KR20090019299A - A color resist remover composition for tft-lcd preparation - Google Patents

Abstract

A colored resist stripper composition is provided to allow a color filter substrate to be reused by removing a resist pattern and overcovering material within a short time. A colored resist stripper composition comprises 1-20 wt% of a hydroxide compound selected from an inorganic alkali hydroxide, ammonium hydroxide, a C1-C4 alkyl ammonium hydroxide, and a phenylalkyl ammonium hydroxide having a C1-C4 alkyl group; 1-70 wt% of at least one compound selected from an alkylene glycol ether and an alkylene glycol having a C1-C4 alkyl group; 0.5-10 wt% of hydroxylamine; 0.5-50 wt% of an alkoxyalkyl amine; and the balance of water.

Description

Color resist stripper composition for TFT LCD {A COLOR RESIST REMOVER COMPOSITION FOR TFT-LCD PREPARATION}

The present invention relates to a color resist stripper composition for TFT-LCD, and more particularly, to remove color resist and overcoat including color resist of a defective substrate generated during a color filter process, and to have a black mask ( The present invention relates to a color resist stripper composition for TFT LCD that can reuse a black resist removed on a black mask or a glass substrate.

The color filter substrate is composed of a black matrix, an overcoat as a protective film, and a common electrode for applying a voltage to the liquid crystal cell, which serve to block the red cyan pattern of the color filter and leakage light between each pixel and to improve contrast.

The process of manufacturing the color filter is as follows.

First, Cr / CrOx or an organic material, which is used as a black matrix material, is coated on a glass substrate, and a pattern is formed on the glass substrate, depending on the use. After forming a black mask pattern, a color resist pattern for realizing color is formed by a photolithography technique. The color resist is coated on a glass substrate and exposed to light to cure the color resist by photopolymerization. After the exposure is completed, the color resist is removed by undeveloped portions, and undergoes a calcination process.

The color resist is produced by a pigment dispersion method, a dyeing method, an electrodeposition method, etc. Among these, the pigment dispersion method is mainly used. Generally, organic pigments that implement color are dispersed in photopolymerization initiators, monomers, binders, and the like, which are photosensitive compositions such as photoresists. The photopolymerization initiator is a highly sensitive compound that receives light to generate radicals, and the monomers are bound to a polymer form after the polymerization reaction is initiated by the radicals, thereby becoming insoluble in the developing solvent. The binder protects the monomer in the liquid state from the developer at room temperature, and determines the stability of the pigment dispersion and the reliability of heat resistance, light resistance, chemical resistance, etc. of the red cyan pattern.

Defects generated in the current color filter process Once the color resist of the color filter substrate is cured, it is almost impossible to repair by removing only the wrong part of the pattern. Also, since the solvent that can remove the color resist is poor, the color filter is repaired. Most of them are disposed of immediately without rework.

The color resist has the characteristics of a negative resist. In general, the negative resist has a strong peeling performance because it is difficult to remove the peel compared with the positive type.

For this reason, conventionally, RIE (reactive ion etching) using an inorganic or organic stripping solution and plasma was used. However, in the case of the organic peeling solution, the treatment time is longer than that of the inorganic peeling solution, and there is a difficulty in peeling the overcoating material which rises over the color filter. In the case of the inorganic stripping solution, the stability is lower than that of the organic stripping solution, and the inorganic salts are precipitated in the liquid when used for a long time. As an example of an organic peeling liquid, it is disclosed in Unexamined-Japanese-Patent No. 51-72503, and a stripper is disclosed in European Patent Publication No. 0119337.

In addition, in order to solve the difficulty of peeling in the organic stripping solution, some patents have been devised to improve the peeling performance of the overcoating material by using an inorganic salt that is well dissolved in an organic solvent, but it does not reach the peeling time of the inorganic stripping solution. There was a downside. For example, the organic peeling solution is disclosed in Korean Patent Laid-Open Publication No. 2005-0006980.

In addition, as a method using reactive ion etching (RIE) using plasma, etching of cured color resists that cannot be removed by general wet etching is continuously removed using O ₂ -RIE and SF ₆ -RIE. Patent 5,756,239 is disclosed. In addition, for a cured color resist using polyester, polyamide, and noblock resin as the absorbent layer and a mixture of polysilane, polysiloxane, organosilicon compound, silica, and silicon nitride as the barrier layer, the absorbent layer uses oxygen. A method using RIE using sulfur hexafluoride or nitrogen trifluoride as a barrier layer and removing the barrier layer is disclosed in US Pat. No. 5,059,500. However, the etching of the color filter using the plasma requires high vacuum, high energy, difficult to set the process conditions, difficult to use in a large area, and has the disadvantages such as expensive equipment.

As such, the conventional color resist removal method is difficult to stably remove a large amount of color resist and overcoating material, there is a problem that the safety of workers, or productivity or yield is low.

Therefore, there is a demand for a method of removing a large amount of color resist through a safe method.

An object of the present invention is to provide a stripper composition for safely removing a large amount of color resist and overcoat used during the color filter manufacturing process of the TFT LCD in order to solve the above problems.

It is another object of the present invention to provide a color resist stripper composition which makes it possible to reuse color resist which has been discarded after being removed.

In order to achieve the above object, the present invention (a) inorganic alkali hydroxide, ammonium hydroxide, alkyl ammonium hydroxide having an alkyl group having 1 to 4 carbon atoms and phenylalkyl ammonium hydride having an alkyl group having 1 to 4 carbon atoms 1 to 20% by weight of a hydroxide compound selected from the group consisting of a hydroxide; (b) 1 to 70% by weight of at least one compound selected from the group consisting of alkylene glycol ethers and alkylene glycols having alkyl groups of 1 to 4 carbon atoms; (c) 0.5 to 10 weight percent hydroxylamine; (d) 0.5 to 50 weight percent of alkoxyalkylamines; And (e) a residual amount of water.

The composition comprises 1 to 30% by weight of a dialkylene glycol dialkyl ether or alkylene glycol dialkyl ether having an alkyl group having 1 to 4 carbon atoms, 0.05 to 10% by weight of an inorganic salt compound, and 1 to 55% by weight of a polar solvent. It may further comprise at least one component selected from the group.

Hereinafter, the present invention will be described in detail.

The present invention has been conducted to effectively remove color resists and overcoats and reuse color filter substrates, which have been mostly discarded, as a result of the present invention, and it is possible to easily remove color resists and overcoats using a stripper composition having a specific composition. To discover and complete the present invention.

The hydroxide compound used in the stripper composition of the present invention is inorganic alkali hydroxide, ammonium hydroxide, alkyl ammonium hydroxide having an alkyl group having 1 to 4 carbon atoms and phenylalkyl having an alkyl group having 1 to 4 carbon atoms. Any one selected from the group consisting of ammonium hydroxide can be used. Since the color filter process is not greatly influenced by the residual metal, inorganic alkali hydroxides can also be used. The amount of the hydroxide compound is preferably used in an amount of 1 to 20% by weight based on the total composition. When the content is less than 1% by weight, the color resist is completely penetrated into the polymer component constituting the color resist. It is difficult to remove, and if it exceeds 20% by weight, the component ratio of other solvents will be lowered, which will adversely affect the removal time. In addition, since alkyl ammonium hydroxide and phenylalkyl ammonium hydroxide are not stable, it is preferable to use it in the state dissolved in water.

The inorganic alkali hydroxide is preferably selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide and mixtures thereof. 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. As the phenylalkyl ammonium hydroxide having an alkyl group having 1 to 4 carbon atoms, it is preferable to use benzyltrimethyl ammonium hydroxide.

The at least one compound selected from the group consisting of alkyleneglycol ether and alkylene glycol having an alkyl group having 1 to 4 carbon atoms is excellent in the ability to reduce solubility and surface tension in color resists. It lowers the surface tension acting between the floating color resist and the glass surface so that the color resist can be easily stripped, and also dissolves the binder or polymer of the stripped color resist. The amount of the alkylene glycol ether is preferably 1 to 70% by weight based on the total composition, wherein if the content is less than 1% by weight, it is difficult to completely remove the color resist. Apart from this, there is a disadvantage in that the performance of dissolving an acrylic resin or a polyimide resin, which is an overcoating material, is poor. 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 monomethylether), diethyleneglycol monomethylether (triethyleneglycol monomethylether), triethyleneglycol monomethylether (triethyleneglycol monomethylether), ethyleneglycol monoethylether (ethyleneglycol monoethylether), ethylene glycol (ethylene glycol), diethylene glycol (diethylene glycol ), Triethylene glycol, hexylene glycol, glycerol (glycerol) and mixtures thereof are preferably used.

The hydroxylamine (hydroxylamine) penetrates into the polymer constituting the color resist and separates the color resist from the organic substrate, and serves to decompose the pigment component. That is, in the case of such hydroxyl amines, when used together with water-soluble amines, it is easy to generate hydroxyl radicals or aluminum radicals, and thus, it is possible to shorten the process time by slowly decomposing and oxidizing pigment components that are not easily dissolved. . The hydroxylamine is used in an amount of 0.5 to 10% by weight based on the total composition. Its content is less than 0.5% by weight and can not maintain the initial performance of the chemical solution has the disadvantage of shortening the service life, and if more than 10% by weight can no longer expect the effect of shortening the process time.

The alkoxyalkylamine penetrates into the polymer constituting the color resist and functions to separate the color resist from the glass substrate. The content of the palkoxyalkylamine is preferably 0.5 to 50% by weight based on the total composition. If the content of the alkoxyalkylamine is less than 0.5% by weight, the penetrating power to the color resist is weakened, so that the color resist may not be completely removed and the inorganic alkali hydroxide and layer separation occur. There is a problem that does not improve the performance by inhibiting the activity of the ion. The alkoxyalkylamine may be used having an alkoxy and alkyl group having 1 to 4 carbon atoms, for example, ethoxypropyl amine, methoxypropyl amine, methoxyethyl amine and It may be selected from the group consisting of a mixture thereof.

Further, the water used in the present invention is preferably pure water filtered through an ion exchange resin, more preferably using ultrapure water having a specific resistance of 18 (MΩ) or more. The amount of water used may be included as a residual amount of the stripping solution composition, preferably 4 to 49% by weight based on the total composition. At this time, when the content of water is less than 4% by weight, the composition of the composition is changed at the process temperature, and inorganic alkali ions are precipitated, which causes a problem of lowering the pot life of the peeling liquid composition for the color filter. If exceeded, there is a problem that the loss of the peeling liquid composition for the color filter increases due to the evaporation of water at the process temperature.

In addition, the composition of the present invention is water-soluble except 1 to 30% by weight of a dialkylene glycol dialkyl ether or alkylene glycol dialkyl ether having an alkyl group having 1 to 4 carbon atoms, in order to further improve the resist removal function It may further include at least one component selected from the group consisting of 0.5 to 50% by weight of the amine, 0.05 to 10% by weight of the inorganic salt compound and 1 to 55% by weight of the polar solvent.

The dialkyleneglycol dialkylether and alkyleneglycol alkylether having an alkyl group having 1 to 4 carbon atoms are similar to an acrylic resin or an imide resin having a solubility parameter of an overcoating material. Thus, the overcoating polymer material peeled from the glass substrate in the chemical solution serves to stably dissolve. The dialkylene glycol dialkyl ether or alkylene glycol dialkyl ether is diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol diflofil ether, ethylene glycol dimethyl ether, ethylene Glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol dipropylene glycol and mixtures thereof may be used.

The amount of the dialkylene glycol dialkyl ether or alkylene glycol dialkyl ether is preferably 1 to 30% by weight based on the total composition, wherein the content is less than 1% by weight to peel off the color resist and overcoating material If it exceeds 30% by weight, the activity of the inorganic alkali metal ion is inhibited, and precipitation is not expected to improve performance.

The water-soluble amine may be selected from the group consisting of diethylamino propylamine, bis 2-methoxyethyl), monoethanolamine, monomethanolamine and mixtures thereof. Can be.

The inorganic salt used in the present invention can be used in conjunction with the hydroxide compound can be expected synergistic effect of the resist removal force. In particular, when inorganic salts are used in combination with alkyl ammonium hydroxide and phenylalkyl ammonium hydroxide, it is possible to increase the penetration and swelling properties of acrylic resins and polyimide resins, which are overcoating materials, thereby significantly reducing the removal time. have. The amount of the inorganic salt used is preferably 0.05 to 10% by weight based on the total composition, when the content is less than 0.05% by weight can not be expected to increase the removal effect on the overcoating material, when the content exceeds 10% by weight of the stripper composition The highest possible residual amount of water can also exceed the saturation limit and cause precipitation quickly, causing equipment problems. Inorganic salts used in the present invention are potassium acetate, potassium nitrate, potassium carbonate, potassium pyrophosphate, potassium oleate, potassium benzoate (potassium oleate) potassium benzoate, potassium laurate, potassium tert-butoxide, potassium sulfate, potassium sorbate, potassium aminobenzoate, potassium dibenzoate Preference is given to using those selected from the group consisting of sulfate disulfate, potassium cyanate, potassium sulfide, sodium xylenesulfonate and mixtures thereof.

In addition, the polar solvent used in the present invention is excellent in the penetration and dissolving power to the color resist to penetrate between the polymer of the color resist causing swelling phenomenon. The amount of the polar solvent is preferably 1 to 55% by weight based on the total composition, in which the content is less than 1% by weight, and the time is greatly increased to completely remove the color resist, and when the content is more than 55% by weight, the inorganic alkali hydroxide is used. The solubility with a compound falls and performance improvement is not expected. 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.

As described above, the present invention identifies the above-mentioned hydroxide compound, alkylene glycol ether, hydroxylamine, water-soluble amine containing alkoxyalkylamine, dialkylene glycol dialkyl ether or alkylene glycol dialkyl ether and water. By using the content, and further using an inorganic salt compound and a polar solvent, the color resist and the overcoating material can be easily removed in a short time by the synergistic effect of each component, in particular easy to remove the color resist pattern The color filter substrate, which has been mostly discarded, can be reused. In the present invention, the preferred composition is a composition comprising a hydroxide compound, alkylene glycol ether, hydroxylamine, alkoxy alkyl amine, dialkylene glycol ether or alkylene glycol dialkyl ether, inorganic salt, polar solvent and water Can be.

As described above, the color resist stripper composition according to the present invention can easily remove the color resist and the overcoating material within a short time, and in the subsequent rinsing process, it is possible to remove organic solvents such as isopropyl alcohol and dimethyl sulfoxide. There is an advantage that it can be rinsed with water only without the need to use, and in particular, the resist pattern can be removed, and the color filter substrate can be reused.

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.

[Examples and Comparative Examples]

Each component was mixed in 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.

TABLE 1

TABLE 2

Color resist stripper composition (% by weight) Comparative example Hydroxide Alkylene glycol ether Dialkylene glycol dialkyl ether Hydroxylamine Water soluble amine Polar solvent Inorganic salt water One TMAH 6 MDG 50 HDA 2 MEA 10 32 2 TMAH 6 HDA 2 DMSO 60 32 3 TMAH 6 DMDG 60 PA 0.2 33.8

KOH: Potassium Hydroxide

TMAH: tetramethylammonium hydroxide

MTG: triethylene glycol monomethyl ether

MDG: diethylene glycol monomethyl ether

MG: ethylene glycol methyl ether

EG: ethylene glycol

DMDG: diethylene glycol dimethyl ether (diglyme)

EPA: ethoxy propyl amine, MEA: mono ethanol amine

HDA: hydroxylamine

DMSO: dimethyl sulfoxide, NMP: n-methyl pyrrolidone

PA: potassium acetate, PB: potassium benzoate, PN: potassium nitrate,

PC: potassium carbonate, PBu: potassium butoxide, PS: potassium sorbate

PAB: Potassium Amino Benzoate

EGDE: ethylene glycol dimethyl ether

Experimental Example

The performance of the color resist stripper composition prepared in Example 1-24 and Comparative Example 1-3 was evaluated using the color filter substrate of the following process, and the color resist removal test was carried out as follows.

Specimen Manufacturing

Color filter patterns were made on LCD corning glass with Cr / CrOx deposited on the bottom, and color resist was applied using the following photographic process in the order of red, green, and blue. A universally used color resist composition (trade name: DCR-725S available from Dongjin Semichem Co., Ltd.) was spin coated to apply a final film thickness of 1.7 μm. Subsequently, the resist film was pre-baked at 90 ° C. for 120 seconds on a hot plate. Subsequently, after exposing and developing for 60 seconds at room temperature with 1% potassium hydroxide (KOH) developer, the specimen in which the said pattern was formed was hard-baked for 20 minutes at 220 degreeC.

Thus, the polyimide or polyacryl, which is used as an overcoating material, was coated on the finished sample of the color filter by spin coating to apply a final film thickness of 3 μm. 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 patterned specimen was hard baked at 220 ° C. for 20 minutes.

color Resist  Removal test

The prepared specimen was immersed in a stripper composition for removing color resist and removing overcoat material at a temperature of 70 ° C. to measure a time for completely peeling the color resist and overcoat from the substrate. Subsequently, the specimen was removed from the color resist stripper composition, 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. Whether or not was observed. Table 3 below shows the time when the overcoating material and the color resist were completely peeled off and no residue was found.

TABLE 3

number Removal time Example One 3 minutes 30 seconds 2 3 minutes 30 seconds 3 4 minutes 4 4 minutes 5 3 minutes 30 seconds 6 3 minutes 7 4 minutes 8 6 minutes 9 6 minutes 10 6 minutes 11 6 minutes 12 6 minutes 13 7 minutes 14 6 minutes 15 7 minutes 16 7 minutes 17 7 minutes 18 7 minutes 19 6 minutes 20 7 minutes 21 8 minutes 22 7 minutes 23 7 minutes 24 7 minutes Comparative example One 60 minutes 2 30 minutes 3 15 minutes

As can be seen in Table 3, the embodiment of the present application can be seen that the color resist removal performance is very excellent compared to the comparative example, diethylene glycol dimethyl ether and ethoxy propyl amine and the like individually affect the removal performance respectively You can see how crazy. In particular, it can be seen that the performance can be improved by 5 to 10 times in the case where the potassium salt, diethylene glycol dimethyl ether, ethoxy propyl amine, and the like are added.

On the other hand, when the potassium salts of Comparative Examples 1 and 2 were not added, the removal performance could hardly be expected. In addition, in the case of Comparative Example 3 also does not contain the amine and alkylene glycol ether compound of the present application it can be seen that the peeling performance is poor.

Claims (10)

(a) a hydroxide selected from the group consisting of inorganic alkali hydroxides, ammonium hydroxides, alkyl ammonium hydroxides having alkyl groups of 1 to 4 carbon atoms and phenylalkyl ammonium hydroxides having alkyl groups of 1 to 4 carbon atoms 1 to 20% by weight of side compound; (b) 1 to 70% by weight of at least one compound selected from the group consisting of alkylene glycol ethers and alkylene glycols having alkyl groups of 1 to 4 carbon atoms; (c) 0.5 to 10 weight percent hydroxylamine; (d) 0.5-50% by weight of alkoxyalkylamine; And (e) remaining water A color resist stripper composition, comprising a. The method of claim 1, The inorganic alkali hydroxide is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide and mixtures thereof. The method of claim 1, The alkyl ammonium hydroxide having an alkyl group having 1 to 4 carbon atoms is composed of tetraethyl ammonium hydroxide, tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, trimethylbenzyl ammonium hydroxide, and mixtures thereof. The color resist stripper composition is selected from the group. The method of claim 1, The alkylene glycol ether or alkylene glycol 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 monomethyl ether And triethylene glycol monomethyl ether, ethylene glycol monoethyl glycol, ethylene glycol, diethylene glycol, triethylene glycol, hexylene glycol, glycerol, and mixtures thereof. The method of claim 1, The alkoxyalkylamine is selected from the group consisting of ethoxypropyl amine, methoxy propyl amine, methoxy ethylamine and mixtures thereof. According to claim 1, wherein the composition is 1 to 30% by weight of dialkylene glycol dialkyl ether or alkylene glycol dialkyl ether having an alkyl group having 1 to 4 carbon atoms, 0.5 to 50% by weight of water-soluble amine excluding alkoxyalkylamine , 0.05 to 10% by weight of the inorganic salt compound and 1 to 55% by weight of the polar solvent further comprises at least one component selected from the group, color resist stripper composition. The method of claim 6, The dialkylene glycol dialkyl ether having an alkyl group of 1 to 4 carbon atoms is a dialkylene glycol dialkyl ether is dimethylene glycol dimethyl ether, diethylene glycol diethyl ether, dibutylene glycol dibutyl ether, diethylene glycol dimethyl A color resist stripper composition, characterized in that it is selected from the group consisting of ether (diethyleneglycol dimethylether), diethylene glycol diethyl ether, dipropylene glycol dimethyl ether (dipropyleneglycol dimethylether) and mixtures thereof. 7. The method of claim 6 wherein the water soluble amine is selected from the group consisting of n-methylmethanolamine, monomethanolamine, ethylenediamine, diethylamino propyl amine, bis 2-methoxyethylamine and mixtures thereof. Color resist stripper composition. The method of claim 6, The inorganic salts include potassium acetate, potassium nitrate, potassium carbonate, potassium pyrophosphate, potassium oleate, potassium benzoate, potassium laurate, potassium tert-butoxide, potassium sulfate, potassium sorbate, potassium amino benzoate Color resist stripper composition, characterized in that it is selected from the group consisting of potassium disulfate, potassium cyanate, potassium sulfide, potassium xylene sulfonate, and sodium xylene sulfonate. The method of claim 6, The polar solvent is selected from the group consisting of dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, sulfolane, n-methylpyrrolidone, pyrrolidone, n-ethylpyrrolidone and mixtures thereof. The color resist stripper composition to be used.