JP4395020B2 - Stripping composition for resist removal - Google Patents

Description

  The present invention relates to a stripping solution composition for removing a color resist for TFT-LCD, and more specifically, for removing only a defective color resist of a substrate generated during a color filter process and reusing a black mask or a glass substrate. The present invention relates to a stripping solution composition for removing the color resist for TFT-LCD.

  The color filter substrate is composed of a black matrix that plays the role of improving the contrast, and a common electrode that applies voltage to the liquid crystal cell, blocking the leakage light between the color filter red, green and blue patterns and each pixel. Yes. The process of making a color filter is as follows.

  Depending on the application, Cr / CrOx or an organic material used as a black matrix material is coated on a glass substrate to form a pattern. After forming the black mask pattern, a color resist pattern for realizing a hue is formed by a photographic process technique. A color resist is applied onto a glass substrate and exposed, and the color resist is cured by a photopolymerization reaction. After the exposure is completed, the unexposed portions of the color resist are removed by development, and a baking process is performed.

  The color resist is manufactured by a pigment dispersion method, a dyeing method, an electrodeposition method or the like, and among these, the pigment dispersion method is mainly used. In general, in a color resist, an organic pigment that realizes a hue is dispersed in a photopolymerization initiator, a monomer, a binder, or the like, which is a photosensitive composition such as a photoresist. The photopolymerization initiator is a high-sensitivity compound that receives light to generate radicals, and the monomer is combined in a polymer form after the polymerization reaction is initiated by the radicals and is not soluble in the developing solvent. The binder protects the monomer in the liquid state at room temperature from the developer, and affects the reliability of the pigment dispersion and the heat resistance, light resistance and chemical resistance of the red, green and blue patterns.

  At present, once the color resist of the defective color filter substrate generated in the color filter process is cured once, it is almost impossible to remove and correct only the defective portion of the pattern, and the color resist is removed. Because there is little solvent available, defective color filters are disposed of almost immediately without reworking.

  Color resists have negative characteristics, but in general, negative resists are more difficult to remove and remove than positive resists. Therefore, negative resists are required to have strong stripping performance. For this reason, conventionally, RIE (reactive ion etching) using an inorganic stripping solution and plasma has been used. In the case of an inorganic stripping solution, heating sulfuric acid, nitric acid, fuming yellow acid, a mixture of nitric acid and hydrogen peroxide, etc., at a high temperature of 120 ° C or higher will only adversely affect the safety of workers. However, there is a problem that requires careful handling because of the increased risk of fire due to heating. Specific examples of the inorganic stripping solution include a mixed solution of an alkylbenzene sulfonic acid and a non-halogenated aromatic hydrocarbon solvent having a boiling point of 150 ° C. or higher (see, for example, Patent Document 1), an alkyl aryl sulfonic acid, A mixed liquid of an aqueous aromatic sulfonic acid and a non-halogenated aromatic hydrocarbon solvent (see, for example, Patent Document 2) is a stripper obtained by adding a polar or nonpolar organic solvent to an organic sulfonic acid and 1,2-dihydroxybenzene. (See, for example, Patent Document 3) Each is disclosed.

In the case of a method using RIE using plasma, etching of a cured color resist, which cannot be removed by general wet etching, can be performed by continuously using O ₂ -RIE and SF ₆ -RIE ( For example, see Patent Document 4), a cured color resist using a polyester, polyamide, novolac resin as an absorption layer, and a mixture of polysilane, polysiloxane, organosilicon compound, silica, silicon nitride as a barrier layer. A method using plasma using oxygen as the absorption layer and RIE using sulfur hexafluoride or nitrogen trifluoride as the barrier layer is disclosed (for example, see Patent Document 5). However, etching of color filters using such plasma requires high vacuum and high energy, making it difficult to match the process conditions, making it difficult to use in large areas, and disadvantages such as expensive equipment. have.

As can be seen from the prior art examples, since it is difficult to stably remove a large amount of color resist by the conventional color resist removing method, the safety of workers becomes a problem, productivity or There is a problem that the yield falls.
JP 51-72503 A US Pat. No. 4,165,294 European Patent Publication No. 0119337 US Pat. No. 5,756,239 US Pat. No. 5,059,500

  Therefore, the present invention is for solving the problems of the prior art as described above, and it is difficult to remove the color resist pattern, and it is difficult to remove the defective color filter substrate which has been almost discarded. It is an object of the present invention to provide a resist remover composition for removing a color resist or the like used in a TFT-LCD color filter manufacturing process that can be improved.

To achieve the above object, the present invention is (a) 1 to 10% by weight of water oxidation alkylammonium,
(B) dimethyl sulfoxide 40-95 wt%, and (c) 4 to 50% by weight of water seen including,
The inorganic alkali acetate, the (a), (b) providing a and resist removing stripping liquid composition, characterized in 0.05 to 111 parts by weight containing Mukoto per 100 parts by weight of the combined (c) .

Preferably, the compositions of the present invention (d) In the water-soluble amine compound, N- alkyl-2-pyrrolidone, alkylene glycol ether, wherein one or more compound selected from the group consisting 及 beauty alkanolamine (a), It may further include 0.05 to 111 parts by weight with respect to 100 parts by weight of the total of (b) and (c) .

  The stripping composition for resist removal according to the present invention can easily remove the color resist within a short time. In addition, the corrosion of the lower metal wiring during the color resist removing process can be minimized, and it is possible to rinse with only water without using an organic solvent such as isopropyl alcohol or dimethyl sulfoxide in the subsequent rinsing process. There is an advantage.

  Hereinafter, the present invention will be described in detail.

  The present invention relates to a stripping solution composition for removing a color resist pattern and the like in order to reuse a defective substrate generated during a color filter process of a TFT-LCD.

  The stripping composition for resist removal of the present invention contains a) inorganic alkali hydroxide or alkylammonium hydroxide. In the case of the color filter process, inorganic alkali hydroxide can be used because it is not greatly affected by the residual metal. Since the alkylammonium hydroxide is not stable, it is preferably used in a state dissolved in water.

  The content of the inorganic alkali hydroxide or alkylammonium hydroxide component is preferably 1 to 10% by weight based on the total composition. If the content of the inorganic alkali hydroxide or alkylammonium hydroxide is less than 1% by weight, it is difficult to completely remove the color resist due to a decrease in the ability to penetrate the polymer component constituting the color resist. If it exceeds 1, only the swelling phenomenon becomes intense, and the dissolution performance of the color resist with respect to the polymer component decreases.

  It is preferable to use at least one inorganic alkali hydroxide selected from the group consisting of sodium hydroxide and potassium hydroxide. The alkyl ammonium hydroxide is preferably used by selecting one or more kinds from the group consisting of tetraethylammonium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, and ammonium hydroxide.

  Moreover, the stripping solution composition for resist removal of this invention contains b) dimethyl sulfoxide. The dimethyl sulfoxide penetrates into a polymer constituting the color resist and plays a role of separating the color resist from the glass substrate. In the stripping composition of the present invention, the content of dimethyl sulfoxide is preferably 40 to 95% by weight with respect to the total composition. If the dimethyl sulfoxide content is less than 40% by weight, there is a problem that it cannot be completely removed because the penetrating power to the color resist is weakened. If it exceeds 95% by weight, the viscosity and melting point of the color resist stripping solution composition. There is a problem in that the convenience is lowered during use.

  In the stripping composition for resist removal of the present invention, c) water is an essential component, and it is preferable to use pure water filtered with an ion exchange resin, and to use ultrapure water having a specific resistance of 18 MΩ or more. Further preferred.

  The water content is preferably 4 to 50% by weight based on the total composition. If the water content is less than 4% by weight, the alkylammonium hydroxide is not activated, so the penetrating power to the color resist is weakened. If the water content exceeds 50% by weight, the water is evaporated at the process temperature. There is a problem in that the composition changes drastically and the lifetime is reduced.

The resist removing stripping liquid composition of the present invention, (d) water-soluble amine compound, N- alkyl-2-pyrrolidone, alkylene glycol ether, a 及 beauty is at least one selected from the group consisting of alkanolamine compound It may further include 0.05 to 111 parts by weight with respect to 100 parts by weight of the above (a), (b) and (c) .

The water-soluble amine compound can be used to improve the performance of the stripping composition. The water-soluble amine compound is preferably a water-soluble hydroxylamine compound. The hydroxylamine exhibits a function of allowing hydroxyl ions generated by reacting with hydrogen ions of water to effectively penetrate into the contact surface between the color resist and the substrate. It has the function of dissolving the pigment bonding agent. The hydroxylamine is preferably used in a 50% aqueous solution state. The use amount of the water-soluble amine compound is preferably 2 to 20 parts by weight with respect to 100 parts by weight of the total of (a), (b) and (c) . If the content of the water-soluble amine compound is less than 2 parts by weight, it is difficult to completely remove the color resist, and if it exceeds 20 parts by weight, the corrosiveness to the lower film quality increases.

In the stripping solution composition for resist removal according to the present invention, the N-alkyl-2-pyrrolidone may be used to improve performance, and N-alkyl-2-pyrrolidone has a function of dissolving and swelling a polymer. is there. The content of the N-alkyl-2-pyrrolidone is preferably 2 to 20 parts by weight with respect to 100 parts by weight of the total of (a), (b) and (c) . If the content of the N-alkyl-2-pyrrolidone is less than 2 parts by weight, the solubility of the polymer as a constituent component in the color resist is reduced, and if it exceeds 20 parts by weight, the content of other components is reduced. There is a problem of weakening the penetrating power to the color resist.

  The N-alkyl-2-pyrrolidone is preferably selected from the group consisting of N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone.

The stripping composition for removing a resist according to the present invention can use an alkylene glycol ether to improve performance, and the alkylene glycol ether has a feature of stripping a color resist from a glass substrate, penetrates the molecule, and It plays the role of dissolving the binder of pigment particles. The content of the alkylene glycol ether is preferably 2 to 50 parts by weight with respect to 100 parts by weight of the total of (a), (b) and (c) . When the content of the alkylene glycol ether is less than 2 parts by weight, the dissolving ability of the color resist is lowered, and when it exceeds 50 parts by weight, the content of dimethyl sulfoxide is reduced and the penetrating power is weakened.

  The alkylene glycol ether is diethylene glycol ethyl ether, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, and dipropylene. It is preferable to use one or more selected from the group consisting of glycol monoethyl ether.

In the resist removing stripping liquid composition according to the present invention, an inorganic alkali acetate to improve performance. The inorganic alkali acetate has a function of improving the functions of alkyl ammonium hydroxide and alkyl aryl ammonium hydroxide by penetrating into the polymer or dye. The content of the inorganic alkali acetate is preferably 0.05 to 1 part by weight with respect to 100 parts by weight of the total of (a), (b) and (c) . If the inorganic alkali acetate content is less than 0.05 parts by weight, it cannot be expected to improve the function of penetrating into the polymer that is a color resist component, and if it exceeds 1 part by weight, There is a problem in that the dissolving ability of the inorganic alkali acetate with respect to parts by weight is lowered to cause precipitation.

  It is preferable to use at least one inorganic alkali acetate selected from the group consisting of potassium acetate and sodium acetate.

In the stripping composition for removing a resist according to the present invention, alkanolamine can be used to improve the performance, and alkanolamine has excellent dissolving power for a photosensitive compound, so that alkylammonium hydroxide penetrates between polymers. It also has the function of dissolving the polymer and pigment binder. The content of the alkanolamine is preferably 2 to 20 parts by weight with respect to 100 parts by weight of the total of (a), (b) and (c) . When the content of the alkanolamine is less than 2 parts by weight, the function of dissolving the photosensitive compound and the bonding agent is lowered and the function cannot be expected to be improved. When the content exceeds 20 parts by weight, the content of other components is decreased. This has the problem of adversely affecting the color resist removal performance.

  The alkanolamine is preferably selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, methylethanolamine, ethylethanolamine, dimethylethanolamine, diethylethanolamine, and aminoethoxyethanol.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail through an Example, the scope of the present invention is not necessarily limited to the following Example. On the other hand, in the following examples, the percentage and the mixing ratio are based on weight unless otherwise mentioned.

  In the examples and comparative examples of the present invention, the performance evaluation for the color resist stripping composition was carried out by the following method for removing the color resist using a color filter substrate of Company A.

(1) Color resist removal test
A color filter pattern was made on LCD corning glass with Cr / CrOx deposited at the bottom of the specimen manufacture , and the color resist was applied in the order of red, green and blue using the following photographic processes. A commonly used color resist composition (Toshin Semi-Chem, trade name: DCR-725S) was spin-coated and applied so that the final film thickness was 1.7 μm. Next, the resist film was pre-baked at 90 ° C. for 120 seconds using a hot plate. Subsequently, after exposure and development with a 2.38% tetramethylammonium hydroxide (TMAH) developer at 21 ° C. for 60 seconds, the specimen on which the pattern was formed was hard baked at 220 ° C. for 20 minutes.

The color resist removal test specimens were immersed in a stripping composition for removing the color resist at a temperature of 60 ° C. for 5 minutes, 10 minutes and 15 minutes, respectively. Subsequently, the specimen was taken out from the color resist stripping composition, washed with ultrapure water and dried with nitrogen gas, and then the presence or absence of the color resist in the pattern was inspected with a scanning electron microscope (SEM). The color resist removal performance was evaluated based on the following criteria, and the results are shown in Table 2 below.

  A: When all of the red, green and blue patterns are completely removed.

  ○: When only green and blue patterns are removed.

  Δ: When only the blue pattern is removed.

  X: When all the red, green and blue patterns are not removed.

(2) Metal film corrosion test
Metal Film Corrosion Test Each of the specimens was immersed in a stripping solution composition for removing a color resist at a temperature of 60 ° C. for 30 minutes. Subsequently, the specimen was taken out from the color resist stripping composition, washed with ultrapure water and dried with nitrogen gas, and then inspected with a scanning electron microscope for the occurrence of undercut phenomenon in the metal part of the pattern. The degree was evaluated based on the following criteria, and the results are shown in Table 3 below.

○: When there is no undercut phenomenon in the lower metal film △: When there is a part of the undercut phenomenon in the lower metal film ×: When the undercut phenomenon is severely shown in the lower metal film
Examples 1-7 and Comparative Examples 1-2
The contents of the components (a) to (d) according to the present invention were mixed at the ratios shown in Table 1 below to prepare color resist stripping liquid compositions of Examples 1 to 7 and Comparative Examples 1 and 2, respectively. The color resist stripping solution composition thus obtained was subjected to the (1) color resist removal test and (2) metal film corrosion test described above, and the results are shown in Tables 2 and 3 below. .

注）
TMAH: 水酸化テトラメチルアンモニウム
DMSO：ジメチルスルホキシド
HDA:ヒドロキシルアミン
NMP:N-メチル-２-ピロリドン
PGME:１-メトキシ-２-プロパノール
カルビトール:ジエチレングリコールモノエチルエーテル。

note)
TMAH: Tetramethylammonium hydroxide
DMSO: Dimethyl sulfoxide
HDA: hydroxylamine
NMP: N-methyl-2-pyrrolidone
PGME: 1-methoxy-2-propanol carbitol: diethylene glycol monoethyl ether.

前記表２及び３の結果から分かるように、本発明の実施例１乃至７の剥離液組成物は比較例１乃至２に比べて金属配線腐食性は従来と同等水準以上であり、特にカラーレジスト除去性能が非常に優れている。

As can be seen from the results shown in Tables 2 and 3, the stripping compositions of Examples 1 to 7 of the present invention have a metal wiring corrosivity higher than that of Comparative Examples 1 and 2 in comparison with the prior art. The removal performance is very good.

  FIG. 1 shows a scanning electron microscope (Hitachi, model name: S-4100) photograph comparing the color resist removal performance of the color resist stripping compositions of Example 5 and Comparative Example 1. FIG. 1 shows the results of testing the color resist stripping composition at a temperature of 60 ° C.

  As shown in FIG. 1, when the stripping composition of Example 5 of the present invention was used, the color resist was removed more cleanly than Comparative Example 1.

The photograph of the scanning electron microscope (Hitachi company, model name; S-4100) which made the temperature of the color resist peeling liquid composition of Example 5 and Comparative Example 1 60 degreeC, and compared the color resist removal performance is shown. .

Claims (9)

(A) water oxidation alkylammonium 1 to 10% by weight,
(B) dimethyl sulfoxide 40-95 wt%, and (c) 4 to 50% by weight of water seen including,
The inorganic alkali acetate, the (a), (b) and resist removing stripping liquid composition, characterized in 0.05 to 111 parts by weight containing Mukoto per 100 parts by weight of the combined (c). 2. The resist removing strip according to claim 1, comprising 0.05 to 1 part by weight of the inorganic alkali acetate with respect to 100 parts by weight of the total of (a), (b), and (c). Liquid composition. The alkyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, claims characterized in that it is at least one selected from the group consisting of trimethyl benzyl ammonium and ammonium hydroxide, Item 2. The stripping composition for resist removal according to Item 1. (D) water-soluble amine compound, N- alkyl-2-pyrrolidone, alkylene glycol ethers, one or more compound selected from the group consisting 及 beauty alkanolamine wherein (a), the combined (b) and (c) the resist removing stripping liquid composition according to claim 1, characterized in that it comprises 0.05 to 111 parts by weight of al relative to 100 parts by weight. The water-soluble amine compound, resist removing stripping liquid composition according to claim 4, characterized in that the hydroxylamine. The N- alkyl-2-pyrrolidone, resist removal according to claim 4, characterized in that it is selected N- ethyl-2-pyrrolidone, and N- 1 or more from the group consisting of methyl-2-pyrrolidone Stripping composition.   The alkylene glycol ether is diethylene glycol ethyl ether, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, and diethylene glycol monobutyl ether. The stripping solution composition for resist removal according to claim 4, wherein at least one selected from the group consisting of propylene glycol monoethyl ether is selected. The stripping composition for removing a resist according to claim 1 , wherein the inorganic alkali acetate is selected from the group consisting of potassium acetate and sodium acetate. The alkanolamine is characterized monoethanolamine, diethanolamine, triethanolamine, methylethanolamine, ethyl ethanolamine, dimethylethanolamine, diethylethanolamine, and that it is at least one selected from the group consisting of amino ethoxy ethanol The stripping solution composition for resist removal according to claim 4.

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