluation (Experimental Example 1) Subsurface membrane damage assessment 1 (SEM, Experimental Example 2) E / R (nm / min)(Experimental Example 3) Si leaching 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 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

[0087] Through Table 2 above, it can be seen that Examples 1 to 11, Examples 13 to 15, and Comparative Examples 1 to 7 all showed good results in the underlayer damage evaluation (Experimental Examples 2 to 4), but there is a significant difference between the Comparative Examples and the Examples in terms of the removal performance of color resist and organic insulating films. While Examples 1 to 11 and Examples 13 to 15 of the present invention all showed excellent removal performance of color resist and organic insulating films, it can be seen that Comparative Examples 1 to 7 showed poor removal performance of color resist and organic insulating films to the extent that they are difficult to use as a stripping solution composition. In particular, Examples 2 to 5, 10, 11, and 14 not only showed very excellent removal performance of color resist and organic insulating films but also outstanding results in the underlayer damage evaluation, indicating that the stripping solution composition according to one embodiment of the present invention has excellent removal performance of color resist and organic insulating films without causing damage to the underlayer material. In addition, it can be seen that Examples 10, 11, and 14, which contain 15% by weight or more of an alkylammonium compound relative to the total stripping solution composition, have superior removal performance compared to Example 13, which contains less than 15% by weight of an alkylammonium compound.

[0088] Figure 1 is an SEM image of a TFT substrate with a color resist (Color Layer) and an organic insulating film (Over Coat, OC) formed before peeling. Figure 2 (a) shows the metal wiring (Cu) and inorganic insulating film (SiO) of Figure 1. x ) and the color resist (Color layer) are laminated, and FIG. 2(b) is a magnified SEM image of the portion where the color resist and the organic insulating film (OC) are completely peeled off and the inorganic insulating film (SiO) is peeled off by the above method after peeling off the peeling solution composition of Example 1 prepared in the above preparation example. x ) is a photograph taken with an SEM of the intact remaining object.

[0089] Figure 4 shows an SEM image of a substrate peeled with a peeling solution composition prepared according to an embodiment of the present invention in the same manner, and the remaining inorganic insulating film (SiO₂) x The thickness of ) is also indicated. Fig. 3 is a substrate prior to the formation of the color resist (Color Layer) and organic insulating film layer (OC), showing metal wiring (Cu) and an inorganic insulating film (SiO). x This is an SEM image taken by magnifying the area where ) is formed, and the inorganic insulating film (SiO) x It can be confirmed that ) is formed at 522 nm. Referring to FIGS. 3 and 4, when the stripping solution 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 (SiO₂) x It can be confirmed that the thickness of ) is well maintained, and in the case of Examples 1 to 3, the inorganic insulating film (SiO) x It can be seen that the thickness of ) is 522 nm, and no damage occurred to the inorganic insulating film even after the peeling evaluation.

[0091] Although embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and it will be obvious to those skilled in the art that various modifications and variations are possible within the scope of the technical concept of the present invention as described in the claims.

Claims

Claim 1 A stripping solution composition comprising: a solvent comprising a first aprotic polar solvent containing a nitrogen atom (N) and a second aprotic polar solvent; a glycol ether compound; an inorganic base or its salt compound; a chain-type amine compound; and an alkylammonium compound; wherein the molecular weights of the first aprotic polar solvent and the second aprotic polar solvent are different, the weight ratio of the first aprotic polar solvent to the second aprotic polar solvent is 1:1 to 1:40, and the alkylammonium compound comprises 15 to 29 weight% based on the total weight of the stripping solution composition. Claim 2 A stripping solution composition according to claim 1, wherein the difference in molecular weight between the first nonprotic polar solvent and the second nonprotic polar solvent is 5 to 65 g / mol. Claim 3 A stripping solution composition according to claim 1, wherein the first non-protic polar solvent comprises one or more selected from N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethylformamide, N-methylformamide, and pyrrolidone. Claim 4 A stripping solution composition according to claim 1, wherein the second aprotic polar solvent has a molecular weight of 70 to 140 g / mol. Claim 5 A stripping solution composition according to claim 1, wherein the second non-protic polar solvent comprises one or more selected from dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, and sulfolane. Claim 6 A stripping solution composition according to claim 1, wherein the first non-protic polar solvent is N-ethyl-2-pyrrolidone. Claim 7 A stripping solution composition according to claim 1, comprising 10 to 100 parts by weight of the glycol ether compound per 100 parts by weight of the solvent. Claim 8 A stripping solution composition according to claim 1, wherein the glycol ether compound comprises one or more selected from 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 glycol dimethyl ether, triethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether. Claim 9 A stripping solution composition according to claim 1, comprising 0.001 to 0.05 parts by weight of the inorganic base or its salt compound per 100 parts by weight of the solvent. Claim 10 A stripping solution composition according to claim 1, wherein the inorganic base or its salt compound comprises one or more selected from potassium acetate, potassium nitrate, potassium carbonate, potassium pyrophosphate, potassium oleate, potassium benzoate, potassium laurate, potassium tert-butoxide, potassium sulfate, potassium sorbate, potassium aminobenzoate, potassium disulfate, potassium cyanate, potassium sulfide, potassium xylene sulfonate, sodium xylene sulfonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium nitrate, sodium sulfate, sodium acetate, sodium silicate, and potassium silicate. Claim 11 A stripping solution composition according to claim 1, comprising 20 to 145 parts by weight of the chain-type amine compound and the alkylammonium compound per 100 parts by weight of the solvent. Claim 12 delete Claim 13 A stripping solution composition according to claim 1, comprising the inorganic base or its salt compound and the alkylammonium compound in a weight ratio of 1:1,000 to 1:20,000. Claim 14 In claim 1, the chain-type amine compound is aminoethanol, diethanolamine, N-methylethanolamine, triethanolamine, glycolamine, diglycolamine, hydroxylamine, methylamine, ethylamine, isopropylamine, monoisopropylamine, diethylamine, diisopropylamine, dibutylamine, ethylenediamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, monoisopropanolamine, aminoethoxyethanol, propoxyethylamine, isopropoxypropylamine, methoxyethoxypropylamine, aminoethylethanol, methoxyethylamine, methoxypropylamine, ethoxypropylamine, 3-methoxypropylamine, 3-ethoxypropylamine, n-methylmethanolamine, monomethanolamine, monoethanolamine, diethylaminopropylamine, bis-2-methoxyethylamine, propylenediamine, 1,3-propanediamine, A stripping solution composition comprising one or more selected from 1,2-propylenediamine, diethylenetriamine, dihexyllentriaamine, triethylenetetramine, tetraethylenepentaamine, oxolan-2-yl-methaneamine, (oxolan-2-yl-methyl)butan-1-amine, and methyloxolan-2-yl-methaneamine. Claim 15 A stripping solution composition according to claim 1, wherein the alkylammonium compound comprises one or more selected from tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. Claim 16 A stripping solution composition comprising a corrosion inhibitor, wherein, in claim 1, the stripping solution composition further comprises a corrosion inhibitor. Claim 17 A stripping solution composition according to claim 16, comprising 0.2 to 25 parts by weight of the corrosion inhibitor per 100 parts by weight of the solvent. Claim 18 In claim 16, the above-mentioned corrosion inhibitor comprises one or more selected from toltriazole, benzotriazole, mercaptomailimidazole, catechol-based compounds and alkyl gallate compounds, forming a stripping solution composition. Claim 19 A stripping solution composition for a silicon oxide film comprising: a glycol ether compound; an inorganic base or its salt compound; a chain-type amine compound; an alkylammonium compound; and a non-protic solvent; wherein, based on 100 parts by weight of the solvent, the inorganic base or its salt compound is contained in an amount of 0.001 to 0.05 parts by weight.

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