KR101205471B1 - Photosensitive resin composition for tft-lcd - Google Patents

Abstract

The present invention relates to a photosensitive resin composition for forming a pattern of a liquid crystal display device, a method for forming a pattern using the same, and a liquid crystal display device manufactured by the method. More specifically, the photosensitive resin composition includes a) an alkali-soluble resin. ; b) photosensitizers; c) a compound represented by Formula 1; And d) an organic solvent.

Photosensitive resin composition, alkali-soluble resin, photosensitive agent, adhesive improving agent, organic solvent

Description

Photosensitive resin composition for liquid crystal display elements {PHOTOSENSITIVE RESIN COMPOSITION FOR TFT-LCD}

1 is a 45 ° C cross-sectional photograph of a molybdenum-deposited wafer according to a result of evaluating substrate adhesion properties of Example 1 according to the present invention.

FIG. 2 is a 45 ° C cross-sectional photograph of a molybdenum-deposited wafer according to a result of evaluating substrate adhesion properties of Comparative Example 1 according to the present invention. FIG.

The present invention relates to a positive photosensitive resin composition comprising an alkali-soluble resin, a photosensitive agent, a compound represented by the formula (1), and an organic solvent. More specifically, defects in the etching process and the stripping process that follow by including in the photosensitive resin composition an adhesive improving agent having excellent adhesion properties to the metal film, semiconductor film, and protective film forming the TFT (Thin Film Transistor) pattern of the liquid crystal display device. It is related with the photosensitive resin composition which improved significantly.

In the TFT circuit manufacturing process of the liquid crystal display device, a photosensitive resin composition is uniformly applied to a conductive metal film such as aluminum, copper, and molybdenum, a semiconductor film such as amorphous silicon, or an insulating film such as a silicon oxide film or a silicon nitride film. Applying and baking to form a photoresist film, selectively exposing and developing the photoresist pattern to form a photoresist pattern, and then wet or dry the conductive metal film, semiconductor film or insulating film using the patterned photoresist film as a mask. After etching to transfer the fine circuit pattern to the lower photoresist layer, the process proceeds to the step of removing the unnecessary photoresist layer with a stripper.

In the above process, when the adhesion property between the photosensitive resin composition or the photoresist film and the lower substrate is very important and lack adhesion, the photoresist pattern is lost due to the high spray pressure of the developing process, or the fine circuit pattern transfer through etching. In the process, the etching solution penetrates between the lower substrate and the photoresist film, thereby causing a defect in which the pattern CD (Critical Dimension) is changed.

Various photosensitive resin compositions have been developed to satisfy such adhesion characteristics, and are specifically as follows.

In JP-A-194-027657, a benzimidazole or polybenzimidazole compound was added to the photosensitive resin composition, and in JP-A-2000-171968, an N-substituted benzotriazole-based compound was used. In Korean Patent Laid-Open No. 10-2006-0020668, there is an example in which a sulfonyl group-substituted nitrogen compound or a thiadiazole compound is added to improve adhesion. However, the above compounds still have much room for improvement in adhesion, and the photo properties change during long-term storage due to precipitation of particulate matter from the photosensitive resin composition or binding with a photosensitive agent or alkali-soluble resin component or reaction during long-term storage. There is a problem of poor stability.

In view of the problems of the prior art, an object of the present invention is to provide a photosensitive resin composition having excellent storage stability and excellent adhesion to a lower substrate.

According to an aspect of the present invention,

a) 3 to 30 parts by weight of alkali-soluble resin;

b) 1 to 10 parts by weight of the photosensitizer;

c) 0.01 to 1 part by weight of a compound represented by Formula 1; And

d) 59 to 95.99 parts by weight of an organic solvent;

It provides a photosensitive resin composition comprising a.

[Formula 1]

In Formula 1,

R ₁ is an alkyl group having 1 to 12 carbon atoms.

In addition,

a) coating and prebaking a photosensitive resin composition comprising an alkali soluble resin, a photosensitive agent, a compound represented by Formula 1, and an organic solvent on a substrate; And

b) forming a photoresist pattern through selective exposure and development of the formed photoresist film;

It provides a method of patterning a photoresist comprising a.

In addition, the present invention provides a liquid crystal display assistant comprising a photoresist pattern produced by the above method.

In addition,

a) coating and prebaking a photosensitive resin composition comprising an alkali soluble resin, a photosensitive agent, a compound represented by Formula 1, and an organic solvent on a substrate;

b) forming a photoresist pattern through selective exposure and development of the formed photoresist film;

c) postbating the photoresist pattern: and

d) patterning the substrate by etching and stripping the photoresist pattern as a mask;

It provides a method of patterning a substrate comprising a.

The present invention also provides a liquid crystal display device comprising a patterned substrate manufactured by the above method.

Hereinafter, the present invention will be described in detail.

The present invention provides a photosensitive resin composition comprising (a) an alkali-soluble resin, (b) a photosensitizer, (c) a compound represented by the formula (1) providing adhesion to the metal film under the photoresist, and (d) an organic solvent. to provide.

Alkali-soluble resin of (a) used in the photosensitive resin composition of this invention is a matrix resin which forms a photoresist film, and uses the novolak resin which has the dissolution characteristic in alkaline developing solution. Novolac resin is synthesized by condensation reaction between phenols and aldehydes. As phenols, phenol, 4-t-butylphenol, 4-t-octylphenol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, o -Cresol, m-cresol, p-cresol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3-methyl-6-t-butyl Phenol, 2-naphthol, 1,3-dihydroxynaphthalene or bisphenol-A and the like are used, and aldehydes include formaldehyde, paraformaldehyde, acetoaldehyde, benzaldehyde or phenylaldehyde. The phenols and aldehydes may be used alone or in a mixture of two or more thereof. As the catalyst used for the condensation reaction, organic acids such as oxalic acid, p-toluenesulfonic acid and trichloroacetic acid or inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, or metal salts such as zinc chloride, aluminum chloride, magnesium acetate and zinc acetate are used. The molecular weight of the novolak resin used in the photosensitive resin composition of this invention uses the product of the weight average molecular weights 2,500-15,000 range on a polystyrene conversion basis.

The alkali-soluble resin is preferably 3 to 30 parts by weight based on the total weight of the composition. If the alkali-soluble resin is less than 3 parts by weight, the adhesiveness to the substrate is lowered. If the alkali-soluble resin is more than 30 parts by weight, it is difficult to obtain a smooth surface.

The photosensitive agent of (b) used in the photosensitive resin composition of the present invention serves to insolubilize the alkali-soluble resin in an alkaline developer, and after exposure, the photosensitive agent is changed into a structure that is well soluble in an alkaline developer so that the exposed portion is developed. It is a key photosensitive component that makes it possible. The photosensitive agent is generally called PAC (Photo Active Compound), and is prepared by esterifying quinonediazides and polyphenols. The quinone diazides include 1,2-diazidonaphthoquinone-4-sulfonyl chloride, 1,2-diazidonaphthoquinone-5-sulfonyl chloride and 1,2-diazidonaphthoquinone-6- Sulfonyl chloride is used, and polyphenols are 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,3 , 4,3 ', 4', 5'-hexahydroxybenzophenone, 4,4 '-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) Bisphenol, bisphenol-A, methyl gallate, propyl gallate, pyrogallol-acetone reaction condensate, phenol novolak resin, m-cresol novolak resin, p-cresol novolak resin and polyvinylphenol resin One or more compounds selected may be used in combination. The reaction is prepared by mixing quinonediazides and polyphenols in a specific molar ratio in the presence of a solvent such as dioxane or acetone, followed by dropwise addition of a catalyst such as triethylamine, followed by esterification. In general, the esterification rate is 10 to 90 mol% of the molar ratio of quinonediazides to the hydroxyl groups of the polyphenols, but preferably 40 to 80 mol% of the reactant is used.

The photosensitive agent is preferably 1 to 10 parts by weight based on the total weight of the composition. If the photosensitizer is less than 1 part by weight, there is a problem that the photosensitivity is increased and the pattern shape is deteriorated. If the photosensitive agent is more than 10 parts by weight, the photosensitivity and heat resistance are deteriorated.

(C) The compound represented by the formula (1) used in the photosensitive resin composition of the present invention serves to provide adhesion to the photoresist and the lower metal film. Specific examples of the compound represented by the formula (1) to impart the adhesion, 5-carboxybenzotriazole methyl ester, 5-carboxybenzotriazole ethyl ester, 5-carboxybenzotriazole propyl ester, 5-carboxybenzotriazole Preference is given to one or more compounds selected from butyl esters, 5-carboxybenzotriazole octyl esters and 5-carboxybenzotriazole dodecyl esters and the like. The adhesion improving agent combines with molybdenum, copper or aluminum, which is a wiring material of the TFT circuit, through chemical adsorption, thereby improving adhesion between the photoresist and the lower substrate. The compound represented by Formula 1 is preferably 0.01 to 1 part by weight based on the total weight of the photosensitive resin composition. If the compound represented by Formula 1 is less than 0.01 parts by weight, there is a problem that the adhesion to the substrate is lowered, and if it exceeds 1 part by weight there is a problem that the storage stability and coating properties of the composition is lowered.

The organic solvent of (d) used in the photosensitive resin composition of the present invention serves to dissolve the alkali-soluble resin, the photosensitive agent and the compound represented by the formula (1) to enable coating on the substrate. Specific examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether Glycol ethers such as diethylene glycol monobutyl ether and dipropylene glycol monomethyl ether; Methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, 3-methoxymethyl propionate, ethyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl Ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate and diethylene One or more compounds selected from the group consisting of acetates such as propylene glycol monomethyl ether acetate can be used in combination.

The photosensitive resin composition of this invention may further contain additives, such as a film | membrane improvement agent, surfactant, a sensitizer, or dye as needed. The film improver may be added to improve the thermal and mechanical properties of the photoresist film, and a plasticizer, an acrylic resin, a polystyrene derivative, or a polyvinyl methyl ether may be used. The surfactant is added for coating uniformity and stain removal of the photoresist film, and a nonionic surfactant, a silicone-based surfactant, or a fluorine-based surfactant is used. A sensitizer is used to improve the sensitivity of the photoresist, and may be 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone or 4,4 '-(1- ( 4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol and the like. Dyes include Victoria Pure Blue, Crystal Violet or Methyl Violet.

In addition,

a) coating and prebaking a photosensitive resin composition comprising an alkali soluble resin, a photosensitive agent, a compound represented by Formula 1, and an organic solvent on a substrate; And

b) forming a photoresist pattern through selective exposure and development of the formed photoresist film;

It provides a method of patterning a photoresist comprising a.

The TFT circuit of the liquid crystal display element is composed of a thin film transistor composed of a gate electrode, a gate insulating film, a semiconductor film (amorphous silicon), a source / drain electrode, a protective film, a gate bus line, a data bus line, and a pixel electrode. The TFT array is formed by arranging the unit pixels thus constructed in matrix. The TFT array is manufactured by performing a photolithography process to pattern each stacked film into a shape having a predetermined shape, and is usually repeated 4 to 5 times. Each photolithography process is subdivided into coating, prebaking, exposure, development, postbaking, etching and stripping processes.

Step a) is a step of coating and prebaking the photosensitive resin composition comprising an alkali-soluble resin, a photosensitive agent, a compound represented by Formula 1, and an organic solvent on a substrate. The substrate may be a metal substrate such as aluminum, molybdenum, copper, ITO or chromium, a semiconductor film such as silicon nitride, amorphous silicon, or an insulating film such as silicon oxide film or silicon nitride film, but is not limited thereto. The photosensitive resin including the alkali-soluble resin, the photosensitizer, the compound represented by Formula 1, and an organic solvent is coated on a substrate using a roll coating, spin coating, slit & spin coating or slit coating method. After coating and prebaking to remove the organic solvent, a photoresist film is formed. At this time, the film thickness is about 1 to 3 µm, and the prebaking is preferably performed at 80 to 115 ° C for 1 to 5 minutes.

Step b) is a step of forming the photoresist pattern through selective exposure and development of the prepared photoresist layer. The exposure is performed by using a photolithography apparatus such as a mask aligner, stepper or scanner, a photoresist of a single or mixed light source of g-line (436 nm), h-line (405 nm) or i-line (365 nm) through a pattern mask. It is exposed on the top. The exposure energy is determined according to the sensitivity of the photoresist, and usually 20 to 200 mJ / cm ² is exposed. The photoresist of the exposed portion is removed by forming a desired pattern by dipping or spraying the substrate after exposure with a developer. As the developer, inorganic alkali compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, and fortesilicate, or organic alkali aqueous solutions such as triethylamine, triethanolamine, tetramethylammonium hydroxide and tetraethylammonium hydroxide can be used. However, in manufacturing liquid crystal display devices, tetramethylammonium hydroxide is widely used due to metal contamination, metal corrosion, and the like. Tetramethylammonium hydroxide is used in the form of 2.0 to 3.0% by weight of an aqueous solution, preferably sprayed at 20 to 30 ° C for 30 to 90 seconds, washed with ultrapure water for 60 to 120 seconds, and then dried.

The present invention provides a liquid crystal display device comprising a photoresist pattern manufactured by the above method.

In addition,

a) coating and prebaking a photosensitive resin composition comprising an alkali soluble resin, a photosensitive agent, a compound represented by Formula 1, and an organic solvent on a substrate;

b) forming a photoresist pattern through selective exposure and development of the formed photoresist film;

c) postbaking the photoresist pattern: and

d) patterning the substrate by etching and stripping the photoresist pattern as a mask;

It provides a method of patterning a substrate comprising a.

Steps a) and b) are performed in the same manner as the method for manufacturing the photoresist pattern.

Step c) is a step of post-baking the prepared photoresist pattern. The photoresist may be post-baked before etching after the development of the photoresist pattern is completed, thereby enhancing adhesion to the lower substrate and enhancing resistance to the etching solution. Post-baking conditions are performed for 2 to 5 minutes at 120-150 degreeC. However, post-baking the photoresist causes thermal denaturation of the photoresist component and the alkali-soluble resin component, resulting in poor solubility in organic solvents, resulting in defects such as photoresist residues remaining in the strip process. Therefore, when using the photosensitive resin composition containing the compound represented by the formula (1) of the present invention it can be omitted or minimized the post-baking process.

Step d) is a step of etching and stripping the substrate using the photoresist pattern as a mask. After the photoresist pattern is formed as described above, the lower substrate is etched by using the photoresist as a mask, and the pattern is transferred. A wet etching using a liquid etching solution or a plasma etching is performed according to the lower substrate film quality. Metal substrates such as aluminum, molybdenum, copper, ITO, and chromium use liquid etching solutions such as a mixed acid solution of phosphoric acid / nitric acid / acetic acid, an aqueous solution of hydrogen peroxide and an aqueous solution of oxalic acid, and a semiconductor film such as silicon nitride and amorphous silicon, or Insulating films such as silicon oxide films and silicon nitride films are subjected to plasma etching.

After the etching is completed, the photoresist film is stripped off. The stripper uses a solvent mixture such as monoethanolamine, alkanolamine of 2- (2-aminoethoxy) ethanol, N-methylpyrrolidone, dimethylacetamide or diethylene glycol monoethyl ether, and the like. After spraying the stripper for 2 to 5 minutes at, it is preferable to wash with ultrapure water for 60 to 120 seconds and then dry.

The present invention also provides a liquid crystal display device comprising a patterned substrate manufactured by the above method.

When the TFT circuit pattern of the liquid crystal display device is formed using the photosensitive resin composition according to the present invention, the adhesion characteristics with the lower substrate may be excellent, thereby significantly reducing the pattern transfer defect in the etching process, and to improve the adhesion. The post-baking process can be omitted or minimized to increase productivity through reduced manufacturing process. In addition, by minimizing photoresist denaturation, it is expected that the residue and foreign material defects in the strip process will be drastically improved to contribute to the yield increase.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are merely to illustrate the invention and the scope of the present invention is not limited to the following examples. In the following Examples and Comparative Examples, unless otherwise indicated, the component ratio of each composition is by weight.

< Example  1>

1 g of novolak resin having a polystyrene reduced weight average molecular weight of 4,500 and 2,3,4,4'-tetrahydroxybenzophenone prepared by mixing m-cresol with p-cresol weight ratio 5: 5 and 1,2-diazido 4 g of a photosensitive agent prepared by reacting 3 mol of naphthoquinone-5-sulfonyl chloride and 0.2 g of 5-carboxybenzotriazole butyl ester as an adhesive improving agent were dissolved in 77.8 g of propylene glycol monomethyl ether acetate (PGMEA), and then filtered to 0.2 µm. The photosensitive resin composition A was manufactured.

With respect to the photosensitive resin composition prepared above, the stability over time and substrate adhesion properties were evaluated in the following manner.

1) Evaluation of stability over time

The photo characteristic evaluation was performed about the said photosensitive resin composition by the following method, and stability was evaluated by measuring the change with time of a photo characteristic. First, the photosensitive resin composition was spin-coated on a 4 ”silicon wafer and then prebaked at 110 ° C. for 180 seconds on a hot plate to form a photoresist film having a thickness of 2 μm. Was pre-baked to complete sequential exposure to 1mJ / cm ² intervals from 20mJ / cm ² to 120mJ / cm ² for a wafer to G-line stepper Nikon NSR 1505 G4, a mask used at this time, the distance from 1㎛ 1㎛ to 10㎛ The line / space pattern and the circular pattern are repeated. After developing at 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, the mixture was washed and dried for 60 seconds with ultrapure water to form a photoresist pattern. The optimum exposure energy for transferring the same pattern as the line / space pattern 6 µm of the mask was found to be 42 mJ / cm ^2, and the residual film ratio of the photoresist film in the non-exposed part after development was 98.5%. After the photosensitive resin composition was stored at 23 ° C. for 30 days, the same photo properties evaluation was performed. As a result, the optimum exposure energy was 44 mJ / cm ² , and the residual film ratio was 98.7%. The stability over time was evaluated based on the following criteria.

○: excellent stability over time (within 5% change in photo properties)

(Triangle | delta): Slightly inferior in stability with time (5 to 10% of photo characteristic change)

X: Poor stability over time (10% or more of photo characteristic change)

2) Evaluation of substrate adhesion

The photosensitive resin composition was spin-coated on each of molybdenum 1000 Å deposited 4 ”silicon wafers and copper 1000 Å deposited 4” silicon wafers, and then prebaked at 110 ° C. for 180 seconds on a hot plate to form a 2 μm thick photoresist film. The prebaked wafer was exposed to 42mJ / cm ² , which is the optimum exposure energy in the stability evaluation, using a G-line stepper Nikon NSR 1505 G4. The mask used at this time was line / space at 1 μm intervals from 1 μm to 10 μm. The pattern and the circular pattern are repeated. After developing at 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, the mixture was washed and dried for 60 seconds with ultrapure water to form a photoresist pattern. Subsequently, each wafer was etched with etching liquid. The molybdenum deposited wafer was carried out at 23 ° C. for 10 seconds with an aqueous solution of nitric acid / phosphate / acetic acid = 10% / 65% / 5%, and the copper deposited wafer was 50% hydrogen peroxide / glycolic acid / iminodiacetic acid / 5-aminotetrazole. Etching was performed at 23 ° C. for 50 seconds with an ultrapure water = 45% / 2% / 1% / 1% / 51% aqueous solution. After etching, the resultant was washed with ultrapure water for 60 seconds and then dried. For each wafer that was etched, the cross section was observed with an electron microscope (FE-SEM) to observe the degree of erosion to the bottom of the photoresist. Erosion of 0.33 µm was observed on the molybdenum deposited wafer and 0.28 µm on the copper deposited wafer. As the erosion was more severe, the substrate adhesion property was inferior, and the evaluation was made based on the following criteria.

○: excellent adhesion performance (within 0.7㎛)

Δ: somewhat inferior in adhesion performance (0.7 μm to 1.5 μm)

×: poor adhesion performance (1.5 μm or more)

< Example  2 to 5 and Comparative example  1 to 3>

Table 1 shows the component ratios for Examples 2 to 5 and Comparative Examples 1 to 3, and the photosensitive resin composition was evaluated in the same manner as in Example 1 to show the results.

division
Composition Components (wt%) Properties a) alkali
Soluble resin b) photosensitizer c) adhesion
Improver d) organic
menstruum depreciation
stability
Mo
Adhesiveness
Cu
Adhesiveness Kinds amount Kinds amount Kinds amount Kinds amount


room
city
Yes
One
A-1
18
B-1
4
C-1
0.2
PEMEA
77.8
○
○
○
2
A-2
17
B-2 2 C-1 0.5 PEMEA
77.2
○ ○ ○
B-3 3 C-2 0.3 3
A-3
16
B-3
6
C-2
0.1
PEMEA
77.9
○
○
○
4
A-2 9 B-1 4
C-2
0.5
PEMEA
77.5
○
○
○
A-3 9 5
A-1
17
B-1 2 C-3
0.5
PEMEA
77.5
○
○ ○
B-2 3
ratio
School
Yes One
A-1
18
B-1
4
-
-
PEMEA
78.0
○
×
×
2
A-1
18
B-1
4
C-4
0.5
PEMEA
77.5
×
○
△
3
A-3
16
B-3
6
C-5
0.5
PEMEA
77.5
△
○
×

week)

A-1: m-cresol / p-cresol = 5: 5, weight average molecular weight = 4,500 novolak resin

A-2: m-cresol / p-cresol = 6: 4, weight average molecular weight = 6,300 novolak resin

A-3: m-cresol / p-cresol = 4: 6, weight average molecular weight = 4,200 novolak resin

B-1: 1 mol of 2,3,4,4'-tetrahydroxybenzophenone and 3 mol of 1,2-diazidonaphthoquinone-5-sulfonyl chloride

B-2: 1 mol of 2,3,4,4'-tetrahydroxybenzophenone and 1,2-diazidonaphthoquinone-5-sulfonyl chloride

B-3: 1 mol of 2,3,4-trihydroxybenzophenone and 2 mol of 1,2-diazidonaphthoquinone-5-sulfonyl chloride

C-1: 5-carboxybenzotriazole butyl ester

C-2: 5-carboxybenzotriazole octyl ester

C-3: 5-carboxybenzotriazole dodecyl ester

C-4: benzimidazole

C-5: Hexamethoxymethylmelamine (Cymel-303)

As shown in Table 1, in the case of the photosensitive resin composition of Examples 1 to 5 including at least one adhesive improver selected from the group consisting of the compound represented by Formula 1, or when there is no adhesive improver or used as an existing adhesive improver Compared with Comparative Examples 1 to 3 containing benzimidazole or hexamethoxymethylmelamine, it was found that the stability with time and adhesion to molybdenum and copper substrates were very excellent.

As described above, the photosensitive resin composition of the present invention has excellent adhesion property with the lower substrate in manufacturing the liquid crystal display device, which can significantly reduce the pattern transfer defect in the etching process, and also has excellent storage stability over time for a long time. Even when used, there is an advantage that there is no alteration of the composition. In addition, it is possible to omit or minimize the post-baking process to improve the adhesiveness, which can be expected to improve productivity by reducing the manufacturing process, and by minimizing photoresist denaturation, it is possible to drastically improve the residue and foreign material defects in the strip process to increase the yield. There is an advantage to contribute.

Claims (19)

a) 3 to 30 parts by weight of alkali-soluble resin; b) 1 to 10 parts by weight of the photosensitizer; c) 0.01 to 1 part by weight of one or more compounds selected from the group consisting of 5-carboxybenzotriazole butyl ester, 5-carboxybenzotriazole octyl ester and 5-carboxybenzotriazole dodecyl ester; And d) 59 to 95.99 parts by weight of an organic solvent Photosensitive resin composition comprising a. The photosensitive resin composition of Claim 1 whose alkali-soluble resin compound of said a) is a novolak resin of the weight average molecular weights 2,500-15,000. The photosensitive resin composition of claim 1, wherein the photosensitive agent of b) is one or more compounds selected from the group consisting of esterification compounds of quinonediazides and polyphenols. The method of claim 3, wherein the quinonediazides are 1,2-diazidonaphthoquinone-4-sulfonylchloride, 1,2-diazidonaphthoquinone-5-sulfonylchloride or 1,2-diazidonaph. Toquinone-6-sulfonylchloride and the polyphenols are 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,3,4,3 ', 4', 5'-hexahydroxybenzophenone, 4,4 '-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) Ethylidene) bisphenol, bisphenol-A, methylgallate, propyl gallate, pyrogallol-acetone reaction condensate, phenol novolak resin, m-cresol novolak resin, p-cresol novolak resin or polyvinylphenol resin Phosphorus photosensitive resin composition. delete The method of claim 1, wherein the organic solvent of d) is acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene Glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, methyl acetate, ethyl Acetate, Butyl Acetate, Methyl Propionate, Ethyl Propionate, 3-methoxymethyl Propionate, Ethyl Lactate, Ethylene Glycol Monomethyl Ether Acetate, Ethylene Glycol Monoethyl Ether Acetate, Ethylene Glycol Monopropyl Ether Acetate, Ethylene Glycol Monobutyl Ether Acetate Yate, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol monomethyl ether acetate The photosensitive resin composition is one or more compounds selected from the group. a) one or more compounds selected from the group consisting of alkali-soluble resins, photosensitizers, 5-carboxybenzotriazole butyl esters, 5-carboxybenzotriazole octyl esters and 5-carboxybenzotriazole dodecyl esters on a substrate, and Coating and prebaking the photosensitive resin composition comprising the organic solvent; And b) forming a photoresist pattern through selective exposure and development of the formed photoresist film; Patterning method of photoresist comprising a. The method of claim 7, wherein the substrate is a metal substrate, a semiconductor film or an insulating film. The method of claim 7, wherein the coated film has a thickness of 1 to 3 μm. The method of claim 7, wherein the prebaking is performed at 80 to 115 ° C. for 1 to 5 minutes. The method of claim 7, wherein the exposure conditions are 20 to 200 mJ / cm ² . A liquid crystal display device comprising a photoresist pattern manufactured by the method of claim 7. a) one or more compounds selected from the group consisting of alkali-soluble resins, photosensitizers, 5-carboxybenzotriazole butyl esters, 5-carboxybenzotriazole octyl esters and 5-carboxybenzotriazole dodecyl esters on a substrate, and Coating and prebaking the photosensitive resin composition comprising the organic solvent; b) forming a photoresist pattern through selective exposure and development of the formed photoresist film; c) postbating the photoresist pattern: and d) patterning the substrate by etching and stripping the photoresist pattern as a mask; Patterning method of the substrate comprising a. The method of claim 13, wherein the substrate is a metal substrate semiconductor film or an insulating film. The method of claim 13, wherein the coated film has a thickness of 1 to 3 μm. The method of claim 13, wherein the prebaking is performed at 80 to 115 ° C. for 1 to 5 minutes. The method of claim 13, wherein the exposure conditions are 20 to 200 mJ / cm ² . The method of claim 13, wherein the post bake is performed at 120 to 150 ° C. for 2 to 5 minutes. A liquid crystal display device comprising a patterned substrate manufactured by the method of claim 13.

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