KR101735155B1 - Photosensitive resin composition, organic film manufactured by using the same and liquid crystal display device comprising the same - Google Patents

Abstract

The present application relates to polymeric compounds; Polymerizable compounds; A photopolymerization initiator; A light absorber decomposed at a temperature of 180 캜 or more; And a solvent, a color filter manufactured using the same, and a liquid crystal display device including the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, an organic film made using the same, and a liquid crystal display device including the same. BACKGROUND OF THE INVENTION 1. Field of the Invention [0002]

This application claims the benefit of Korean Patent Application No. 10-2013-0069939 filed on June 18, 2013 with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.

The present invention relates to a photosensitive resin composition, an organic film produced using the same, and a liquid crystal display device including the same.

Recently, attempts have been made to increase the aperture ratio of liquid crystal display elements in order to reduce the power consumption and improve the quality of the display screen. In order to effectively improve the aperture ratio, the size of a thin film transistor used in a liquid crystal display device is reduced and the area of a pixel electrode formed of a transparent electrode such as ITO is increased. At this time, an insulating organic film is used to prevent a short-circuit (Shot) or a signal cross-talk between the electrode of the thin-film transistor and the pixel driving electrode. At this time, a hole pattern is formed in the organic film to apply a voltage or a capacitance to the pixel driving electrode and connect the electrodes.

 The organic film is positioned between the thin film transistor and the pixel driving electrode. Generally, dry etching is used to remove the passivation layer under the organic layer, and then a chemical or physical vapor deposition method is used to form an electrode of a pixel electrode or a capacitance. In order to form a hole of a certain size in a large area, an organic film is usually composed of a thin film produced by an optical etching method. Since the aperture ratio of the device increases as the size of the hole formed becomes smaller, it is required to manufacture a small hole. However, when a small hole is formed in a large area, the defective rate may be increased due to problems such as hole clogging due to diffraction of light or the like.

When manufacturing an organic film having a small-sized hole in a large area, in order to lower the defect rate, the hole should not be blocked in the optical etching process, and a hole of a uniform shape should be formed.

Korean Laid-Open Patent Publication No. 2011-0073261

The present invention is directed to a photosensitive resin composition capable of realizing a uniform pattern of holes without causing clogging of holes when an organic film including a fine hole pattern is produced, a color filter manufactured using the same, And a liquid crystal display element.

One embodiment of the present application includes a polymeric compound; Polymerizable compounds; A photopolymerization initiator; A light absorber decomposed at a temperature of 180 캜 or more; And a solvent.

One embodiment of the present application provides an organic film produced using the photosensitive resin composition.

One embodiment of the present application provides a liquid crystal display device comprising the organic film

One embodiment of the present application provides a photosensitive material produced using the photosensitive resin composition.

The photosensitive resin composition provided through the present application is advantageous for realizing a certain type of hole pattern without causing a lot of hole clogging when a small size organic film including a hole pattern is manufactured by the optical etching method. It is also advantageous in the development of various photosensitive materials.

Fig. 1 shows an enlarged image using electron scanning microscopes of the hole pattern shapes of Examples 1 to 3.
Fig. 2 is an enlarged image obtained by using electron scanning microscopes of the hole pattern shapes of Examples 4 to 5 and Comparative Example 1. Fig.
Fig. 3 shows the transmittance after the pre-heat treatment in Examples 1 to 5 and Comparative Example 1. Fig.
Fig. 4 shows the transmittances after the post-heat treatment in Examples 1 to 5 and Comparative Example 1. Fig.

The advantages and features of the present application, and how to accomplish them, will become apparent with reference to the embodiments described below in detail. It should be understood, however, that the present application is not limited to the illustrated embodiments but is to be accorded the widest scope consistent with the teachings of the present application. To fully disclose the scope of the invention to those skilled in the art, and this application is only defined by the scope of the claims.

Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this application belongs. In addition, commonly used predefined terms are not ideally or excessively interpreted unless explicitly defined otherwise.

Hereinafter, the present application will be described in detail.

The photosensitive resin composition according to one embodiment of the present application includes a polymer compound; Polymerizable compounds; A photopolymerization initiator; A light absorber decomposed at a temperature of 180 캜 or more; And a solvent.

The photosensitive resin composition according to one embodiment of the present application is advantageous for realizing a certain type of hole pattern without occurrence of hole clogging when a small-sized organic film including a hole pattern is manufactured by the optical etching method. Diffraction of light is a major cause of hole clogging when manufacturing small size holes. The light emitted from the exposer mainly uses an i-line with a wavelength of 365 nm, but a g-line at 436 nm and an h-line at 405 nm are also generated. The g-line and the h-line of long wavelength are partially diffracted at the boundary of the mask, penetrate into the non-visible portion, and contact the photoinitiator. At this time, when the photoinitiator generates radicals, the shape of the holes is irregular, and in severe cases, the holes are blocked. When the photosensitive resin composition according to one embodiment of the present application is used, it is possible to prevent hole clogging or the like, which may occur when light having a long wavelength is diffracted to absorb light of a small size, thereby making it possible to manufacture a hole pattern in a desired state .

The light absorber should decompose and be easily removed at a temperature of 180 ° C or higher. When a light absorber that is not decomposed at a temperature of 180 ° C or higher is used, the light absorber remains in the transparent film even after the lithography process, so that the transparent film absorbs light of wavelengths of 405 nm and 436 nm, Thereby causing color distortion. The light absorber decomposed at a temperature of 180 ° C or higher absorbs light until the exposure step to prevent light of a long wavelength to be diffracted, and in the post-heating step, the light absorber is decomposed and removed to make the organic film transparent.

The light absorbing agent may have an absorbance in a region between 300 and 500 nm. Since the region of light emitted from the exposure apparatus used in the photolithography method is 300 nm to 500 nm, it is preferable that the light absorbing region of 300 nm to 500 nm is not overlapped with the light absorbing region of the light absorbing agent, .

The light absorber specifically includes 2 - ((9- (2-ethylhexyl) -9H-carbazol-3-yl) methylene) malononitrile, 2- Acrylate and 2 - ((2-cyano-3- (4- (dimethylamino) phenyl) acryloyl) oxy) propane-1,3-dimethyl ether Or more.

The content of the light absorbent may be 0.02 to 2% by weight based on the total weight of the composition. Alternatively, the content of the light absorbing agent may be 0.05 to 5% by weight, based on the solid content excluding the solvent in the composition. If the content of the light absorbent is less than 0.02 wt% based on the total weight of the composition, the effect of adding the light absorbent is insignificant. If the content of the light absorbent is more than 2 wt%, the amount of light exposure by the light absorbent is reduced, And there is a problem that the decomposed light absorbent byproducts in the post heat treatment process can contaminate the heating chamber of the post heat process.

In one embodiment of the present application, the polymer compound is a polymer compound used in a transparent photosensitive resin composition, and may be at least two kinds of copolymers selected from the group consisting of an acrylate monomer, a methacrylate monomer, a styrene monomer, and an epoxy monomer. Further, it may be a copolymer further comprising at least two monomers selected from the group consisting of unsaturated ether monomers, N-vinyl tertiary amine monomers, unsaturated imide monomers, maleic anhydride monomers and unsaturated glycidyl compound monomers. These monomers may include a benzene group, a hydrocarbon group, a polycyclic group, and the like to control the physical properties of the organic layer.

The weight average molecular weight of the polymer compound may range from 1,000 to 100,000. When the weight average molecular weight of the polymer compound is less than 1,000, heat resistance and chemical resistance deteriorate. When the weight average molecular weight exceeds 100,000, the solubility of the polymer compound in the developer is lowered, and the viscosity of the solution is excessively increased.

Examples of the methacrylate monomer or acrylate monomer include benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (Meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl Hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Methoxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, 2- Late, ethoxydiene (Meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, phenoxydiethylene glycol Acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, (Meth) acrylate, hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl Acrylate, ethyl? -Hydroxymethylacrylate, propyl? -Hydroxymethylacrylate, butyl? -Hydroxymethylacrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl And the like other) acrylate, dicyclopentanyl oxyethyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate.

Examples of the styrene monomer include aromatic vinyls such as styrene,? -Methylstyrene, (o, m, p) -vinyltoluene, (o, m, p) -methoxystyrene, .

Examples of the epoxy monomer include allyl glycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl 5-norbornene- Carboxylate (endo, exo mixture), 1,2-epoxy-5-hexene, or 1,2-epoxy-9-decene.

Examples of other monomers include unsaturated ether monomers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; N-vinyl tertiary amine monomers such as N-vinyl pyrrolidone, N-vinyl carbazole, N-vinyl morpholine; Unsaturated imides such as N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide and N-cyclohexylmaleimide; Maleic anhydride monomers such as maleic anhydride and methyl maleic anhydride; Or unsaturated glycidyl compound monomers such as allyl glycidyl ether, glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate, or mixtures thereof.

The polymer compound may be used in admixture with those generally used in the art, such as an alkali-soluble binder resin, depending on the purpose, so long as the effect of the present invention is not impaired. By including an alkali-soluble binder resin, there is an effect of controlling the viscosity and effecting patterning using an alkaline developer. The alkali-soluble binder resin used in the present application may have an acid value of about 30 to 300 KOH mg / g. When the acid value is less than 30 KOH mg / g, the development is not performed well and a clear pattern can not be obtained. When the acid value is more than 300 KOH mg / g, the washing property is excessively improved and the pattern may be detached.

An example of such an alkali-soluble binder resin is an acrylic binder resin containing a carboxyl group as an alkali-soluble. More specifically, it may be a copolymer of a monomer containing an acid functional group and a monomer giving a film strength copolymerizable with the monomer.

The polymer compound may be at least one selected from the group consisting of an acrylate monomer, a methacrylate monomer, a styrene monomer, an epoxy monomer, an unsaturated ether monomer, an N-vinyl tertiary amine monomer, an unsaturated imide monomer, a maleic anhydride monomer, an unsaturated glycidyl compound monomer, Monomers, and mixtures thereof.

Examples of the monomer containing an acid group include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprenesulfonic acid, styrenesulfonic acid, (Meth) acryloyloxy) ethyl phthalate, mono-2 - ((meth) acryloyloxy) ethyl succinate, omega -carboxylic polycaprolactone mono (meth) acrylate or mixtures thereof.

In the photosensitive resin composition according to one embodiment of the present application, the content of the polymer compound may be 8 to 32% by weight based on the total weight of the photosensitive resin composition. Alternatively, the content of the polymer compound may be 20 to 80% by weight based on the solid content excluding the solvent in the composition. When the content of the light absorbent is 8% by weight or more based on the total weight of the composition, patterning using an alkaline aqueous solution is effective, and the problem that the hole pattern is not formed to the bottom can be prevented, If the content is below% by weight, the problem that the surface of the thin film is damaged and the roughness is increased can be prevented.

The photosensitive resin composition according to one embodiment of the present application may contain a polymerizable compound. The polymerizable compound serves as a crosslinking agent. Specifically, a polymerizable compound containing an ethylenic unsaturated group can be used. More specifically, a polymerizable compound containing two or more unsaturated acrylic groups and a polymerizable compound containing three or more unsaturated acrylic groups can be used. As a specific example, ethylene glycol di (meth) acrylate, an ethylene group having 2 to 14 polyethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2-trisacryloyloxymethyl ethyl phthalic acid, propylene glycol di (meth) acrylate having 2 to 14 propylene groups, dipentaerythritol penta A mixture of an acidic modification of dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate (trade name TO- 2348, TO-2349), which is obtained by esterifying a polyhydric alcohol with an?,? - unsaturated carboxylic acid; A compound obtained by adding (meth) acrylic acid to a compound containing a glycidyl group such as trimethylol propane triglycidyl ether acrylic acid adduct and bisphenol A diglycidyl ether acrylic acid adduct; ester compounds of a compound having a hydroxyl group or an ethylenically unsaturated bond such as a phthalic acid diester of? -hydroxyethyl (meth) acrylate and a toluene diisocyanate adduct of? -hydroxyethyl (meth) acrylate with a polyvalent carboxylic acid , Or adducts with polyisocyanates; Alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate; And 9,9'-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, and it is not limited to these, and any of those known in the art Compounds may be used. In some cases, silica dispersions can be used for these compounds, for example, Nanocryl XP series (0596, 1045, 21/1364) and Nanopox XP series (0516, 0525) manufactured by Hanse Chemie.

In the photosensitive resin composition according to one embodiment of the present application, the content of the polymerizable compound may be 8 to 32% by weight based on the total weight of the photosensitive resin composition, or the content of the polymerizable compound may be And may be 20 to 80% by weight on a solid basis. If the content of the light absorbent is 8 wt% or more based on the total weight of the composition, the problem that the crosslinking reaction due to light may not proceed can be prevented. When the content of the light absorbent is less than 32 wt%, the alkali becomes insoluble and the pattern formation becomes difficult There is an advantage to be able to avoid problems.

In the photosensitive resin composition according to one embodiment of the present application, the photopolymerization initiator specifically includes a triazine-based compound, a nonimidazole-based compound, an acetophenone-based compound, an O-acyloxime-based compound, a benzophenone- A phosphazene compound, a phosphazene compound, a phosphazene compound, a phosphazene compound, a phosphazene compound, a phosphazene compound, a phosphazene compound, a phosphazene compound, a phosphazene compound, More specifically, the photopolymerization initiator may be 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'- methoxystyryl) Azine, 2,4-trichloromethyl- (triphenyl) -6-triazine, 2,4-trichloromethyl- (3 ', 4'-dimethoxyphenyl) - [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propanoic acid, 2,4-trichloromethyl- (4'-ethylbiphenyl) Triazine-based compounds such as 2,4-trichloromethyl- (4'-methylbiphenyl) -6-triazine;

Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 5'-tetraphenylbiimidazole;

2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- (4-methylthiophenyl) -2-morpholinocyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 1-one (Irgacure-907) such as polymethyl-1-propanol, Nonnary compounds;

O-acyloxime compounds such as Irgacure OXE 01, Irgacure OXE 02 from BASF, N-1919, NCI-831 and NCI-930 from ADEKA;

Benzophenone compounds such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone; Thioxanthone compounds such as 2,4-diethylthioxanthone, 2-chlorothioxanthone, isopropylthioxanthone and diisopropylthioxanthone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dichlorobenzoyl) propylphosphine oxide Phosphine oxide-based compounds;

(Diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl- Benzoyl-7-methoxy-coumarin, 10,10'-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H- -Benzopyrano [6,7,8-ij] -quinolizine-11-one, and the like.

In one embodiment of the present application, the photopolymerization initiator is preferably contained in an amount of 0.04 to 2% by weight. Alternatively, the content of the photopolymerization initiator may be 0.1 to 5% by weight based on the solids content of the composition excluding the solvent.

In the photosensitive resin composition according to one embodiment of the present application, examples of the solvent include methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 2-ethoxypropanol, 2-methoxypropanol, 3-methoxybutanol, cyclohexanone, cyclopentanone, Propyleneglycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, and dipropylene glycol monomethyl ether May be one or a mixture of two or more selected from the group The.

In the photosensitive resin composition according to one embodiment of the present application, the content of the solvent may be 40 to 80% by weight based on the total weight of the photosensitive resin composition.

The photosensitive resin composition according to one embodiment of the present application comprises 8 to 32% by weight of a polymer compound, 8 to 32% by weight of a polymerizable compound, 0.02 to 2% by weight of a light absorber, 0.04 to 2% by weight of a photopolymerization initiator, %. ≪ / RTI >

The photosensitive resin composition according to one embodiment of the present application may further comprise a colorant.

As the colorant, one or more pigments, dyes, or mixtures thereof may be used. Examples of coloring agents which are colored include carmine 6B (CI12490), phthalocyanine green (CI 74260), phthalocyanine blue (CI 74160), perylene black (BASF K0084.K0086), cyanine black, linool yellow (CI 21090) GRO (CI 21090), Benzidine Yellow 4T-564D, Victoria Pure Blue (CI42595), CI PIGMENT RED 3, 23, 97, 108, 122, 139, 140, 141, 142, 143, 144, 149, 166, 168, 175, 177, 180, 185, 189, 190, 192, 220, 221, 224, 230, 235, 242, 254, 255, 260, 262, 264, 272; C.I. PIGMENT GREEN 7, 36, 58; C.I. PIGMENT blue 15: 1, 15: 3, 15: 4, 15: 6, 16, 22, 28, 36, 60, 64; C.I. PIGMENT yellow 13, 14, 35, 53, 83, 93, 95, 110, 120, 138, 139, 150, 151, 154, 175, 180, 181, 185, 194, 213; C.I. PIGMENT VIOLET 15, 19, 23, 29, 32, 37, etc. In addition, white pigments and fluorescent pigments can be used. As the phthalocyanine-based complex compound used as the pigment, a material having zinc as a central metal in addition to copper may be used.

As the black pigment, metal oxides such as carbon black, graphite, titanium black and the like can be used. Examples of carbon blacks are cysteine 5HIISAF-HS, cysto KH, cysteo 3HHAF-HS, cysteo NH, cysto 3M, cysto 300HAF-LS, cysto 116HMMAF-HS, , SISTO SOFEF, SISTO VGPF, SISTO SVHSRF-HS and SISTO SSRF (Donghae Carbon Co., Ltd.); Diagram Black II, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E Diagram G Diagram R Diagram N760M Diagram LR, # 2700, # 25, # 45, # 45, # 45, # 45, # 45, # 25, # CF9, # 95, # 20, # 2300, # 2350, # 2300, # 2200, # 1000, # 980, # 900, 3030, # 3050, MA7, MA77, MA8, MA11, MA100, MA40, OIL7B, OIL9B, OIL11B, OIL30B and OIL31B (Mitsubishi Chemical); PRINTEX-25, PRINTEX-25, PRINTEX-55, PRINTEX-55, PRINTEX-45, PRINTEX-35, PRINTEX- 200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100 and LAMP BLACK-101 (Daegu; 890, RAVEN-880ULTRA, RAVEN-880ULTRA, RAVEN-850R, RAVEN-1080ULTRA, RAVEN-1080ULTRA, RAVEN-1080ULTRA, RAVEN-1080ULTRA, RAVEN-1040ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN- 820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN- RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, RAVEN-1170 (Colombia Carbon) or mixtures thereof.

In the photosensitive resin composition according to one embodiment of the present application, the content of the coloring agent may be 0.4 to 32% by weight based on the total weight of the photosensitive resin composition. Alternatively, the content of the coloring agent may be 1 to 80% by weight based on the solid content excluding the solvent in the composition.

The photosensitive resin composition according to one embodiment of the present application comprises 8 to 32% by weight of a polymer compound, 8 to 32% by weight of a polymerizable compound, 0.02 to 2% by weight of a light absorbent, 0.04 to 2% by weight of a photopolymerization initiator, % And 0.4 to 32% by weight of a coloring agent.

The photosensitive resin composition according to one embodiment of the present application may further contain a curing accelerator, a thermal polymerization inhibitor, a dispersant, an antioxidant, an ultraviolet absorber, a plasticizer, an adhesion promoter, a filler, a photosensitizer, May further include one or two or more additives. In addition, other acrylate compounds may be further included.

When the additive is added in one embodiment of the present application, it is preferably contained in an amount of 0.004 to 8% by weight based on the total weight of the composition. Or the content of the additive may be 0.01 to 20% by weight, respectively, based on the solids content of the composition excluding the solvent. In an embodiment of the present application, the content of the other acrylate compound may be 2 to 20 wt% based on the total weight of the composition, or 5 to 50 wt% based on the solids content of the composition excluding the solvent.

In the photosensitive resin composition according to one embodiment of the present application, examples of the curing accelerator include 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimer (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate (3-mercaptopropionate), pentaerythritol tetrakis ), Pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tris (2-mercaptoacetate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate) , Trimethylol ethane tris (2-mercaptoacetate), and trimethylol ethane tris (3-mercaptopropionate). However, the present invention is not limited thereto. It is not known in the art Which can include things turned.

In the photosensitive resin composition according to one embodiment of the present application, the thermal polymerization inhibitor includes p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, But are not limited to, a mixture of one or more selected from the group consisting of phenylhydroxyamine ammonium salt, N-nitrosophenylhydroxyamine aluminum salt, and phenothiazine, , ≪ / RTI >

In the photosensitive resin composition according to one embodiment of the present application, a polymer type, nonionic, anionic, or cationic dispersing agent may be used as the dispersing agent. Non-limiting examples of such dispersants include polyalkylene glycols and esters thereof, polyoxyalkylene polyhydric alcohols, ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonates, carboxylic acid esters, Alkyl amide alkylene oxide adducts, alkyl amines, and the like, and may be used alone or in admixture of two or more selected from them, but is not limited thereto.

In the photosensitive resin composition according to one embodiment of the present application, non-limiting examples of the antioxidant include 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6- And butyl phenol, but are not limited thereto.

In the photosensitive resin composition according to one embodiment of the present application, a non-limiting example of the ultraviolet absorber is 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) And alkoxybenzophenone, but is not limited thereto.

In the photosensitive resin composition according to one embodiment of the present application, the surfactant may include MCF 350SF, F-475, F-488 and F-552 (hereinafter referred to as DIC) no.

Other plasticizers, adhesion promoters, fillers, and the like can be used as well as any compounds that can be included in conventional photosensitive resin compositions.

In one embodiment of the present application, the photosensitive resin composition may be a photosensitive resin composition for an organic film. Specifically, it may be for a photo-acryl organic film of a thin film transistor liquid crystal display element.

One embodiment of the present application provides an organic film produced using the photosensitive resin composition.

In the present application, the organic film can form a predetermined pattern using the photosensitive resin composition.

When a photosensitive resin composition according to an embodiment of the present invention is used to produce an organic film, the photosensitive resin composition is used to form a film, followed by exposure and development to form a pattern. Specifically, the photosensitive resin composition is coated on the substrate to form a film, and then exposed to light and developed. The heating process may be further performed after the development.

The photosensitive resin composition may be applied on a support such as a substrate using a roll coater, a curtain coater, a spin coater, a slot die coater, various printing, or a deposition method. The substrate may be glass, plastic, or silicon.

It is also possible to apply it onto a support such as a film and then transfer it onto another support or coat it on a first support, transfer it to a blanket or the like, and transfer it to the second support again, and its application method is not particularly limited.

As a light source for curing the photosensitive resin composition of the present application, for example, a mercury vapor arc, carbon arc or Xe arc, which emits light having a wavelength of 250 to 450 nm, may be used.

The photosensitive resin composition film exposed to light and cured may be patterned by a developing method using a spraying method or a dipping method. The pattern in which the development is completed can further perform a curing step after cleaning.

One embodiment of the present application provides a liquid crystal display device comprising an organic film produced using a photosensitive resin composition.

The liquid crystal display device may be a thin film transistor liquid crystal display device, and the organic film may be an insulating photo-acryl.

One embodiment of the present application provides a photosensitive material comprising the photosensitive resin composition.

One embodiment of the present application provides a photosensitive material produced using the photosensitive resin composition.

The photosensitive resin composition is present in a state in which at least part of the solvent is removed or cured by drying and / or curing in the photosensitive material.

The photosensitive resin composition according to one embodiment of the present application can be applied to various applications such as a pigment dispersing type photosensitive material for forming a TFT LCD color filter, a photosensitive material for forming a black matrix of a TFT LCD or an organic light emitting diode, a photosensitive material for forming an overcoat layer, It is preferably used for photosensitive materials for printing and wiring boards and other transparent photosensitive materials. However, it can be used for photo-curable paints, photo-curable inks, photo-curing adhesives, printing plates, and PDP production.

One embodiment of the present application provides an electronic device manufactured using the photosensitive resin composition.

Synthesis Example 1 Synthesis of polymer compound

36.5 g, 21.9 g, 36.5 g, 2.5 g and 2.5 g of glycidyl methacrylate, methacrylic acid, styrene, benzyl methacrylate and cyclohexyl methacrylate were dissolved in an excess amount of methyl-3-methoxy propionate ), And the temperature is raised to 60 ° C. 12 g of 2,6'-azobis (2,4-dimethyl valeronitrile, Wako) as an initiator was dissolved in a small amount of MMP and then injected into a monomer mixture solution heated at 60 ° C. for 16 hours under nitrogen atmosphere 0.5 g of BHT was diluted in a small amount of MMP, and the resultant mixture was further reacted under air atmosphere for 1 hour to prepare a polymer compound. The molecular weight of the prepared polymer compound was 7300.

≪ Example 1 >

20 parts by weight (50% based on the solid content) of the polymer compound obtained in Synthesis Example 1, 18 parts by weight (45% based on the solid content) of dipentaerythritol hexaacrylate as a polymerizable compound, 1 part by weight of 2 - ((9- (2-ethylhexyl) -9H-carbazol-3-yl) methylene) malononitrile as a light absorber was dissolved in an organic solvent MMP And the mixture was stirred for 3 hours using a shaker to obtain a 5-micron filter.

The photosensitive resin composition is applied by a spin coating method to form a uniform thin film, followed by pre-baking at 100 ° C for 200 seconds to volatilize the solvent. The thickness of the dried thin film was about 2 탆. Thereafter, a photomask having a square shielding pattern with a width of 10 mu m was used to expose under a high-pressure mercury lamp. The exposed substrate was developed with a 2.35% aqueous solution of TMAH (tetramethylammonium hydroxide) at a temperature of 25 캜 by dipping, washed with pure water, and dried by air blowing. Thereafter, the film was left in a convection oven at 220 캜 for 20 minutes to obtain a thin film having a hole pattern.

In order to observe the surface state of the thin film and the shape of the hole pattern obtained in the above experiment, an enlarged image was obtained using a scanning electron microscope. Also, the transmittance in the visible region was measured using an ultraviolet ray and a visible ray spectrometer.

≪ Example 2 >

The same amount of 2-cyano-3- (9- (2-ethylhexyl) -9H-carbazol-3-yl) methylene) malononitrile was used in place of 2 - Ethylhexyl) -9H-carbazol-3-yl) acrylic acid was used as the initiator.

≪ Example 3 >

The same parts by weight of 2 - ((2-cyano-3- (4 (methylsulfanyl) - (dimethylamino) phenyl) acryloyl) oxy) propane-1,3-dimethyl ether.

<Example 4>

Except that 0.5 part by weight of 2 - ((9- (2-ethylhexyl) -9H-carbazol-3-yl) methylene) malononitrile was used instead of 1 part by weight in Example 1, &Gt;.

&Lt; Example 5 >

Except that 0.2 part by weight of 2 - ((9- (2-ethylhexyl) -9H-carbazol-3-yl) methylene) malononitrile was used instead of 1 part by weight in Example 1, &Gt;.

&Lt; Comparative Example 1 &

Example 1 is the same as Example 1 except that the light absorber is not used in the <Example 1> for the comparative evaluation.

<Experimental Example 1> Comparison of hole shapes

1 and 2 show an enlarged image of the hole pattern shape electron microscope of Examples 1 to 5 and Comparative Example 1, respectively.

As shown in FIGS. 1 and 2, the photosensitive resin composition containing the light absorber according to one embodiment of the present application has a hole with a smaller size than that of the composition not containing the light absorber, and has a diffraction pattern of light . It can be seen that the sharpness of the shape of the hole and the degree of the diffraction pattern are influenced by the amount of the light absorbing agent.

It is confirmed that the capability of forming a fine pattern varies depending on the use of the light absorbent according to the present invention. 1 and 2, the fine holes were well formed in Examples 1 to 4, and the amount of the light absorber was small in Example 5, so that diffraction occurred to form small holes. However, In the case of Comparative Example 1, which is not provided, a fine pattern is not formed well.

&Lt; Experimental Example 2 >

The transmittances of Examples 1 to 5 and Comparative Example 1 were measured and are shown in Table 1 below. The permeability after the pre-heat treatment is shown in FIG. 3, and the transmittance after the post-heat treatment is shown in FIG.

The transmittance was measured using a UV-Vis spectroscopy and a 2 μm film was formed on a 0.45 mm transparent glass after the post-heat treatment.

[Table 1]

Further, as shown in [Table 1], FIG. 3 and FIG. 4, the photosensitive resin composition according to one embodiment of the present application is transparent after the photolithography process and can be used as a transparent organic film material. Since the photosensitive resin composition of the present application contains a light absorber having an absorbance in the visible light region, the transmittance in the visible light region is low before and sometimes after exposure. Especially, it has yellowish color because it has absorbance in the range of 380 to 450 nm. However, since the light absorber is easily decomposed in a post-heat treatment process at 230 deg. C, light absorption is lost and transparency is obtained, and the material can be used as a transparent material. The overall transparency of the material is at least 98% and is not different from the sample without the light absorber.

It is preferable that the present invention is transparent after the post-heat treatment which is the final process. According to the present invention, it was confirmed that the light absorber was decomposed during the pattern formation process even though the light absorber was added, so that there was no problem in the transparency of the final product.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Having described specific portions of the present application in detail, it will be apparent to those skilled in the art that such specific embodiments are merely preferred embodiments and that the scope of the present application is not limited thereto. Accordingly, the actual scope of the present application will be defined by the appended claims and their equivalents.

Claims (19)

Polymer compound;
Polymerizable compounds;
A photopolymerization initiator;
A light absorber decomposed at a temperature of 180 캜 or more; And
A solvent,
The light absorber may be selected from the group consisting of 2 - ((9- (2-ethylhexyl) -9H-carbazol-3-yl) methylene) Acrylate and 2 - ((2-cyano-3- (4- (dimethylamino) phenyl) acryloyl chloride in the presence of 2-cyano- 1) oxy) propane-1,3-dimethyl ether. The photosensitive resin composition for forming a transparent organic film according to claim 1, The method according to claim 1,
Wherein the light absorbing agent has an absorbance at 300 to 500 nm. delete The method according to claim 1,
Wherein the content of the light absorbing agent is 0.02 wt% to 2 wt% based on the total weight of the composition. The method according to claim 1,
Wherein the polymer compound is at least one polymer selected from the group consisting of acrylate monomers, methacrylate monomers, styrene monomers and epoxy monomers. The method according to claim 1,
Wherein the weight average molecular weight of the polymer compound is 4,000 to 100,000. The method according to claim 1,
Wherein the content of the polymer compound is 8 wt% to 32 wt% based on the total weight of the photosensitive resin composition. The method according to claim 1,
Wherein the content of the polymerizable compound is 8 wt% to 32 wt% based on the total weight of the photosensitive resin composition. The method according to claim 1,
Wherein the content of the photopolymerization initiator is 0.04 wt% to 2 wt% based on the total weight of the photosensitive resin composition. The method according to claim 1,
Wherein the content of the solvent is 40 wt% to 80 wt% based on the total weight of the photosensitive resin composition. The method according to claim 1,
The photosensitive resin composition for forming a transparent organic film according to claim 1, wherein the photosensitive resin composition further comprises a colorant. The method of claim 11,
Wherein the content of the coloring agent is 0.4 wt% to 32 wt% based on the total weight of the photosensitive resin composition. The method according to claim 1,
The photosensitive resin composition further comprises one or two or more additives selected from the group consisting of a curing accelerator, a thermal polymerization inhibitor, a dispersant, an antioxidant, an ultraviolet absorber, an adhesion promoter, a photosensitizer, a plasticizer, a filler and a surfactant By weight based on the total weight of the photosensitive resin composition. 14. The method of claim 13,
Wherein the additive is contained in an amount of 0.004 wt% to 8 wt% based on the total weight of the photosensitive resin composition. delete An organic film produced by using the photosensitive resin composition for forming a transparent organic film according to any one of claims 1, 2 and 4 to 14. A liquid crystal display element comprising the organic film of claim 16. A photosensitive material produced by using the photosensitive resin composition for forming a transparent organic film according to any one of claims 1, 2 and 4 to 14. 19. The method of claim 18,
The light-sensitive material may be a pigment-dispersed photosensitive material for forming a color filter of a thin film transistor liquid crystal display, a photosensitive material for forming a black matrix of a thin film transistor liquid crystal display or an organic light emitting diode, a photosensitive material for forming an overcoat layer, And a light-sensitive material for a light-sensitive material.

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