KR20130115925A - A composition for removing organic-inorganic hybrid alignment layer - Google Patents

Abstract

PURPOSE: A composition for eliminating an organic-inorganic hybrid alignment layer is provided to have a powerful removal strength to an organic alignment layer, to be able to effectively remove an alignment layer existing on the surface of a liquid crystal display panel, and to have the anti-corrosion property to the aluminum wiring. CONSTITUTION: A composition for eliminating an organic-inorganic hybrid alignment layer is characterized in comprising (A) an inorganic alkali compound; (B) more than one kind or two kinds of organic solvents; (C) an aliphatic polyhydric alcohol; and the residual amount of water. The composition for eliminating an organic-inorganic hybrid alignment layer is characterized in further comprising an organic alkali compound. The composition for eliminating an organic-inorganic hybrid alignment layer is characterized in comprising (A) 0.1-5 weight% of an inorganic alkali compound; (B) 30-80 weight% of more than one kind or two kinds of organic solvents; (C) 10-50 weight% of an aliphatic polyhydric alcohol; and the residual amount of water.

Description

Organic-inorganic hybrid alignment film removal composition {A COMPOSITION FOR REMOVING ORGANIC-INORGANIC HYBRID ALIGNMENT LAYER}

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

In general, a liquid crystal display device includes a liquid crystal display panel including a TFT substrate, a color filter substrate facing the TFT substrate, and a liquid crystal interposed between both substrates to determine whether light is transmitted as an electric signal is applied. .

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 the two substrates, so that an alignment film is formed by treating the inner wall of the substrate.

The alignment layer should be able to form a film at 200 ° C. or lower, and have good adhesion properties to an ITO substrate. The most important point in the alignment film application process is to apply the alignment film uniformly and uniformly over a large area. Usually, the thickness of the alignment film is about 500 to 1,000 mm 3, and defects such as spots may occur due to a thickness difference of about 100 mm 3 on the same substrate, so the thickness management of the alignment film is an important process control item.

The alignment layer is generally classified into an organic alignment layer and an inorganic alignment layer, and the organic alignment layer is dried by dissolving a polyimide polymer compound in an organic solvent at a constant film thickness on an ITO substrate and then uniformly applying the applied alignment layer. Go through the process. In addition, as an inorganic alignment film, a SiO ₂ oxide film is generally applied to an ITO substrate by vacuum deposition or the like. However, the organic alignment film such as polyimide described above is not easy to uniformly dry due to the difference in the evaporation rate of the solvent in the process of drying after coating on the ITO substrate, and stains may occur due to the difference in thickness applied during drying. . In addition, when rubbing the polyimide-based film through a process called rubbing after drying, the liquid crystal is aligned, which may cause many defects during the rubbing process. In addition, since the inorganic alignment film, which is an SiO ₂ oxide film system, can be used without going through a rubbing process, it is possible to reduce defects due to rubbing, but it has other problems such as an alignment effect of liquid crystals. For this reason, the development of an organic-inorganic hybrid type alignment film using an organic-inorganic mixed material such as polydimethylsiloxane has been in progress. 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 an allyl group having a structure of 1 to 10 carbon atoms) and polydimethylsiloxane When acid-organic hybrid materials are applied to ITO substrates and heat treated at a constant temperature for a certain time, the silicon (Si) component has a bonding force in the part in contact with the ITO substrate and has a bonding force between ITO-Si, but not in contact with the ITO substrate. The upper layer does not have organic groups such as alkyl or allyl groups in the polydimethylsiloxane. As such, the organic-inorganic hive contains SiO _x material, which is a kind of inorganic alignment film, and an organic material (corresponding to R group of polydimethylsiloxane), which is a kind of organic alignment film, in the portion contacting ITO. A li type alignment film is formed. In the case of such an organic-inorganic hybrid type alignment film, since the organic liquid alignment film removal liquid must remove even the SiO _x component having the property of the inorganic alignment film, it is difficult to expect a satisfactory removal effect. There is a difficulty in getting rid of.

As the invention for removing the liquid crystal alignment layer as described above, Korean Patent Registration No. 10-0733554 describes a liquid crystal alignment layer removal liquid and a method of cleaning the liquid crystal display panel using the same, but there is no problem in removing the organic-inorganic hybrid alignment layer. In addition to this, there is a limitation in that an amine is necessary. Korean Patent Registration No. 10-0361481 also has no removal property for an organic-inorganic hybrid alignment layer. Therefore, there is an increasing need for development of an organic-inorganic hybrid type alignment film removing composition which has removability to an organic-inorganic hybrid alignment film and has corrosion resistance to aluminum wiring.

KR 10-0733554 B KR 10-0361481 B

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and in order to ensure excellent removability with respect to the liquid crystal alignment film of the liquid crystal display panel, it has removability not only for the organic alignment film but also for the organic-inorganic hybrid alignment film. It is an object of the present invention to provide an organic-inorganic hybrid type alignment film removing composition having corrosion protection against.

In order to achieve the above object,

The present invention (A) an inorganic alkali compound; (B) one or two or more organic solvents; (C) aliphatic polyhydric alcohols; And it provides an organic-inorganic hybrid type alignment film removal composition comprising a residual amount of water.

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

The organic-inorganic hybrid alignment layer removing composition according to the present invention not only has a strong removal force on the organic alignment layer, but also has a removal force on the organic-inorganic hybrid alignment layer, and can effectively remove the alignment layer present on the surface of the liquid crystal display panel. It has corrosion protection against aluminum wiring. In addition, when using the organic-inorganic hybrid type alignment film removal composition of the present invention, it is possible to reduce the defect rate of the liquid crystal display device to reduce the cost of the entire manufacturing process.

1 is a photograph of a substrate before cleaning using the organic-inorganic hybrid type alignment film removal composition of the present invention.
2 is a photograph of a substrate after cleaning using the organic-inorganic hybrid type alignment film removal composition of the present invention.

Hereinafter, the organic-inorganic hybrid type alignment film removing composition according to the present invention will be described in detail.

The organic-inorganic hybrid type alignment film removing composition according to the present invention comprises (A) an inorganic alkali compound; (B) one or two or more organic solvents; (C) aliphatic polyhydric alcohols; And residual water.

In the present invention, the inorganic alkali compound is any one or two or more selected from the group consisting of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, and a combination thereof. It may be used, it is preferably included in 0.1 to 5.0% by weight, more preferably 0.3 to 3.0% by weight relative to the total weight of the composition. When the alkali compound is included in less than 0.1% by weight, the alignment film removal rate is slow or not removed. When the alkali compound is included in an amount of more than 5% by weight, corrosion of the wiring material cannot be prevented.

In the present invention, as the organic solvent, 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 Formamide (DMF), N-methylformamide, dimethylacetamide (DMAc), N-methylacetamide, diethylacetamide (DEAc), N-methyl pyrrolidone (NMP), N-ethyl pyrrolidone ( NEP), N-propyl pyrrolidone (NPP), N-hydroxymethyl pyrrolidone, N-hydroxyethyl pyrrolidone, etc. can be used 1 type or in mixture of 2 or more types.

In the present invention, the organic solvent is preferably included in 30 to 80% by weight, more preferably in 40 to 60% by weight relative to the total weight of the composition. When the organic solvent is included in less than 30% by weight, the alignment film peeling rate is not slowed or removed. When the organic solvent is included in an amount of more than 80% by weight, the content of other components is insufficient, which increases corrosion of the wiring material.

In the present invention, as the aliphatic polyhydric alcohol, any one or a mixture of two or more selected from the group consisting of glycerol, glucose, mannose, galactose, sorbitan, mannitol, and polyethylene glycol can be used, and the total weight of the composition is 10 It is preferably included in the 50 to 50% by weight, more preferably included in 20 to 40% by weight. When the aliphatic polyhydric alcohol is included in less than 10% by weight, the corrosion of the wiring material is increased, and when included in excess of 50% by weight, the alignment film removal property is inferior.

In the present invention, the water is not particularly limited, but as the water for the semiconductor process, it is preferable to use deionized water having a specific resistance value of 18 MPa / cm or more. 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 organic-inorganic hybrid alignment layer removing composition according to the present invention may further include an organic alkaline compound. Examples of the organic alkali compound include tetramethyl ammonium hydroxide (CH ₃ ) ₄ NOH, tetraethyl ammonium hydroxide (C ₂ H ₅ ) ₄ NOH, and tetrapropyl ammonium hydroxide. (tetrapropyl ammonium hydroxide, (C ₃ H ₇ ) ₄ NOH), tetrabutyl ammonium hydroxide ((C ₄ H ₉ ) ₄ NOH), carbonate, phosphate, ammonia and amines selected from the group consisting of One or a mixture of two or more may be used.

Examples of the amines include primary amines such as methylamine, ethylamine, monoisopropylamine, n-butylamine, sec-butylamine, isobutylamine, t-butylamine and pentylamine; Secondary such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, methylethylamine, methylpropylamine, methylisopropylamine, methylbutylamine, methylisobutylamine, etc. Amines; Tertiary amines such as diethyl hydroxyamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, dimethylethylamine, methyldiethylamine and methyldipropylamine; Choline, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, 2-aminoethanol, 2- (ethylamino) ethanol, 2- (methylamino) ethanol, N-methyl diethanolamine, N, N-dimethyl Ethanolamine, N, N-diethylaminoethanol, 2- (2-aminoethylamino) -1-ethanol, 1-amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol, Alkanolamines such as 4-amino-1-butanol and dibutanolamine; (Butoxymethyl) diethylamine, (methoxymethyl) diethylamine, (methoxymethyl) dimethylamine, (butoxymethyl) dimethylamine, (isobutoxymethyl) dimethylamine, (methoxymethyl) diethanolamine , (Hydroxyethyloxymethyl) diethylamine, methyl (methoxymethyl) aminoethane, methyl (methoxymethyl) aminoethanol, methyl (butoxymethyl) aminoethanol, 2- (2-aminoethoxy) ethanol Alkoxyamines; 1- (2-hydroxyethyl) piperazine, 1- (2-aminoethyl) piperazine, 1- (2-hydroxyethyl) methylpiperazine, N- (3-aminopropyl) morpholine, 2-methyl Piperazine, 1-methylpiperazine, 1-amino-4-methylpiperazine, 1-benzyl piperazine, 1-phenyl piperazine, N-methylmorpholine, 4-ethylmorpholine, N-formylmorpholine, N And cyclic amines having a ring such as-(2-hydroxyethyl) morpholine or N- (3-hydroxypropyl) morpholine.

The organic alkali compound is preferably included in 0.1 to 5.0% by weight, more preferably 0.3 to 3.0% by weight relative to the total weight of the composition. When the organic alkali compound is included in less than 0.1% by weight, not only the removal rate of the alignment film is slow or not removed, and when the anticorrosive effect is eliminated, when the organic alkali compound is contained in an amount of more than 5% by weight, corrosion of the wiring material may be prevented. none.

The organic-inorganic hybrid alignment layer removing composition according to the present invention may further include additives such as surfactants commonly used in the art. The additives include nonionic surfactants, cationic surfactants and anionic surfactants which are generally used, and these may be used alone or in combination.

As a method for removing the organic-inorganic hybrid alignment film using the organic-inorganic hybrid alignment film removal composition of the present invention, the dipping method is generally used, but other methods such as a spraying method may also be used. As a 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 only washing with water is sufficient.

The organic-inorganic hybrid alignment layer removing composition of the present invention can be usefully used in the process of removing the organic-inorganic hybrid alignment layer of a semiconductor or electronic product, especially 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

Examples 1-6 and Comparative Examples 1-7: Preparation of Organic-Inorganic Hybrid Alignment Film-Removing Composition

The components shown in Table 1 were mixed at the corresponding 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 Polyhydric alcohol water Kinds amount Kinds amount Kinds amount Example 1 KOH 0.1 MTG 30 Glycerin 50 Balance Example 2 KOH 3 BDG 60 Glycerin 30 Balance Example 3 KOH 5 MTG 80 Glycerin 10 Balance Example 4 NaOH 3 MTG 60 Glycerin 30 Balance Example 5 KOH 3 BDG 60 PEG 30 Balance Example 6 KOH / TMAH 1.5 / 1.5 BDG 60 Glycerin 30 Balance Comparative Example 1 - - MTG 20 Glycerin 50 Balance Comparative Example 2 KOH 10 MTG 20 Glycerin 50 Balance Comparative Example 3 KOH 5 - - Glycerin 30 Balance Comparative Example 4 KOH 0.1 MTG 60 - - Balance Comparative Example 5 KOH 3 MTG 90 Glycerin 5 Balance Comparative Example 6 KOH 3 MTG 30 Glycerin 60 Balance Comparative Example 7 KOH 3 BDG 20 Glycerin 30 Balance

KOH: Potassium Hydroxide

NaOH: Sodium Hydroxide

BDG: diethylene glycol monobutyl ether

MTG: triethylene glycol monomethyl ether

PEG: Polyethylene glycol

TMAH: tetramethyl ammonium hydroxide

Experimental Example: Evaluation of Properties of Organic-Inorganic Hybrid Alignment Film-Removing Composition

1) Evaluation of Removal Force of Organic-Inorganic Hybrid Alignment Layer

In order to evaluate the organic-inorganic hybrid alignment layer removal ability, a glass substrate coated with an organic-inorganic hybrid alignment layer (Butyl-Si- (O-Me) 3) was prepared in a size of 1.5 cm × 6 cm. The prepared substrates were immersed in the compositions of Examples 1 to 6 and Comparative Examples 1 to 7 for 1 minute and 3 minutes, and then washed. After washing for 30 seconds with ultrapure water and dried with nitrogen, the evaluation results are shown in Table 2 below.

<Evaluation Criteria>

○: when the organic-inorganic hybrid type alignment film is removed,

?: When about 50% was removed,

X: When no removal was made

In addition, the results before and after removing the organic-inorganic hybrid alignment layer with the cleaning liquid composition of Example 1 are shown in Figs.

2) aluminum etching rate measurement

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

Al etching rate (A / min) Organic-inorganic hybrid type alignment film removal force 1 minute 3 minutes Example 1 0.33 △ ○ Example 2 0.95 ○ ○ Example 3 1.32 ○ ○ Example 4 1.22 ○ ○ Example 5 0.75 ○ ○ Example 6 1.23 ○ ○ Comparative Example 1 0.07 × × Comparative Example 2 9.23 ○ ○ Comparative Example 3 1.21 × △ Comparative Example 4 7.79 ○ ○ Comparative Example 5 7.92 ○ ○ Comparative Example 6 0.21 × × Comparative Example 7 1.02 × △

From the test results of Table 2, the composition of Examples 1 to 6, which is the cleaning composition of the present invention, has a superior organic-inorganic hybrid type alignment film removal force at room temperature, and a method for aluminum, compared to the compositions of Comparative Examples 1 to 7 It was confirmed that the castle is generally excellent.

Claims (10)

(A) an inorganic alkali compound;
(B) one or two or more organic solvents;
(C) aliphatic polyhydric alcohols;
And remaining amount of water, characterized in that the organic-inorganic hybrid type alignment film removal composition. The method of claim 1,
An organic-inorganic hybrid type alignment film removal composition, further comprising an organic alkali compound. The method of claim 1,
(A) 0.1 to 5% by weight of an inorganic alkali compound;
(B) 30 to 80% by weight of one or two or more organic solvents;
(C) 10 to 50% by weight aliphatic polyhydric alcohol;
And remaining amount of water, characterized in that the organic-inorganic hybrid type alignment film removal composition. 3. The method according to claim 1 or 2,
The inorganic alkali 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 type alignment film removal composition. 3. The method of claim 2,
The organic alkali compound is tetramethyl ammonium hydroxide (CH ₃ ) ₄ NOH, tetraethyl ammonium hydroxide (C ₂ H ₅ ) ₄ NOH, tetrapropylammonium hydroxide Tetrapropyl ammonium hydroxide, (C ₃ H ₇ ) ₄ NOH, tetrabutyl ammonium hydroxide, (C ₄ H ₉ ) ₄ NOH, carbonate, phosphate, ammonia and alkylamine, allylamine, alkanes An organic-inorganic hybrid alignment layer removing composition, characterized in that any one or a mixture of two or more selected from the group consisting of amines selected from the group consisting of olamines, alkoxyamines and cyclic amines. The method according to claim 2 or 5
The organic-alkali compound contains 0.1 wt% to 5 wt% of an organic-inorganic hybrid alignment layer removing composition. 3. The method according to claim 1 or 2,
The organic solvent is 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-methylformamide, dimethylacetamide (DMAc), N-methylacetamide, diethylacetamide (DEAc), N-methyl pyrrolidone (NMP), N-ethyl pyrrolidone (NEP), N- Removal of organic-inorganic hybrid alignment layer, characterized in that any one or a mixture thereof selected from the group consisting of propyl pyrrolidone (NPP), N-hydroxymethyl pyrrolidone, N-hydroxyethyl pyrrolidone and the like Composition. 3. The method according to claim 1 or 2,
The aliphatic polyhydric alcohol is any one or a mixture of two or more selected from the group consisting of glycerol, glucose, mannose, galactose, sorbitan, mannitol and polyethylene glycol. 3. The method according to claim 1 or 2,
An organic-inorganic hybrid alignment layer removing composition further comprising any one or a mixture of two or more selected from the group consisting of nonionic surfactants, cationic surfactants and anionic surfactants. A method for manufacturing an array substrate for a liquid crystal display device comprising the step of cleaning the substrate using the organic-inorganic hybrid type alignment film removing composition of claim 1.

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