KR101895621B1 - A composition for removing organic-inorganic hybrid alignment layer - Google Patents

Abstract

The present invention relates to (A) an inorganic alkali compound; (B) one or more organic solvents; (C) a thiol compound; And (D) water. The present invention also relates to a composition for removing an organic-inorganic hybrid film.
The present invention also relates to a method of manufacturing an array substrate for a liquid crystal display device, which comprises a step of cleaning the substrate using the composition for removing an organic-inorganic hybrid film.

Description

TECHNICAL FIELD [0001] The present invention relates to a composition for removing an organic-inorganic hybrid film,

The present invention relates to a composition for removing an organic-inorganic hybrid film, and a method for manufacturing an array substrate for a liquid crystal display including the step of cleaning a substrate using the composition.

In general, a liquid crystal display device includes a TFT substrate, a color filter substrate opposed to the TFT substrate, and a liquid crystal display panel interposed between both substrates, the liquid crystal display panel including a liquid crystal for determining whether light is transmitted when an electrical signal is applied .

Since it is difficult to obtain the same molecular alignment state simply by sandwiching the liquid crystal between the TFT substrate and the color filter substrate between both substrates, the alignment film is formed on the inner wall of the substrate.

The alignment layer can form a film at a temperature of 200 ° C or less and has good adhesion properties to the ITO substrate. The most important point in the alignment film coating process is to apply the alignment film uniformly and uniformly over a large area. Usually, the thickness of the alignment layer is about 500 to 1,000 angstroms. On the same substrate, the thickness difference of about 100 angstroms can cause defects such as stains. Therefore, thickness control of the alignment layer is an important process control item.

As the organic alignment layer, a polyimide-based polymer compound dissolved in an organic solvent is applied on an ITO substrate to a predetermined thickness, and then dried to uniformly coat the applied alignment layer. Go through the process. As the inorganic alignment film, a SiO ₂ oxide film is generally applied on an ITO substrate through vacuum deposition or the like. However, in the organic alignment film such as the polyimide system described above, it is not easy to uniformly dry due to the difference in the evaporation rate of the solvent during the process of coating and drying on the ITO substrate, and the difference in thickness applied during drying may cause unevenness . Further, when rubbing the polyimide film through the process of rubbing after drying, the liquid crystal aligns, which causes a lot of defects in the rubbing process. In addition, since the inorganic alignment film, which is a SiO ₂ oxide film system, can be used without rubbing, defects due to rubbing can be reduced, but such problems as alignment effect of liquid crystal are accompanied. For this reason, the development of an organic-inorganic hybrid alignment layer using a material mixed with an organic-inorganic material such as polydimethylsiloxane is under development. The polydimethylsiloxane is a material having a structure of SiO _x R _y (0 <x = 1, 0 <y = 1, R is an alkyl group or allyl group having a carbon atom in the structure of 1 to 10, When the organic-inorganic hybrid material is applied to the ITO substrate and then annealed at a constant temperature for a certain period of time, the silicon (Si) component bonds to the ITO substrate and has a bonding force between ITO-Si The upper layer will contain an organic group such as an alkyl or allyl group in the polydimethylsiloxane. As described above, the SiO _x material, which is a kind of inorganic alignment film, is in contact with the ITO, and the upper part, which is not in contact with ITO, is the organic material (R group of polydimethylsiloxane) A recrystallized orientation film is formed. In the case of such an organic-inorganic hybrid alignment film, it is difficult to expect a satisfactory removal effect because the removal liquid of the organic alignment film needs to remove SiO _x -type components having the property of the inorganic alignment film. Moreover, There is a difficulty in removing.

Korean Patent Laid-Open No. 10-2002-0049448 discloses a chemical rinse composition for cleaning a resist stripper as an invention for removing such a liquid crystal alignment film. However, the application is limited to a chemical rinse composition for cleaning a resist stripper, There is a problem that there is no removability in the organic-inorganic hybrid alignment film. In addition, Korean Patent No. 10-0733554 also has a limitation that it does not have a removability to the organic-inorganic hybrid alignment film, and it also essentially requires an amine. Accordingly, there is a growing need to develop a composition for removing an organic-inorganic hybrid alignment film having a removability against an organic-inorganic hybrid alignment film and having corrosion resistance against aluminum wiring.

KR 10-2002-0049448 A KR 10-0733554 B

Disclosure of Invention Technical Problem [8] The present invention has been made to solve the problems of the prior art described above, and it is an object of the present invention to provide a liquid crystal alignment film which has removability not only for an organic alignment film but also for an organic- An organic-inorganic hybrid-orientation film removing composition having a corrosion inhibiting property.

In order to achieve the above object,

The present invention relates to (A) an inorganic alkali compound; (B) one or more organic solvents; (C) a thiol compound, and (D) water. The present invention also provides a composition for removing an organic-inorganic hybrid film.

In addition, the present invention provides a method of manufacturing an array substrate for a liquid crystal display, comprising the step of cleaning the substrate using the composition for removing an organic-inorganic hybrid film.

The composition for removing the organic-inorganic hybrid layer according to the present invention is not only strong in removing the organic alignment layer but also has the ability to remove the organic-inorganic hybrid layer, thereby effectively removing the alignment layer existing on the surface of the liquid- Corrosion resistance against aluminum wiring. In addition, when the composition for removing an organic-inorganic hybrid film of the present invention is used, it is possible to reduce the defective rate of the liquid crystal display device, thereby reducing the cost of the entire manufacturing process.

BEST MODE FOR CARRYING OUT THE INVENTION The composition for removing an organic-inorganic hybrid type orientation film according to the present invention will now be described in detail.

The composition for removing an organic-inorganic hybrid film according to the present invention comprises (A) an inorganic alkali compound; (B) one or more organic solvents; (C) a thiol compound and (D) water.

(A) an inorganic alkali compound

In the present invention, the inorganic alkaline compound may be any one selected from the group consisting of potassium hydroxide, sodium hydroxide, sodium carbonate, and potassium carbonate, or a combination of two or more thereof And it is preferably contained in an amount of 0.1 to 5.0% by weight, more preferably 0.3 to 3.0% by weight, based on the total weight of the composition. When the alkali compound is contained in an amount of less than 0.1% by weight, the removal rate of the alignment layer is slow or can not be removed, and corrosion of the wiring material can not be prevented if it exceeds 5.0% by weight.

(B) Organic solvents

In the present invention, examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dimethyl (DMF), N-methylformamide, dimethylacetamide (DMAc), N-methylacetamide, diethylacetamide (DEAc), N-methylpyrrolidone (NMP) NEP), N-propylpyrrolidone (NPP), N-hydroxymethylpyrrolidone, N-hydroxyethylpyrrolidone, and the like.

In the present invention, the organic solvent is preferably contained in an amount of 30 to 80% by weight, and more preferably 40 to 60% by weight based on the total weight of the composition. When the organic solvent is contained in an amount of less than 30% by weight, the separation rate of the alignment film is slow or can not be removed. When the organic solvent is contained in an amount exceeding 80% by weight, the content of other components is insufficient and corrosion of the wiring material is increased.

(C) Thiol compound

The composition of the present invention contains a thiol compound to prevent corrosion of the wiring material.

In the present invention, the thiol compound may be a compound selected from the group consisting of thioglycerol, thioglycol, thioethanol, thiomethanol, thiobutanol, thiopropanol, Any one or a mixture of two or more selected may be used, and it is preferably contained in an amount of 10 to 50% by weight, more preferably 20 to 40% by weight based on the total weight of the composition. When the thiol compound is contained in an amount of less than 10% by weight, corrosion of the wiring material increases. When the thiol compound is contained in an amount exceeding 50% by weight, the ability to remove the alignment film is deteriorated. When the thiol compound is used, since the -S-, which is a functional group of the thiol, adsorbs to the metal faster than the case where the polyhydric alcohol is used, the effect of the metal can be further improved.

(D) Water

In the present invention, the water is not particularly limited, but it is preferable to use deionized water having a specific resistance value of 18 M? / Cm or more as water for semiconductor processing. The water is included in the remaining amount such that the total weight of the entire composition is 100% by weight, so that it can be adjusted according to the contents of other components.

The composition for removing the organic-inorganic hybrid alignment film according to the present invention may further comprise an organic alkaline compound. Examples of the organic alkaline compound include tetramethyl ammonium hydroxide (CH ₃ ) ₄ NOH, tetraethyl ammonium hydroxide (C ₂ H ₅ ) ₄ NOH, tetrapropylammonium hydroxide (C ₄ H ₉ ) ₄ NOH), carbonates, phosphates, ammonia, amines, and the like, in addition to the above-mentioned compounds, such as tetrapropyl ammonium hydroxide (C ₃ H ₇ ) ₄ NOH, tetrabutyl ammonium hydroxide One or a mixture of two or more species may be used.

The amines include primary amines such as methylamine, ethylamine, monoisopropylamine, n-butylamine, sec-butylamine, isobutylamine, t-butylamine and pentylamine; Examples of the secondary amine such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, methylethylamine, methylpropylamine, methylisopropylamine, methylbutylamine and methylisobutylamine Amine; Tertiary amines such as diethylhydroxyamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, dimethylethylamine, methyldiethylamine and methyldipropylamine; But are not limited to, choline, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, 2-aminoethanol, 2- (ethylamino) ethanol, 2- (methylamino) ethanol, Amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol, Alkanolamines such as 4-amino-1-butanol and dibutanolamine; (Methoxymethyl) dimethylamine, (methoxymethyl) dimethylamine, (butoxymethyl) dimethylamine, (isobutoxymethyl) dimethylamine, (methoxymethyl) diethanolamine (Methoxymethyl) aminoethanol, methyl (butoxymethyl) aminoethanol, 2- (2-aminoethoxy) ethanol and the like Alkoxyamine; 1- (2-hydroxyethyl) piperazine, 1- (2-aminoethyl) piperazine, 1- Methylpiperazine, 1-amino-4-methylpiperazine, 1-benzylpiperazine, 1-phenylpiperazine, N-methylmorpholine, 4-ethylmorpholine, N-formylmorpholine, N - (2-hydroxyethyl) morpholine, N- (3-hydroxypropyl) morpholine and the like.

When the organic alkaline compound is further contained in the composition for removing the organic-inorganic hybrid alignment film according to the present invention, a mixture of the organic alkaline compound and the inorganic alkaline compound is contained in an amount of 0.1 to 5 wt% , More preferably from 0.3 to 3.0% by weight. When the amount of the mixture of the organic alkali compound and the inorganic alkaline compound is less than 0.1% by weight, the removal rate of the alignment film is slow or is not removed, and the effect of the system is lost. Corrosion of the material can not be prevented.

The composition for removing the organic-inorganic hybrid alignment film according to the present invention may further comprise a surfactant commonly used in this field and a corrosion inhibitor for Cu as an additive. Examples of the additives include nonionic surfactants, cationic surfactants, and anionic surfactants that are commonly used. As the corrosion inhibitor for Cu, 2,2 '- [[[benzotriazole] Methyl] imino] bis-methanol, 2,2 '- [[[ethyl-1-hydrogen- Benzotriazol-1-yl] methyl] imino] bisethanol, 2,2 '- [[methyl hydrogen- Methyl] imino] biscarboxylic acid, 2,2 '- [[[methyl-1-hydrogen-benzotriazol- A mixture of any one or a mixture of two or more selected from the group consisting of bismethylamine, 2,2 '- [[[amine-1-hydrogen-benzotriazol-1-yl] methyl] imino] bisethanol and benzotriazole derivatives Can be used.

The dipping method is generally used as a method for removing the organic-inorganic hybrid alignment film using the composition for removing the organic-inorganic hybrid alignment film of the present invention, but other methods such as a spraying method may also be used. As the cleaning agent after treatment with the composition according to the present invention, it is not necessary to use an organic solvent such as alcohol, and it is sufficient to wash with water.

The composition for removing an organic-inorganic hybrid alignment film of the present invention can be usefully used in a process for removing an organic-inorganic hybrid-orientation film of a semiconductor or an electronic product, particularly a liquid crystal panel.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Example

Example  1 to 6 and Comparative Example  1-7: Weapon - Weapon Hybrid type  Preparation of alignment film removing composition

The components listed in Table 1 were mixed in the composition ratios to prepare cleaning compositions for removing the organic-inorganic hybrid type alignment films of Examples 1 to 6 and Comparative Examples 1 to 7.

alkali solvent Thiol compound water Kinds amount Kinds amount Kinds amount Example 1 KOH 0.1 MTG 30 Thioglycerol 50 Balance Example 2 KOH 3 BDG 60 Thioglycerol 30 Balance Example 3 KOH 5 MTG 80 Thioglycerol 10 Balance Example 4 NaOH 3 MTG 60 Thioglycerol 30 Balance Example 5 KOH 3 BDG 60 Thioglycol 30 Balance Example 6 KOH / TMAH 1.5 / 1.5 BDG 60 Thioglycerol 30 Balance Comparative Example 1 - - MTG 20 Thioglycerol 50 Balance Comparative Example 2 KOH 10 MTG 20 Thioglycerol 50 Balance Comparative Example 3 KOH 5 - - Thioglycerol 30 Balance Comparative Example 4 KOH 0.1 MTG 60 - - Balance Comparative Example 5 KOH 3 MTG 90 Thioglycerol 5 Balance Comparative Example 6 KOH 3 MTG 30 Thioglycerol 60 Balance Comparative Example 7 KOH 3 BDG 20 Thioglycerol 30 Balance

KOH: Potassium hydroxide

NaOH: Sodium hydroxide

BDG: diethylene glycol monobutyl ether

MTG: triethylene glycol monomethyl ether

TMAH: tetramethyl ammonium hydroxide &lt; RTI ID = 0.0 &gt;

Experimental Example : Weapon - Weapon Hybrid type  Characterization of composition for removing alignment film

1) Evaluation of removability of organic-inorganic hybrid alignment film

In order to evaluate the removability of the organic-inorganic hybrid alignment film, a glass substrate coated with an organic-inorganic hybrid alignment film (Butyl-Si- (O-Me) 3) was prepared in a size of 1.5 cm x 6 cm. The prepared substrate was immersed in the compositions of Examples 1 to 6 and Comparative Examples 1 to 7 by soaking at room temperature for 1 minute and 3 minutes. Washed, washed with ultrapure water for 30 seconds, and dried with nitrogen. The evaluation results are shown in Table 2 below.

<Evaluation Criteria>

&Amp; cir &amp;: When the organic-inorganic hybrid alignment film was removed,

?: When about 50% was removed,

X: When no removal was made

2) Aluminum etching rate measurement

First, a glass substrate on which aluminum was formed to a thickness of 2500 Å was immersed in the compositions of Examples 1 to 6 and Comparative Examples 1 to 7 for 10 minutes. At this time, the temperature of the cleaning liquid was 25 占 폚. The thickness of the aluminum film was measured before and after immersion, and the dissolution rate of the aluminum film was measured by calculating the etching rate from the change in the thickness of the aluminum film. The results are shown in Table 2 below.

Al etching rate (A / min) Removal ability of organic-inorganic hybrid alignment film 1 minute 3 minutes Example 1 0.35 △ ○ Example 2 1.00 ○ ○ Example 3 1.37 ○ ○ Example 4 1.29 ○ ○ Example 5 0.83 ○ ○ Example 6 1.30 ○ ○ Comparative Example 1 0.09 × × Comparative Example 2 9.33 ○ ○ Comparative Example 3 1.29 × △ Comparative Example 4 7.87 ○ ○ Comparative Example 5 8.01 ○ ○ Comparative Example 6 0.24 × × Comparative Example 7 1.06 × △

From the test results of Table 2, the compositions of Examples 1 to 6, which are the detergent compositions of the present invention, are superior in removing ability of the organic / inorganic hybrid alignment film at room temperature, It was confirmed that the saints were generally excellent.

Claims (11)

With respect to the total weight of the composition,
(A) from 0.1 to 5.0% by weight of an inorganic alkali compound;
(B) 30 to 80% by weight of one or more organic solvents;
(C) 10 to 50% by weight of a thiol compound; And
(D) residual water. The composition for removing an organic-inorganic hybrid film according to claim 1, The method according to claim 1,
Wherein the organic-inorganic hybrid composition further comprises an organic alkaline compound. delete The method of claim 2,
Wherein the mixture of the organic alkaline compound and the inorganic alkaline compound is contained in an amount of 0.3% by weight to 3.0% by weight. The method according to claim 1 or 2,
Wherein the inorganic alkaline compound is any one or a mixture of two or more selected from the group consisting of potassium hydroxide, sodium hydroxide, sodium carbonate, and potassium carbonate. Inorganic hybrid alignment film removing composition. The method of claim 2,
The organic alkaline compound may be selected from the group consisting of tetramethyl ammonium hydroxide (CH ₃ ) ₄ NOH, tetraethyl ammonium hydroxide (C ₂ H ₅ ) ₄ NOH, tetrapropylammonium hydroxide Or a mixture of two or more selected from the group consisting of tetrapropyl ammonium hydroxide (C ₃ H ₇ ) ₄ NOH), tetrabutyl ammonium hydroxide (C ₄ H ₉ ) ₄ NOH) Inorganic hybrid film. The method of claim 6,
Wherein the amines are selected from the group consisting of primary amines, secondary amines, tertiary amines, alkanol amines, alkoxy amines and cyclic amines, or a mixture of two or more thereof. . The method according to claim 1 or 2,
The organic solvent is selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dimethylformamide (DMF) , N-methyl formamide, dimethylacetamide (DMAc), N-methylacetamide, diethylacetamide (DEAc), N-methylpyrrolidone (NMP) Wherein the organic solvent is any one selected from the group consisting of propylpyrrolidone (NPP), N-hydroxymethylpyrrolidone, and N-hydroxyethylpyrrolidone, or a mixture thereof. The method according to claim 1 or 2,
Wherein the composition further comprises at least one selected from the group consisting of a nonionic surfactant, a cationic surfactant, and an anionic surfactant as a surfactant. The method according to claim 1 or 2,
Methyl] imino] bisethanol, 2,2 '- [[[methyl hydrogen-benzotriazol-1-yl] methyl] Methyl] imino] bisethanol, 2,2 '- [[[methyl-1-hydrogen-benzotriazol- 1-yl] methyl] ] Imino] biscarboxylic acid, 2,2 '- [[[methyl-1-hydrogen-benzo Triazol-1-yl] methyl] imino] bismethylamine and 2,2 '- [[[amine-1-hydrogen-benzotriazol- 1-yl] methyl] imino] bisethanol Wherein the composition further comprises one or a mixture of two or more thereof as a corrosion inhibitor for Cu. A method for manufacturing an array substrate for a liquid crystal display, comprising the step of cleaning a substrate using the composition for removing an organic-inorganic hybrid film as set forth in claim 1 or claim 2.