KR101326595B1 - Photosensitive resin composition and method of manufacturing a thin film transistor substrate and method of manufacturing a common electrode substrate using the same - Google Patents

Abstract

The photosensitive resin composition comprises (A) 5 to 60% by weight of isobornyl carboxylate compound, 10 to 40% by weight of unsaturated carboxylic acid, unsaturated carboxylic anhydride or a mixture thereof, 20 to 40% by weight of epoxy group-containing unsaturated compound and olefin 100 parts by weight of an acrylic copolymer obtained by copolymerizing 20 to 40% by weight of an unsaturated compound; And (B) 5 to 100 parts by weight of 1,2-quinonediazide compound. The photosensitive resin composition may prevent the unevenness of the organic film pattern when the organic film pattern is formed in an acid structure.

Description

PHOTOSENSITIVE RESIN COMPOSITION AND METHOD OF MANUFACTURING A THIN FILM TRANSISTOR SUBSTRATE AND METHOD OF MANUFACTURING A COMMON ELECTRODE SUBSTRATE USING THE SAME}

1 is a cross-sectional view of an organic film pattern having a conventional acid structure.

2A to 2G are cross-sectional views illustrating a method of manufacturing a thin film transistor substrate according to an exemplary embodiment of the present invention.

3A to 3C are cross-sectional views illustrating a method of manufacturing a common electrode substrate according to an exemplary embodiment of the present invention.

4 is a cross-sectional view of an organic film pattern formed using the photosensitive resin composition according to the present invention.

The present invention relates to a photosensitive resin composition, a method of manufacturing a thin film transistor substrate using the same, and a method of manufacturing a common electrode substrate. More specifically, the present invention relates to a photosensitive resin composition capable of improving the flatness of an organic film surface, a method of manufacturing a thin film transistor substrate using the same, and a method of manufacturing a common electrode substrate.

In general, a method of forming an alignment layer for orienting a liquid crystal in a liquid crystal display device includes a horizontal alignment method such as twisted nematic (TN) mode and an in plane switch (IPS) mode, and a VA according to a liquid crystal alignment direction in an initial state where an electric field is not applied. It is classified into a vertical alignment method such as (Vertical Alignment) mode or Patterned Vertical Alignment (PVA) mode.

Currently, while the VA mode implements a high wide viewing angle using a multi-domain and a compensation film, there is a problem of showing a slow response time compared to the IPS and TN modes. In driving the liquid crystal using a fringe field in the VA mode, a method of forming an organic layer (orientation layer) in an acid structure to improve a response speed has been proposed (Patent Application 2004-0046102).

1 is a cross-sectional view of an organic film pattern having a conventional acid structure. Referring to FIG. 1, although the response speed of the liquid crystal may be increased by the organic layer having an acid structure, the unevenness 15 may be generated on the acid forming surface 10 when the acid structure is formed. When the irregularities 15 are generated on the acid forming surface 10, the behavior of the liquid crystal becomes uneven.

In view of the above problems, the present invention provides a photosensitive resin composition capable of preventing the occurrence of irregularities on the surface of an organic film pattern having an acid structure.

       Another object of the present invention is to provide a method for manufacturing a thin film transistor substrate using the photosensitive resin composition.

       Still another object of the present invention is to provide a method of manufacturing a common electrode substrate using the photosensitive resin composition.

Photosensitive resin composition according to an embodiment of the present invention is 5 to 60% by weight of isobornyl carboxylate compound, unsaturated carboxylic acid, unsaturated carboxylic anhydride or mixtures thereof 10 to 40% by weight, epoxy group-containing unsaturated compound 20 It includes 100 parts by weight of the acrylic copolymer (A) and 5 to 100 parts by weight of the 1,2-quinonediazide compound (B) obtained by copolymerizing from 40 to 40% by weight and 20 to 40% by weight of the olefinically unsaturated compound.

       In another embodiment, a method of manufacturing a thin film transistor substrate includes forming a gate metal pattern including a gate electrode on a base substrate, forming a gate insulating layer on the gate metal pattern, and a gate corresponding to the gate electrode. Forming a channel layer on the insulating layer, forming a source metal pattern including a source electrode and a drain electrode on the gate insulating layer on which the channel layer is formed, covering the gate insulating layer, the channel layer, and the source metal pattern, Forming an overcoating layer including a contact hole exposing a part of the substrate, forming a pixel electrode layer electrically connected to the drain electrode through the contact hole, and having a boundary portion that is a domain dividing means, on the pixel electrode layer (A 5 to 60% by weight of isobonyl carboxylate compound; 10 to 40% by weight unsaturated carboxylic acid, unsaturated carboxylic anhydride or mixtures thereof; 20 to 40% by weight of an epoxy group-containing unsaturated compound; And applying a photosensitive resin composition comprising 100 parts by weight of an acrylic copolymer obtained by copolymerizing 20 to 40% by weight of an olefinically unsaturated compound and 5 to 100 parts by weight of (B) 1,2-quinonediazide compound and the photosensitive resin. Exposing and developing the composition to form an inclined film of tapered structure.

      In another embodiment, a method of manufacturing a common electrode substrate includes forming a light blocking layer on a base substrate, forming a color filter layer covering a portion of the light blocking layer on the base substrate, the light blocking layer, and the Forming an insulating layer covering the color filter layer, forming a common electrode layer having a boundary portion which is a domain dividing means on the insulating layer, and (A) 5 to 60% by weight of an isobornyl carboxylate compound on the common electrode layer; 10 to 40% by weight unsaturated carboxylic acid, unsaturated carboxylic anhydride or mixtures thereof; 20 to 40% by weight of an epoxy group-containing unsaturated compound; And applying a photosensitive resin composition comprising 100 parts by weight of an acrylic copolymer obtained by copolymerizing 20 to 40% by weight of an olefinically unsaturated compound and 5 to 100 parts by weight of (B) 1,2-quinonediazide compound and the photosensitive resin. Exposing and developing the composition to form an inclined film of tapered structure.

When the organic film is formed using the photosensitive resin composition according to the present invention, the organic film flows when the organic film pattern is formed to form a flat film without bending.

Hereinafter, the present invention will be described in detail.

In order to form an organic film pattern on a board | substrate, a board | substrate is wash | cleaned and the photosensitive resin composition is apply | coated on a board | substrate. The photosensitive resin composition is applied on a substrate by a spin coating method, a slit coating method or a slit / spin coating method. The coated photosensitive resin composition is dried to form an organic film pattern on the substrate by an exposure and development process. The formed organic film pattern is cured.

(A) an acrylic copolymer

The acrylic copolymer serves to prevent scum from occurring on the surface of the organic layer during development.

The acrylic copolymer may comprise i) an isobornyl carboxylate compound, ii) an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, or a mixture thereof, iii) an epoxy group-containing unsaturated compound and iv) an olefinically unsaturated compound. It can be obtained by polymerization in the presence of a solvent and a polymerization initiator.

When the content of the isobornyl carboxylate-based compound is less than 5% by weight relative to the total weight of the monomers, the heat resistance is inferior, whereas when it is more than 40% by weight, the solubility in aqueous alkali solution is inferior. Thus, the isobonyl carboxylate compound has a content of 5 to 60% by weight relative to the total weight of the total monomers. Preferably it has a content of 10 to 40% by weight. The i) isobonyl carboxylate compound includes a compound represented by the following formula (1). The following compounds may be used alone or in combination of two or more.

In the formula (1), X is an alkenyl group of C1-C10, and R1, R2, R3 and R4 are hydrogen or an alkyl group of C1-C10.

In addition, specific examples of the isobonyl carboxylate compound include isobonyl acrylate, isobonyl methacrylate, and the like.

Ii) if the content of the total monomers of the unsaturated carboxylic acid, the unsaturated carboxylic anhydride, or a mixture thereof is less than 10% by weight, it is difficult to dissolve in the aqueous alkali solution, whereas if it exceeds 35% by weight, the solubility in the aqueous alkali solution It becomes too large. Accordingly, the content of ii) unsaturated carboxylic acid, unsaturated carboxylic anhydride or mixtures thereof is 5 to 40% by weight based on the total total monomers. Preferably it is used in 10 to 30% by weight.

Examples of the above ii) unsaturated carboxylic acid include unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid. These may be used alone or in combination of two or more. It is preferable to use acrylic acid, methacrylic acid, or maleic anhydride excellent in copolymerization reactivity and the solubility with aqueous alkali solution among these.

If the content of the iii) epoxy group-containing unsaturated compound with respect to the total monomers is less than 10% by weight, the heat resistance of the resulting pattern tends to decrease, and if it exceeds 70% by weight, the storage stability of the copolymer is lowered. Therefore, the content of the iii) epoxy group-containing unsaturated compound with respect to the total monomers is 10 to 70% by weight. The content of the epoxy group-containing unsaturated compound is preferably 20 to 60% by weight.

As said epoxy-containing unsaturated compound, glycidyl acrylate, glycidyl methacrylate, glycidyl (alpha)-ethyl acrylate, glycidyl (alpha)-n-propyl acrylate, glycidyl (alpha)-n-butyl acrylate, acrylic acid (beta)- Methylglycidyl, methacrylic acid-β-methylglycidyl, acrylic acid-β-ethylglycidyl, methacrylic acid-β-ethylglycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid- 3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethyl acrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m -Vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like. These may be used alone or in combination of two or more. Preferably glycidyl methacrylate, methacrylic acid-β-methylglycidyl, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether , p-vinylbenzyl glycidyl ether or the like is preferable in terms of enhancing the copolymerization reactivity and the heat resistance of the obtained pattern.

When the amount of the olefinically unsaturated compound is less than 10% by weight of the total monomers, the storage stability of the acrylic copolymer tends to be lowered, and when it exceeds 70% by weight, the acrylic copolymer is difficult to dissolve in an aqueous alkali solution. Therefore, the content of the olefinically unsaturated compound with respect to the total monomer is 10 to 70% by weight. The content of the olefinically unsaturated compound is preferably 20 to 50% by weight.

Specific examples of the olefinically unsaturated compound include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate, cyclo Hexyl methacrylate, 2-methylcyclo hexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, dicyclopentanyloxyethyl methacrylate Latex, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl acrylate, isobornyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate Oxyethyl methacrylate, styrene, α-methyl styrene, m-methyl styrene, p-methyl styrene, b Nyl toluene, p-methyl styrene, 1,3-butadiene, isoprene 2,3-dimethyl 1,3-butadiene, and the like. These may be used alone or in combination of two or more. Preferably styrene, dicyclopentanyl methacrylate, or p-methoxystyrene is advantageous in terms of copolymerization reactivity and solubility in aqueous alkali solution.

  Examples of the solvent used for the polymerization of the acrylic copolymer include methanol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, and diethylene. Glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol methyl Ethyl Acetate, Propylene Glycol Ethyl Acetate, Propylene Glycol Propyl Ether Acetate, Propylene Glycol Butyl Ether Acetate, Propylene Glycol Methyl Ethyl Propionate, Propylene Glycol Ethyl Propionate, Propylene Glycol Recall propyl ether propionate, propylene glycol butyl ether propionate, toluene, xylene, methyl ethyl ketone, cyclohexanone, 4-hydroxy 4-methyl 2-pentanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate , 2-hydroxy ethyl propionate, 2-hydroxy 2-methyl methyl propionate, 2-hydroxy 2-methyl ethyl propionate, hydroxy methyl acetate, hydroxy ethyl acetate, hydroxy butyl acetate, methyl lactate, ethyl lactate, lactic acid Propyl, butyl lactic acid, 3-hydroxy methyl propionate, 3-hydroxy ethyl propionate, 3-hydroxy propyl propionate, 3-hydroxy butyl propionate, 2-hydroxy 3-methylbutyrate, methyl methoxy acetate, meth Ethyl oxyacetate, methoxy propyl acetate, methoxy butyl acetate, ethoxy acetate, ethyl ethoxy acetate, ethoxy acetate, butyl ethoxy acetate, methyl propoxy acetate, ethyl propoxy acetate, propoxy acetate Lofil, Butyl propoxy acetate, Butoxy acetate methyl, Butoxy acetate, Butoxy acetate propyl, Butoxy acetate, Butyl 2-methoxypropionate, 2-methoxypropionate, 2-methoxypropionate, 2- Butyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-part Propyl propyl propionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionic acid, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, 3-ethoxypropionic acid propyl, 3-ethoxypropionate butyl, 3-propoxypropionate methyl, 3-propoxypropionate propyl, 3-propoxypropionic acid propyl, 3-propoxypropionate butyl, Ethers such as methyl 3-butoxypropionate, ethyl 3-butoxy propionate, propyl 3-butoxypropionate and butyl 3-butoxypropionate. These may be used alone or in combination of two or more.

As a polymerization initiator used in the synthesis of the acrylic copolymer, a radical polymerization initiator is used, and specific examples thereof include 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvalle). Ronitrile)), 2,2'-azobis (4-methoxy 2,4-dimethylvaleronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), dimethyl 2,2'- Azobisisobutyrate etc. can be used.

The polystyrene reduced weight average molecular weight (Mw) of the (A) acrylic copolymer used by this invention is 5000-30,000, Preferably it is 5000-20,000. If the molecular weight is less than 5000, developability, residual film ratio, etc. of the formed organic film may be lowered, or the pattern shape, heat resistance, etc. may be inferior. When the molecular weight is more than 30,000, sensitivity may be reduced or the shape of the pattern may be rough. .

(B) 1,2-quinonediazide compound

In the photosensitive resin composition of this invention, (B) 1,2-quinone diazide compound is used as a photosensitive compound.

Specific examples of the 1,2-quinonediazide compound include 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, 1,2-quinonediazide 6-sulfonic acid ester, and the like. There is this.

The quinone diazide compound is obtained by reacting a naphthoquinone diazide sulfonic acid halogen compound and a phenol compound under a weak base.

Specific examples of the phenolic compound include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2 'or 4,4'-tetrahydroxybenzophenone, 2,3 , 4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy 4'-methylbenzophenone, 2,3, 4,4'-tetrahydroxy 3'-methoxybenzophenone, 2,3,4,2 'or 2,3,4,6'-pentahydroxybenzophenone, 2,4,6,3', 2 , 4,6,4 'or 2,4,6,5'-hexahydroxybenzophenone, 3,4,5,3', 3,4,5,4 'or 3,4,5,5'- Hexahydroxybenzophenone, bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, 1,1,1-tri (p-hydroxy Hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5 -Dimethyl 4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis ( 2,5- And the like, methyl 4-hydroxyphenyl) -2-hydroxy-phenyl-methane, which can be used alone or in combination of two or more.

In the synthesis of the compound, the esterification degree is preferably 50 to 85%, and when the esterification degree is less than 50%, the residual film ratio tends to be worse, and when it exceeds 85%, the storage stability may tend to be inferior.

When the content of the 1,2-quinone diazide compound is less than 5 parts by weight based on 100 parts by weight of the acrylic copolymer, the difference in solubility between the exposed part and the non-exposed part becomes small, and thus pattern formation is difficult, and when the content exceeds 100 parts by weight When the light is irradiated for a short time, a large amount of unreacted 1,2-quinonediazide compound remains and solubility in an aqueous alkali solution becomes too low, making it difficult to develop. Therefore, the content of the 1,2-quinonediazide compound is 5 to 100 parts by weight based on 100 parts by weight of the acrylic copolymer. The content of the 1,2-quinonediazide compound is preferably 10 to 50 parts by weight based on 100 parts by weight of the acrylic copolymer.

In addition, the photosensitive resin composition of the present invention may further include additives such as an epoxy resin, an adhesive, an acrylic compound, and a surfactant.

The said epoxy resin can improve the heat resistance, a sensitivity, etc. of the pattern obtained from the photosensitive resin composition. Specific examples of the epoxy resins include bisphenol A epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, cycloaliphatic epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, and heterocyclic compounds. And resins obtained by polymerizing glycidyl methacrylate different from epoxy resins and acrylic copolymers. Preferably, bisphenol A type epoxy resin, cresol novolac type epoxy resin, or glycidyl ester type epoxy resin is preferably used. The content of the epoxy resin is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the alkali-soluble resin, and if the amount of use exceeds 30 parts by weight, the compatibility with the alkali-soluble resin is poor and sufficient coating performance cannot be obtained. .

The adhesive may be used to improve adhesion to the substrate, and may be used in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the acrylic copolymer. As such an adhesive, a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryl group, an isocyanate group, an epoxy group, or the like can be used. Specific examples include γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3 , 4-epoxy cyclohexylethyltrimethoxysilane, etc. These may be used alone or in combination of two or more.

The acrylic compound can improve the transmittance, heat resistance, sensitivity and the like of the pattern obtained from the photosensitive resin composition. The content of the acrylic compound is preferably 0.1 to 30 parts by weight, more preferably 0.1 to 15 parts by weight based on 100 parts by weight of the acrylic copolymer.

In addition, the said surfactant is used in order to improve the applicability | paintability and developability of a photosensitive composition. Such surfactants include polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, F171, F172, F173 (trade name; Nippon Ink, Japan), FC430, FC431 (trade name; Sumitomo Triem, Japan), KP341 (Brand name; Shinwol Chemical, Korea). The amount of the surfactant is preferably used in 0.0001 to 2 parts by weight based on 100 parts by weight of the solid content.

On the other hand, the present invention provides a photosensitive resin composition coating solution by adding a solvent to the photosensitive resin composition containing the acrylic copolymer, 1,2-quinonediazide compound, and further comprises the additive component as necessary.

The solid content concentration of the photosensitive resin composition coating solution of the present invention is preferably 15 to 50% by weight, which is used after filtration using a pore filter of 0.1 to 0.2 μm in advance.

Examples of the solvent used for preparing the photosensitive resin composition coating solution include alcohols such as methanol and ethanol; Ethers such as tetrahydrofuran, glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl ether; Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and propylene glycol butyl ether acetate; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, and 4-hydroxy 4-methyl 2-pentanone; And methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxy propionate, methyl 2-hydroxy 2-methylpropionate, ethyl 2-hydroxy 2-methylpropionate, methyl hydroxy acetate, ethyl hydroxy acetate , Butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxy propionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy Methyl 3-methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, propyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl acetate, ethoxy propyl acetate, butyl ethoxy acetate, propoxy acetate Methyl, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, 2-methoxypropy Ethyl acid, 2-methoxypropionic acid propyl, 2-methoxypropionic acid butyl, 2-ethoxypropionic acid methyl, 2-ethoxypropionic acid ethyl, 2-ethoxypropionic acid propyl, 2-ethoxypropionic acid butyl, 2- Methyl butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropionate, 3- Butyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propionate Esters such as propyl propoxy acid, butyl 3-propoxy propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionic acid and butyl 3-butoxypropionate. Preferably, it is preferable to use glycol ethers, ethylene glycol alkyl ether acetates, and diethylene glycols, which have solubility, reactivity with each component, and easy formation of a coating film.

This invention applies the photosensitive resin composition obtained above to the surface of a board | substrate by the spray method, the roll coater method, and the rotary coating method, and removes a solvent by prebaking, and forms a coating film. The prebaking condition is preferably carried out at 70 to 110 for about 1 to 15 minutes. Thereafter, visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like are irradiated onto the coating film and then developed with a developer to remove unnecessary portions to form an organic film pattern.

As the developing solution, an aqueous alkali solution is used. For example, inorganic alkali ethylamines, such as sodium hydroxide, potassium hydroxide, and sodium carbonate, primary amines, such as n-propylamine, secondary amines, such as diethylamine and n-propylamine, trimethylamine, methyldiethylamine, and dimethylethyl Tertiary amines, such as amine and triethylamine, Alcohol amines, such as dimethylethanolamine, methyldiethanolamine, and triethanolamine, The aqueous solution of quaternary ammonium salts, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, can be used. . The developer is used by dissolving an alkaline compound at a concentration of 0.1 to 10%, and an appropriate amount of a water-soluble organic organic solvent and a surfactant such as methanol and ethanol can be added.

After the development, washing with ultrapure water for 30 to 90 seconds to remove unnecessary parts and dry to form a pattern. After irradiating the formed pattern with light such as ultraviolet rays, the pattern may be heated by 150 to 250 to 30 to 90 minutes by a heating apparatus such as an oven to obtain a final pattern.

Method for manufacturing thin film transistor substrate

2A to 2G are cross-sectional views illustrating a method of manufacturing a thin film transistor substrate according to an exemplary embodiment of the present invention.

Referring to FIG. 2A, after forming a metal layer (not shown) on the first base substrate 101, the metal layer is etched by a photolithography process to form a gate wiring (not shown), a gate electrode 111, and a storage common wiring. A gate metal pattern including (not shown) is formed.

The metal layer (not shown) may be formed of, for example, a metal such as chromium, aluminum, tantalum, molybdenum, titanium, tungsten, copper, silver, or an alloy thereof, or the like, and is deposited by a sputtering process.

Referring to FIG. 2B, a gate insulating layer 102 made of silicon nitride (SiNx), an amorphous silicon layer 112a, and in-situ doped on the first base substrate 101 on which the gate metal pattern is formed. The n + amorphous silicon layer 112b is formed sequentially. Subsequently, the amorphous silicon layer 112a and the n + amorphous silicon layer 112b are photo-etched to form the channel layer 112 in the region corresponding to the gate electrode 111.

Referring to FIG. 2C, a metal layer (not shown) is formed on the gate insulating layer 102 on which the channel layer 112 is formed. The metal layer (not shown) may be formed of, for example, a metal such as chromium, aluminum, tantalum, molybdenum, titanium, tungsten, copper, silver, or an alloy thereof, or the like, and is deposited by a sputtering process.

Subsequently, the metal layer (not shown) is etched to form a source metal pattern including a source electrode 113, a drain electrode 114, and a source wiring (not shown) of the switching device. The source electrode 113 and the drain electrode 114 are formed at predetermined intervals.

Subsequently, the n + amorphous silicon layer 112b exposed between the source electrode 113 and the drain electrode 114 is etched to expose the amorphous silicon layer 112a.

Referring to FIG. 2D, a photoresist film (not shown) is coated to cover the source metal pattern and the gate insulating layer. The overresist layer 120 including the contact hole 125 is formed by exposing and developing the photoresist film. The contact hole exposes a part of the drain electrode 114.

Referring to FIG. 2E, a transparent conductive layer (not shown) is formed on the overcoat layer 120 on which the contact hole 125 is formed. The transparent conductive layer is made of, for example, indium tin oxide or indium zinc oxide. Subsequently, the transparent conductive layer is etched by a photolithography process to form the pixel electrode layer 130. The pixel electrode layer 130 is electrically connected to the drain electrode 114 through the contact hole 125 and includes a boundary portion 135 that is a domain dividing means.

Referring to FIG. 2F, an organic film 140 is formed by applying the photosensitive resin composition on the pixel electrode layer 130. The photosensitive resin composition is a photosensitive resin composition according to the present invention described above, 5 to 60% by weight of isobornyl carboxylate compound, unsaturated carboxylic acid, unsaturated carboxylic anhydride or a mixture thereof, 10 to 40% by weight, epoxy group 100 parts by weight of the acrylic copolymer (A) and 5 to 100 parts by weight of the 1,2-quinonediazide compound (B) obtained by copolymerizing 20 to 40% by weight of the containing unsaturated compound and 20 to 40% by weight of the olefinically unsaturated compound. .

Next, the organic layer 140 is exposed using the mask 150. The mask 150 includes a transparent substrate 151 and a plurality of light blocking patterns 153. The light blocking patterns 153 are spaced apart from each other by a predetermined distance, and a gap between the light blocking patterns 153 corresponds to a slit. An exposure amount of the organic layer 140 under the light blocking patterns 153 is adjusted according to the distance between the light blocking patterns 153. In more detail, as the distance between the light blocking patterns 153 increases, the exposure amount of the organic layer 140 positioned under the light blocking patterns 153 increases.

Referring to FIG. 2G, after exposing the organic layer 140, the organic layer 140 is developed using a developer to form an inclined layer 145 having a tapered structure. Since the amount of light exposed to the organic layer 140 is not uniform, the inclined layer 145 formed through development has an uneven thickness. The inclined layer 145 covers the boundary 135 of the pixel electrode layer 130.

Method of manufacturing common electrode substrate

3A to 3C are cross-sectional views illustrating a method of manufacturing a common electrode substrate according to an exemplary embodiment of the present invention.

Referring to FIG. 3A, the light blocking layer 202 is formed on the base substrate 210. The light blocking layer may be made of an organic material including a black pigment, chromium, chromium oxide, and the like. Next, a photosensitive organic film (not shown) including a pigment is formed on the base substrate 210, and the photosensitive organic film is exposed and developed to form a color filter layer 203 covering a part of the light blocking layer 202. .

Referring to FIG. 3B, an insulating layer 204 covering the light blocking layer 202 and the color filter layer 203 is formed. The insulating layer 204 may protect the light blocking layer 202 and the color filter layer 203, and may be formed of, for example, silicon nitride, silicon oxide, or an organic film.

Next, a transparent conductive layer (not shown) is laminated on the insulating layer 204. The transparent conductive layer is made of, for example, indium tin oxide or indium zinc oxide. Subsequently, the transparent conductive layer is etched by a photolithography process to form a common electrode layer 205. The common electrode layer 205 includes a boundary portion 206 which is a domain dividing means.

Referring to FIG. 3C, an organic film (not shown) is formed by applying the photosensitive resin composition on the common electrode layer 205. The photosensitive resin composition is a photosensitive resin composition according to the present invention described above, 5 to 60% by weight of isobornyl carboxylate compound, unsaturated carboxylic acid, unsaturated carboxylic anhydride or a mixture thereof, 10 to 40% by weight, epoxy group 100 parts by weight of the acrylic copolymer (A) and 5 to 100 parts by weight of the 1,2-quinonediazide compound (B) obtained by copolymerizing 20 to 40% by weight of the containing unsaturated compound and 20 to 40% by weight of the olefinically unsaturated compound. .

Next, the organic film is exposed using a mask (not shown), and then the organic film is developed using a developer to form an inclined film 207 having a tapered structure. The inclined film 207 covers the boundary 206 of the common electrode layer 205. The method of forming the gradient film 207 by developing the organic film is the same as the method of manufacturing the thin film transistor substrate described above.

Hereinafter, the present invention will be described in more detail with reference to specific embodiments. However, these examples are only for illustrating the present invention, and the present invention is not limited thereto.

Preparation of Acrylic Copolymer

Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 parts by weight of propylene glycol monomethyl ether acetate, 20 parts by weight of methacrylic acid, and methacrylic acid 20 parts by weight of glycidyl, 30 parts by weight of isobonyl acrylate of Formula (1), and 30 parts by weight of styrene were added, followed by nitrogen substitution, and gently stirring was started. The reaction solution was raised to 62 to maintain this temperature for 5 hours to obtain a polymer solution containing the copolymer [A-1]. Solid content concentration of the obtained polymer solution was 45 weight%, and the weight average molecular weight of the polymer was 12000. In this case, the weight average molecular weight is a polystyrene reduced average molecular weight measured using Gel Permeation Chromatography (GPC).

Synthesis Example 2

Preparation of 1,2-quinonediazide compound

1 mol of 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide 5-sulfonic acid [chloride] Condensation reaction of 2 mol [4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol 1,2-naphthoquinonediazide-5 -Sulfonic acid ester].

Preparation of Photosensitive Resin Composition

Example 1

100 parts by weight of the polymer solution (copolymer [A-1]) obtained in Synthesis Example 1, the condensate [4,4 '-[1- [4- [1- [4-hydroxy] obtained in Synthesis Example 5 above. Phenyl] -1-methylethyl] phenyl] ethylidene] bisphenol 1,2-naphthoquinonediazide 5-sulfonic acid ester] 25 parts by weight of the mixture was dissolved in diethylene glycol dimethyl ether so that the solid concentration was 35% by weight. After filtration with a 0.2 μm Millipore filter to prepare a photosensitive resin composition solution.

Organic film pattern formation

In order to form the organic film pattern according to the present invention, the photosensitive resin composition solution of Example 1 was applied through a slit / spin coater, followed by drying for 100 to 150 seconds, followed by an exposure apparatus (trade name: MPA-2000, Exposure was performed by Cannon Co., Japan. Then, the development was performed for 150 seconds, followed by exposure at the front exposure machine, and heat treatment at 220 for 60 minutes. At this time, the conditions of the heat treatment can be from 180 to 250 and the heat treatment time is in the range possible from 20 minutes to 90 minutes, but preferably from 220 to 30 minutes to 60 minutes. After confirming the sensitivity, the exposure sensitivity was excellent, 150 to 250 mJ / cm2, excellent spreadability was able to form a pattern without the occurrence of irregularities (unevenness) in the uneven portion formed.

4 is a cross-sectional view of an organic film pattern formed using the photosensitive resin composition according to the present invention.

Referring to FIG. 4, unlike the surface of the organic film of FIG. 1, an organic film having a flat structure may be formed on the acid formation surface 10 without irregularities.

Since the organic film pattern formed using the photosensitive resin composition which concerns on this invention has an acid structure, it is excellent in response speed. In addition, since the surface of the organic film pattern is very flat, it can be applied to the liquid crystal display device to prevent uneven behavior of the liquid crystal.

Although the present invention has been described with reference to the above embodiments, those skilled in the art can variously modify and change the present invention without departing from the spirit and scope of the invention as set forth in the claims below. I can understand that.

Claims (15)

delete delete delete delete delete delete delete delete delete Forming a gate metal pattern including a gate electrode on the base substrate; Forming a gate insulating film on the gate metal pattern; Forming a channel layer on the gate insulating layer corresponding to the gate electrode; Forming a source metal pattern including a source electrode and a drain electrode on the gate insulating layer on which the channel layer is formed; Forming an overcoat layer covering the gate insulating layer, the channel layer, the source metal pattern, and including a contact hole exposing a portion of the drain electrode; Forming a pixel electrode layer electrically connected to the drain electrode through the contact hole and having a boundary portion that is a domain dividing means; 10 to 40 wt% of (A) isobornyl carboxylate compound on the pixel electrode layer; 10 to 40% by weight unsaturated carboxylic acid, unsaturated carboxylic anhydride or mixtures thereof; 20 to 40% by weight of an epoxy group-containing unsaturated compound; And applying a photosensitive resin composition comprising 100 parts by weight of an acrylic copolymer obtained by copolymerizing 20 to 40% by weight of an olefinically unsaturated compound and (B) 5 to 100 parts by weight of the 1,2-quinonediazide compound; And Exposing and developing the photosensitive resin composition to form an inclined film having a tapered structure. The method of claim 10, wherein the isobonyl carboxylate compound comprises a compound represented by the following general formula (1).

                           (One) In the formula (1), X is an alkenyl group of C1-C10, and R1, R2, R3 and R4 are hydrogen or an alkyl group of C1-C10. The method of manufacturing a thin film transistor substrate for a liquid crystal display device according to claim 10, wherein the exposure of the photosensitive resin composition is performed using a mask including a plurality of light blocking patterns spaced at predetermined intervals.      Forming a light blocking layer on the base substrate;      Forming a color filter layer on the base substrate to cover a portion of the light blocking layer;      Forming an insulating layer covering the light blocking layer and the color filter layer;      Forming a common electrode layer having a boundary portion which is a domain dividing means on the insulating layer; 10 to 40% by weight of the (A) isobornyl carboxylate compound on the common electrode layer; 10 to 40% by weight unsaturated carboxylic acid, unsaturated carboxylic anhydride or mixtures thereof; 20 to 40% by weight of an epoxy group-containing unsaturated compound; And applying a photosensitive resin composition comprising 100 parts by weight of an acrylic copolymer obtained by copolymerizing 20 to 40% by weight of an olefinically unsaturated compound and (B) 5 to 100 parts by weight of the 1,2-quinonediazide compound; And Exposing and developing the photosensitive resin composition to form an inclined film having a tapered structure. The method of claim 13, wherein the isobonyl carboxylate-based compound comprises a compound represented by the following general formula (1):

(One) In the formula (1), X is an alkenyl group of C1-C10, and R1, R2, R3 and R4 are hydrogen or an alkyl group of C1-C10. The method of manufacturing a common electrode substrate for a liquid crystal display device according to claim 13, wherein the exposure of the photosensitive resin composition is performed using a mask including a plurality of light blocking patterns spaced at predetermined intervals.

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