TWI408517B - A color resist remover composition for tft-lcd preparation - Google Patents

Abstract

The invention relates to a color composition of a resist and a remover for removing a color resist and a coating from a thin film transistor LCD in order to reusing bad substrates generated during a manufacturing process of a TFT-LCD color screen, in particular relates to a color composition of a resist and a remover comprising: (a) 1-50 wt.% hydroxid selected from inorganic base hydroxid, alkyl group ammonium hydroxide and phenyl alkyl group ammonium hydroxide, wherein the alkyl group ammonium hydroxide contains alkyl group of C1-C4; (b) 5-30 wt.% polar sulphide; (c) 5-35 wt.% alkylene glycol ether having alkyl group of C1-C4; (d) 2-30 wt.% alkylene glycol dialkyl ether having alkyl group of C1-C4; (e) 2-30 wt.% water solubility amine compound; (f) and the remainder water.

Description

Color resist stripping liquid composition for thin film transistor liquid crystal display

The present invention relates to a stripping liquid composition for a color resist liquid crystal display (hereinafter referred to as "TFT-LCD"), and more particularly to a color for removing a defective substrate generated in a color filter process. The resist and the overcoat containing the color resist enable it to be used as a TFT-LCD color resist stripper composition for recycling a black mask or a glass substrate.

The color filter substrate is composed of a red-green-blue pattern, a black matrix, a protective film (ie, a film), and a common electrode. Among them, the black matrix is used to prevent light leakage between the pixels, the contrast is improved, and the common electrode is used to apply a voltage to the liquid crystal cell.

The manufacturing process of the color filter is as follows. First, chromium/chromium oxide (Cr/CrOx) or an organic material as a black matrix material is coated on a glass substrate according to the use to form a pattern. After the black film pattern is formed, a color resist pattern is formed by photolithography in order to develop color. A color resist is applied on a glass substrate and exposed to light to cure the color resist by photopolymerization. After the exposure step, the unexposed portion of the color resist is removed by a developing step, and then the firing step is performed.

The color resist can be produced by a method such as a pigment dispersion method, a dyeing method, or an electrodepersition method, and a commonly used method is a pigment dispersion method. Among them, an organic pigment for realizing color is usually dispersed in a photopolymerization initiator such as a photoresist, a monomer, or a binder. The photopolymerization initiator is a highly photosensitive compound which generates a radical after receiving light, and the monomer is combined with a polymer form by a radical polymerization reaction to form a form which is insoluble in a developing solvent. The adhesive protects the liquid monomer at a normal temperature from being easily dissolved in the developer, and determines the stability of the pigment dispersion and the reliability of heat resistance, light resistance, chemical resistance, and the like of the red, green, and blue patterns.

At present, in the color filter substrate produced by the color filter, the color resist is hardly removed once it is hardened, so that the erroneous portion in the pattern cannot be corrected, and there is almost no color resist that can be removed at present. The solvent of the agent, so most of the bad color filters are not subjected to the re-treatment process such as correction, and the disposal is directly performed.

The above-described color resist has the characteristics of a negative resist. Generally, a negative resist is more difficult to peel off than a positive resist, and therefore a negative resist requires strong peeling performance.

Therefore, a reactive ion etching method (RIE) using an inorganic stripping solution and a plasma has been conventionally used. However, when the above inorganic stripping solution is used, if a mixture of sulfuric acid, nitric acid, fuming sulfuric acid, nitric acid, and hydrogen peroxide is heated to 120 ° C or higher, not only poses a threat to the safety of the operator but also increases due to heating. The danger of fire, so you must be careful when using it. For example, a mixture of an alkylbenzenesulfonic acid and a non-halogenated aromatic hydrocarbon solvent having a boiling point of 150 ° C or higher is disclosed in Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. A mixture of aromatic aromatic sulfonic acid and non-halogenated aromatic hydrocarbon solvent; European Patent No. 0119337 discloses a stripping agent for adding a polar or non-polar organic solvent to an organic sulfonic acid and 1,2-dihydroxybenzene.

In addition, U.S. Patent No. 5,756,239 discloses a reactive ion etching (RIE) method using plasma by continuous use of oxygen-reactive ion etching (O ₂ -RIE), sulfur hexafluoride-reactive ions. Etching (SF ₆ -RIE) to remove hardened color resists that cannot be removed by conventional wet etching; and U.S. Patent No. 5,059,500 discloses a reactive ion etching (RIE) method using plasma, which is used for Polyester, polyamine, novolac resin to form an absorbing layer, a hardened color resist formed of a mixture of polydecane, polyoxane, organic cerium compound, cerium oxide or cerium nitride to form a barrier layer, using oxygen The plasma removes the absorber layer and removes the barrier layer by using sulfur hexafluoride or nitrogen trichloride. However, the above-described color filter etching method using plasma requires a high vacuum environment and high energy, is difficult to control the process conditions, is difficult to use on a large-area color filter, and is expensive in equipment.

As described above, in the conventional color resist peeling method, there is a problem that it is difficult to stably remove a large amount of color resist, and the safety of the operator is threatened, and the production efficiency or the yield is lowered.

Therefore, there is currently a need for a method to remove a large amount of color resist in a safe manner.

In view of the above problems, it is an object of the present invention to provide a peeling liquid composition capable of largely removing a color resist and a coating used in a process of a TFT-LCD color filter in a safe manner.

In order to achieve the above object, the present invention provides a color resist stripping liquid composition comprising: a) 1-50 wt% selected from the group consisting of an alkali hydroxide, an alkyl ammonium hydroxide ( Alkyl ammonium hydroxide) and a hydroxide of an alkyl phenyl ammonium hydroxide comprising a C ₁ -C ₄ alkyl group; b) 5-30 wt% of a polar sulfide ; c) 5-35 wt% of an alkylene glycol ether comprising a C ₁ -C ₄ alkyl group; d) 2-30 wt% of an alkene group An alkylene glycol dialkyl ether comprising a C ₁ -C ₄ alkyl group; e) 2-30 wt% of a water soluble amine compound; f) Residual amount of water.

The color resist stripping liquid composition of the present invention can easily remove the color resist in a short time, and in the subsequent rinsing step, it is not necessary to use an organic solvent such as isopropyl alcohol or dimethyl hydrazine, and only pure The water can be washed.

Hereinafter, the present invention will be described in detail.

In order to develop a more effective peeling method for color resists and coatings, it has been found that a color filter substrate which has been largely discarded in the past can be recycled and used as a peeling liquid having a specific composition. The composition is easy to remove the color resist and the coating, thereby completing the invention.

The a) hydroxide used in the stripping liquid composition of the present invention is preferably selected from the group consisting of inorganic alkali hydroxides, alkyl ammonium hydroxides and phenylalkyl ammonium hydroxides, wherein the alkyl ammonium hydroxides comprise C _1- C ₄ alkyl group. In the process of the color filter, since the residual metal is not greatly affected, an inorganic alkali hydroxide can also be used. The above hydroxide may preferably contain 1 to 50% by weight based on the total amount of the above composition, and if it is less than 1% by weight, the penetration of the polymer component constituting the color resist is lowered, thereby It is difficult to completely remove the color resist; and if the content exceeds 50 wt%, the swelling phenomenon is deepened, and the inorganic base is precipitated to change the composition of the stripping liquid, thereby causing delamination under specific components to produce peeling properties. Negative impact. Further, since the properties of the alkyl ammonium hydroxide and the alkyl allyl ammonium hydroxide are unstable, it is preferably used after being dissolved in water.

The above a) inorganic alkali hydroxide is preferably selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, and mixtures thereof. The above alkyl ammonium hydroxide containing a C ₁ -C ₄ alkyl group is preferably selected from the group consisting of tetraethylammonium hydroxide, tetramethylammonium hydroxide, and tetrabutylammonium. Hydroxide) and mixtures thereof. Further, as the phenylalkylammonium hydroxide, Benzyltrimethylammonium hydroxide is preferably used.

Further, in the present invention, the above b) polar sulfide has excellent penetration and dissolving power to the color resist, and therefore can penetrate between the polymers of the color resist to cause swelling. It is preferred to use 5-30 wt% of polar sulfide based on the total amount of the composition. At this time, if the content is less than 5 wt%, it is difficult to remove all of the color resist; and if the content is more than 30 wt%, the fusion with the inorganic alkali hydroxide is lowered, so that it is difficult to expect peeling property. Improvement. The polar sulfide of the present invention is preferably selected from the group consisting of Dimethylsulfoxide, ethylsulfoxide, dipropyl sulfoxide, Sulfolane, and mixtures thereof.

The above c) olefin-based glycol ether containing a C ₁ -C ₄ alkyl group has excellent dissolving power for a color resist and has excellent surface tension reducing ability, which can reduce suspended color resist and glass substrate The tension between the surfaces causes the color resist to be easily peeled off, and dissolves the components such as the binder or the polymer in the above-mentioned peeled color resist. It is preferred to use 5 to 35 wt% of the above olefin-based glycol ether based on the total amount of the composition, and at this time, if the content is less than 5 wt%, it is difficult to completely remove the color resist; and if the content is higher than 35 When wt%, the activity of the inorganic alkali metal ion is hindered, and it is difficult to expect an improvement in peeling performance.

The olefin-based glycol ether used in the present invention is preferably selected from the group consisting of ethylene glycol monobutyl Ether, diethylene glycol monobutyl Ether, and triethylene glycol monobutyl ether ( Triethylene glycol Monobutyl Ether), ethylene glycol monomethyl Ether, diethylene glycol Monomethyl Ether, triethylene glycol monomethyl Ether, ethylene glycol ether Glycol Monoethylether) and mixtures thereof.

The above d) alkylene glycol dialkyl ether containing a C ₁ -C ₄ alkyl group has excellent solubility to a color resist, and thus is permeable to a polymer chain of a color resist. In the middle, it functions as a chain scission and a melting, so that the color resist is easily peeled off, and a component such as a binder or a polymer in the peeled color resist is dissolved. It is preferred to use 2 to 30% by weight of the above-mentioned olefinic ethylene glycol dialkyl ether, preferably 5 to 30% by weight, based on the total amount of the composition. At this time, if the content is less than 2% by weight, it is difficult to completely remove the color resist, and if the content exceeds 30% by weight, the activity of the inorganic alkali metal ion is hindered, and it is difficult to expect an improvement in the peeling property. The olefinic ethylene glycol dialkyl ether in the present invention is preferably selected from the group consisting of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether ( Triethylene glycol dimethyl ether), diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and mixtures thereof.

The above e) water-soluble amine compound can be permeable to the polymer constituting the color resist, and the color resist is peeled off from the glass substrate. It is preferred to use 2-30 wt% of the above water-soluble amine compound, preferably 5 to 30 wt%, based on the total amount of the composition. At this time, if the content of the water-soluble amine compound is less than 2% by weight, the penetration of the color resist is lowered, so that it is difficult to completely remove the color resist, thereby causing delamination between the inorganic alkali hydroxides. Phenomenon; if the content exceeds 30% by weight, the activity of the inorganic alkali metal ion is hindered, and it is difficult to expect an improvement in the peeling property. The water-soluble amine compound is preferably selected from the group consisting of n-methyl methanol amine, mono methanol amine, ethylene diamine, and hydroxylolamine.

Further, in the f) water in the present invention, it is preferred to use pure water filtered by an ion exchange resin, and it is preferable to use ultrapure water having a specific resistance equal to or higher than 18 MΩ. In the composition of the present invention, a residual amount of the above pure water may be contained, and based on the total amount of the composition, it is preferred to use 4-49 wt% of pure water. At this time, if the pure water content is less than 4 wt%, the composition of the composition changes at the process temperature, thereby precipitating the inorganic alkali ions, thereby lowering the activation period of the composition for the color filter stripping solution. Pot stability; and if its content exceeds 49 wt%, the loss of the stripping solution composition will increase due to evaporation of water under engineering temperature conditions.

The stripping liquid composition of the present invention can easily remove the color resist and the coating layer as compared with the prior art, and can minimize corrosion of the underlying metal wiring in the color resist stripping step.

Hereinafter, the present invention will be described in further detail with reference to examples. However, the following examples are merely illustrative of the invention, and the following examples are not intended to limit the scope of the invention.

In the following examples, the percentages and mixing ratios are based on weight unless otherwise stated.

Examples 1-8 and Comparative Examples 1-14

Mix a to f ingredients according to the ratios shown in Table 1 and Table 2 below. A color resist stripper composition of Examples 1-8 and Comparative Examples 1-14 was prepared.

Note: In Tables 1 and 2 above, nMEA: n-methylmethanolamine

DMSO: dimethyl hydrazine

MEA: monoethanolamine

DESO: Ethylene

HDA: Hydroxylamine

Experimental example

Next, the color resist peeling liquid compositions obtained in the above Examples 1-8 and Comparative Examples 1-14 were evaluated for performance using a color filter substrate obtained in the following procedure.

Peeling experiment on color resist

Manufacturing test piece

On a Corning glass plate with chrome or chromium oxide on the bottom Forming a color filter pattern, and applying a color resist by a photolithography process in the order of red, green, and blue, that is, applying a common color resist composition by spin coating (Dongjin Shimeiken Co., Ltd.) The company, product name: DCR-725S), and its final film thickness of 1.7 μm.

Thereafter, the resist film was placed on a hot plate, and pre-baked for 120 seconds at a temperature of 90 °C. Then, the exposure was carried out, and development was carried out for 60 seconds at a normal temperature with a 1% potassium hydroxide (KOH) developing solution, and then the patterned test piece was allowed to stand in an oven at a temperature of 220 ° C for 20 minutes. Hard baked.

Color resist stripping experiment

The test pieces prepared above were each immersed in a color resist stripper composition at a temperature of 50 ° C for 2 minutes, 5 minutes, and 10 minutes. Next, the test piece was taken out from the color resist stripping liquid composition, washed with ultrapure water, and then dried with nitrogen, and then detected by a scanning electron microscope (SEM, Hitachi, Ltd., product name: S-4100). After the residual color resist in the pattern, the removal performance of the color resist was evaluated in accordance with the following criteria, and the results are shown in Table 3.

◎: All were removed.

○: 70% removed.

△: 30% was removed.

×: All are not removed.

As is apparent from the above Table 3, in Examples 1-8, even in the initial stage of impregnation, the removal rate of the red, green and blue color patterns was excellent, and after 5 minutes, the red, green and blue patterns were completely removed, and in contrast, Comparative Example 1 14 At the beginning of the impregnation, the red, green and blue patterns were not removed at all, and after 5 minutes, some patterns remained, and after a longer period of time, all the patterns were completely removed.

Claims (6)

A color resist stripping liquid composition comprising: a) 1-50 wt% of a hydroxide selected from the group consisting of inorganic alkali hydroxides, alkyl ammonium hydroxides, and phenylalkyl ammonium hydroxides, The alkyl ammonium hydroxide comprises a C ₁ -C ₄ alkyl group; b) 5-30 wt% of a polar sulfide; c) 5 to 35 wt% of an alkene glycol ether, the alkenyl glycol The ether comprises a C ₁ -C ₄ alkyl group; d) 2-30 wt% of an alkene glycol dialkyl ether, the alkene glycol dialkyl ether comprising a C ₁ -C ₄ alkyl group; 2-30 wt% of a water-soluble amine compound; f) a residual amount of water; wherein the polar sulfide is selected from the group consisting of dimethyl hydrazine, diethyl hydrazine, dipropyl hydrazine, cyclobutyl hydrazine, and mixtures thereof. The color resist stripper composition according to claim 1, wherein the olefin-based ethylene glycol dialkyl ether containing the C ₁ -C ₄ alkyl group is selected from the group consisting of ethylene glycol dimethyl ether Diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, diethylene glycol methyl ether and mixtures thereof. The color resist stripper composition of claim 1, wherein the inorganic alkali hydroxide is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, and mixtures thereof. The color resist stripper composition according to claim 1, wherein the alkyl ammonium hydroxide containing the C ₁ -C ₄ alkyl group is selected from the group consisting of tetraethylammonium hydroxide and tetramethylhydrogen. Ammonium oxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, ammonium hydroxide, and mixtures thereof. The color resist stripping liquid composition according to claim 1, wherein the olefin-based glycol ether containing the C ₁ -C ₄ alkyl group is selected from the group consisting of ethylene glycol monobutyl ether and diethyl Glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol methyl ether, diethylene glycol methyl ether, triethylene glycol methyl ether, ethylene glycol ethyl ether, and mixtures thereof. The color resist stripper composition according to claim 1, wherein the water-soluble amine compound is selected from the group consisting of n-methylmethanolamine, monomethanolamine, ethylenediamine, and hydroxylamine.