KR20150062995A - Photo-sensitive resin composition - Google Patents

Abstract

The present invention relates to a photosensitive resin composition. The photosensitive resin composition according to the present invention is excellent in processability, excellent in chemical resistance, and is capable of forming a precise hole pattern.

Description

[0001] PHOTO-SENSITIVE RESIN COMPOSITION [0002]

The present application claims the benefit of Korean Patent Application No. 10-2013-0148021 filed on November 29, 2013, filed 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, and more particularly to a photosensitive resin composition which is excellent in chemical resistance and capable of forming a fine pattern.

Various photosensitive materials are used for manufacturing color filters of liquid crystal display elements. For example, a pigment-dispersed photosensitive material may be used to form color pixels. The black matrix, which is a black diaphragm serving as a light shielding film for blocking light, can also be produced by using a solution in which a black pigment, carbon black, perylene black, titanium dioxide or the like is dispersed in a photosensitive material. An overcoat for correcting a step between pixels and a column spacer for maintaining a cell gap of a liquid crystal display element can be manufactured using a transparent photosensitive material not containing a pigment. The photosensitive composition used in the production of the column spacer or the overcoat can also be used for passivation of the thin film transistor layer. The above photosensitive material is coated on a glass substrate or a glass substrate coated with indium tin oxide and then processed through a photolithography process to complete a color filter single plate.

At present, there are many studies on the photosensitive resin composition according to the demand for continuous improvement of the industry. For example, in order to improve the sensitivity, a color filter composition and a high sensitivity photopolymerization initiator using a newly developed binder, A black matrix resin composition improved in sensitivity by introducing an organic phosphoric acid compound into the composition, and the like.

Korean Patent Publication No. 10-2009-0081049

The technical problem to be solved by the present invention is to provide a photosensitive resin composition capable of forming a fine hole pattern smoothly by reducing the CD of the pattern while having excellent chemical resistance.

In one embodiment of the present application,

1) an alkali-soluble binder resin,

2) Multifunctional monomers,

3) photoinitiator,

4) colorant,

5) solvent, and

6) An antioxidant comprising a compound represented by the following formula

The present invention provides a photosensitive resin composition.

[Chemical Formula 1]

In Formula 1,

R 1 to R 4 are the same or different and each independently represents a linear or branched alkylene group having 1 to 10 carbon atoms,

R5 to R12 are the same or different and each independently is a straight or branched alkyl group having 1 to 10 carbon atoms.

Another embodiment of the present application provides a photosensitive material formed using the photosensitive resin composition for a black matrix.

Further, another embodiment of the present application,

a) applying the photosensitive resin composition onto a substrate, and

b) exposing and developing the applied photosensitive resin composition

The present invention also provides a method for producing a photosensitive material.

The photosensitive resin composition according to one embodiment of the present application is characterized by being excellent in processability, excellent in chemical resistance, and capable of forming a precise hole pattern by including the antioxidant represented by the above formula (1).

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram showing pattern characteristics of Example 1 of the present invention. Fig.
2 is a diagram showing pattern characteristics of Comparative Example 1 of the present invention.
3 is a graph showing pattern characteristics of Comparative Example 2 of the present invention.

The present application will be described in more detail below.

The conventional TFT-LCD is manufactured by attaching a bottom plate glass on which a TFT array is formed and a top plate glass on which a color filter is formed. In this case, in consideration of the cohesion margin between the upper plate and the lower plate, there is a disadvantage that the line width of the BM (black matrix) is large and the aperture ratio is small in order to prevent color mixing between sub-pixels due to light leakage.

In contrast, in a COT or COA (color filter on TFT array) structure in which a color filter is formed directly on a TFT array substrate, there is no light leakage due to a cell gap between the upper plate and the lower plate, The transmittance of the panel is increased, and the process defect due to the deviation when the substrate is attached is eliminated, so that the cell process management is simplified, and the top plate glass can be applied to a low cost glass product .

However, in order to connect the TFT and the pixel electrode after directly forming the color filter on the TFT substrate of the lower panel, a via hole must be formed together with the color filter pattern to form a color filter pattern, hole are formed in a small size of 10 to 20 mu m.

Since a negative type in which a crosslinking reaction is caused by a radical generated by decomposition of a photoinitiator contained in an exposed region is mainly used as a photosensitive material used for manufacturing a color filter, The CD of the formed pattern tends to be larger. Particularly, in order to shorten the process time and reduce the cost, the pattern is formed to be formed even at a low exposure dose using a high-sensitivity photoinitiator, so that the CD (CD bias) of the mask-CD contrast pattern tends to become larger.

As described above, when a high sensitivity initiator is used, the CD bias becomes large and the formation of holes becomes difficult. In order to overcome this problem, it is possible to increase the hole size of the mask. However, due to the limitation of the entire pattern line width, there is a limitation in increasing the hole size of the mask.

Therefore, it is preferable that the CD bias (pattern CD mask CD) of the hole pattern formed when the color filter pattern is formed does not exceed a maximum of 10 mu m, preferably 5 mu m.

In order to form a smooth hole pattern in a color filter process, a hole pattern can be formed by lowering the sensitivity of a color photosensitive material by using a low sensitivity photo initiator, a decrease in photoinitiator content, and a decrease in a crosslinking agent content. In this case, The degree of the reaction may decrease, and the chemical resistance and heat resistance may be decreased. In addition, the surface of the substrate may be scratched during the development process.

Accordingly, in the present application, it is an object of the present invention to use a high sensitivity initiator to improve process sensitivity, and to improve the hole pattern formation by reducing the CD of the pattern by using the antioxidant simultaneously while having excellent chemical resistance and heat resistance.

The photosensitive resin composition according to one embodiment of the present application is characterized by containing 1) an alkali-soluble binder resin, 2) a polyfunctional monomer, 3) a photoinitiator, 4) a colorant, 5) a solvent, and 6) And an antioxidant.

In the photosensitive resin composition according to one embodiment of the present application, the content of the antioxidant may be 0.01 to 5% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.

The antioxidant may include the compound represented by Formula 1 alone, and may further include a general antioxidant known in the art. Examples of the additional antioxidant include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-g, t-butylphenol and the like. The content of the additional antioxidant may be 0.01 to 5% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.

The formula (1) may be represented by the following formula (2), but is not limited thereto.

(2)

In the photosensitive resin composition according to one embodiment of the present application, the alkali-soluble binder resin may be a copolymer resin of a monomer giving mechanical strength and a monomer giving alkali solubility.

Monomers that can contribute to the mechanical strength of the film include benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) (Meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, ethylhexyl- Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, 3-methoxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, glycerol Ethoxydiethylene glycol (Me Acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, glycidyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, (Meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate, Dicyclopentenyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl acrylate, isobornyl methacrylate, adamantyl methacrylate, methyl? -Hydroxymethyl Methacrylate, ethyl α- hydroxymethyl acrylate, propyl α- hydroxy methyl acrylate, and butyl α- hydroxymethyl-unsaturated carboxylic acid ester at least one selected from the group consisting of acrylates;

At least one aromatic compound selected from the group consisting of styrene,? -Methylstyrene, (o, m, p) -vinyltoluene, (o, m, p) -methoxystyrene, and (o, m, p) Vinyl;

One or more unsaturated ethers selected from the group consisting of vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether;

At least one unsaturated imide selected from the group consisting of N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide and N-cyclohexylmaleimide; And

Maleic anhydride, and maleic anhydride such as maleic anhydride and methylmaleic anhydride may be used alone, but not limited thereto.

Examples of the monomer capable of imparting alkali solubility include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, 5-norbornene- It is preferable to use at least one member selected from the group consisting of ethyl phthalate, mono-2 - ((meth) acryloyloxy) ethyl succinate, and omega -carboxylic polycaprolactone mono (meth) But is not limited thereto.

In addition to the above monomers, a binder resin represented by the following formula (3) may also be used.

(3)

Rx is a structure in which a carboxylic acid anhydride or diisocyanate of a 5-membered ring is subjected to addition reaction to form an ester bond, Ry is selected from hydrogen, acryloyl, and methacryloyl, n is 3 Lt; / RTI >

Examples of the specific compound of carboxylic acid anhydride constituting Rx include succinic anhydride, methyl succinic anhydride, 2,2-dimethyl succinic anhydride, isobutenyl succinic anhydride, 1,2-cyclohexanedicarboxylic anhydride, hexahydro- 4-methylphthalic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, mell-5-norbornene-2,3-dicarboxylic anhydride, 1,2,3 , 4-cyclobutane tetracarboxylic dianhydride, maleic anhydride, citraconic anhydride, 2,3, -dimethyl maleic anhydride, 1-cyclopentene-1,2-dicarboxylic dianhydride, 3,4,5,6 -Tetrahydrophthalic anhydride, phthalic anhydride, bisphthalic anhydride, 4-methylphthalic anhydride, 3,6-dichlorophthalic anhydride, 3-hydrophthalic anhydride, 1,2,4-benzenetricarboxylic anhydride, 4-nitrophthalic anhydride , And diethylene glycol-1,2-bistrimelic acid anhydride. Group, but is not limited thereto.

Specific examples of the diisocyanate constituting Rx include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1 , 3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, w, w'-diisocyanate-1,3-dimethylbenzene, w, w'-diisocyanate- Dimethylbenzene, w, w'-diisocyanate-1,3-diethylbenzene, 1,4-tetramethylxylene diisocyanate, 1,3-tetramethylxylene diisocyanate, isophorone diisocyanate, 1,3- Cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6- Cyanate, 4,4'-methylene bisisocyanate methylcyclohexane, 2,5-isocyanate methylbicyclo [2,2,2] heptane, and 2,6-isocyanate methylbicyclo [2,2,1] heptane , But is not limited thereto.

The alkali-soluble binder resin preferably has a weight average molecular weight of 1,000 to 50,000 g / mol, preferably 2,000 to 10,000 g / mol, and an acid value of 30 to 150 KOH mg / mg.

The content of the alkali-soluble binder resin is preferably 1 to 10% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.

In the photosensitive resin composition according to one embodiment of the present application, the multifunctional monomer may include a multifunctional monomer known in the art. More specific examples include pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, But is not limited thereto.

In the photosensitive resin composition according to one embodiment of the present application, the total content of the polyfunctional monomer is preferably 1 to 10% by weight based on the total weight of the photosensitive resin composition.

In the photosensitive resin composition according to one embodiment of the present application, the photoinitiator is a material that generates radicals by light to induce crosslinking, and may be an acetophenone compound, a nonimidazole compound, a triazine compound, and a oxime compound Is preferably used in combination with at least one compound selected from the group consisting of

Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2- - (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, 2-methyl-2- (4-methylthio) phenyl-2-morpholino-1-propan-1-one, 2-benzyl- Amino-1- (4-morpholinophenyl) -butan-1-one, 2- (4-bromo-benzyl- And 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one,

Examples of the nonimidazole-based compounds include 2,2-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- 4 ', 5,5'-tetrakis (3,4,5-trimethoxyphenyl) -1,2'-biimidazole, 2,2'-bis (2,3-dichlorophenyl) ', 5,5'-tetraphenylbiimidazole, and a group consisting of 2,2'-bis (o-chlorophenyl) -4,4,5,5'-tetraphenyl-1,2'-biimidazole , ≪ / RTI >

Examples of the triazine compound include 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propionic acid, 1,1,1,3,3,3- (Trichloromethyl) -s-triazine-6-yl] phenylthio} propionate, ethyl 2- {4- [2,4 Bis (trichloromethyl) -s-triazin-6-yl] phenylthio} acetate, 2- epoxyethyl-2- {4- [ Yl] phenylthio} acetate, benzyl-2- {4- [2- (4-fluorophenyl) (Trichloromethyl) -s-triazine-6-yl] phenylthio} acetate, 3- {chloro-4- [ (Phenylthio) propionic acid, 2,4- bis (trichloromethyl) -s-triazine-6-yl] Methyl) -6- p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p- Aminophenyl) -1,3-butadienyl -s- triazine, and 2-trichloromethyl-4-amino -6-p- methoxy styryl -s- will selected from the group consisting of a triazine,

Examples of the oxime compounds include 1,2-octadione-1- (4-phenylthio) phenyl-2- (o-benzoyloxime) (Ciba Geigy, CGI 124), and ethanone- (2-methylbenzoyl-3-yl) -1- (o-acetyloxime) (CGI 242).

The photoinitiator is preferably used in an amount of 1 to 300 parts by weight based on 100 parts by weight of the sum of the alkali-soluble binder resin and the unsaturated double bond contained in the multifunctional monomer. In particular, 1 to 30 parts by weight of the acetophenone compound, 1 to 30 parts by weight of a triazine compound, 1 to 30 parts by weight of a triazine compound, or 1 to 30 parts by weight of a oxime compound.

The photoinitiator may further include 0.01 to 10 parts by weight of a photo-crosslinking sensitizer and 0.01 to 10 parts by weight of a curing accelerator for accelerating the curing, relative to 100 parts by weight of the photoinitiator.

The photo-crosslinking sensitizer may be at least one selected from the group consisting of benzophenone, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylaminobenzophenone, Benzoate compounds such as benzoate, 3,3-dimethyl-4-methoxybenzophenone, and 3,3,4,4-tetra (t-butylperoxycarbonyl) benzophenone; Fluorene-based compounds such as 9-fluorenone, 2-chloro-9-proprenone and 2-methyl-9-fluorenone; Thioxanthone systems such as thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propyloxytioxanthone, isopropylthioxanthone and diisopropylthioxanthone compound; Xanthone compounds such as xanthone and 2-methylxanthone; Anthraquinone compounds such as anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone, and 2,6-dichloro-9,10-anthraquinone; (9-acridinylpentane), 1,3-bis (9-acridinyl) propane, and the like Acridine-based compounds; Dicarbonyl compounds such as benzyl, 1,7,7-trimethyl-bicyclo [2,2,1] heptane-2,3-dione, and 9,10-phenanthrenequinone; Phosphine oxide-based compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; Benzophenone compounds such as methyl-4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate and 2-n-butoxyethyl-4- (dimethylamino) benzoate; (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-diethylaminobenzal) cyclohexanone, 2,6-bis Amino-synergists such as methyl-cyclopentanone; (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- Pyran o [6,7,8-ij] -quinolizine-11-one; Chalcone compounds such as 4-diethylaminokalone and 4-azidobenzalacetophenone; 2-benzoylmethylene, or 3-methyl-b-naphthothiazoline.

Examples of the curing accelerator include 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, 2- (3-mercaptopropionate), pentaerythritol-tris (3-mercaptopropionate), pentaerythritol-tetrakis (2-mercaptoacetate) , Trimethylolpropane-tris (2-mercaptoacetate), trimethylolpropane-tris (3-mercaptopropionate), pentaerythritol-tris Can be used.

The content of the photoinitiator is preferably 0.5 to 5% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.

In the photosensitive resin composition according to one embodiment of the present application, the solvent is selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, Propylene glycol dimethyl ether, propylene glycol methyl ether acetate, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, chloroform, chloride Methylene, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,2-trichloroethene, hexane, heptane, octane, cyclohexane, benzene , Toluene, xylene, methanol, ethanol, isopropanol, propanol, butanol, t-butanol, 2- ethoxypropanol, 2- methoxypropanol, 3- Propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, and butyl acetate, dipropylene glycol monomethyl ether And the like. However, it is not limited to these, and a solvent known in the art may also be used.

The content of the solvent is preferably 65 to 90% by weight based on the total weight of the photosensitive resin composition.

In the photosensitive resin composition according to one embodiment of the present application, the colorant may be at least one pigment, a dye, or a mixture thereof.

Specifically, examples of the black pigment include metal oxides such as carbon black, graphite, titanium black, and the like. 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.

Examples of coloring agents that can be colored include carmine 6B (CI12490), phthalocyanine green (CI 74260), phthalocyanine blue (CI 74160), perylene black (BASF K0084. K0086), cyanine black, lino yellow (CI 21090) Linol Yellow 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; 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.

The content of the colorant is preferably 5 to 20% by weight based on the total weight of the photosensitive resin composition.

The photosensitive resin composition according to one embodiment of the present application may further include at least one additive selected from the group consisting of a dispersant, an adhesion promoter, an ultraviolet absorber, a thermal polymerization inhibitor, and a leveling agent.

The adhesion promoter may be selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) -silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- 2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- glycidoxypropylmethyldimethoxysilane, 2- 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane, And trimethoxysilane can be used.

The ultraviolet absorber may be 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chloro-benzotriazole, or alkoxybenzophenone.

The thermal polymerization inhibitor may be at least one selected from the group consisting of hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t- butylcatechol, benzoquinone, 4,4- -Butylphenol), 2,2-methylenebis (4-methyl-6-t-butylphenol), or 2-mercaptoimidazole.

In addition, the photosensitive resin composition may further include at least one secondary additive selected from the group consisting of a carbon black dispersion, a functional resin binder, a polyfunctional monomer, a radiation-sensitive compound, and other additives have.

In addition, one embodiment of the present application provides a photosensitive material formed using the photosensitive resin composition.

In addition, a method of manufacturing a photosensitive material according to an embodiment of the present application includes the steps of: a) coating the photosensitive resin composition on a substrate; and b) exposing and developing the applied photosensitive resin composition.

In the method of manufacturing a photosensitive material according to an embodiment of the present application, the step a) is a step of applying a photosensitive resin composition onto a substrate, and may be applied, for example, onto a substrate using a method known in the art. More specifically, the method of applying the photosensitive resin composition may be a spraying method, a roll coating method, a spin coating method, a bar coating method, a slit coating method, or the like. However, the present invention is not limited thereto.

At this time, the substrate may be made of metal, paper, glass, plastic, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide and the like. Treatment, plasma treatment, ion plating, sputtering, gas phase reaction, vacuum deposition, or the like. In addition, the substrate may have an optional thin film transistor for driving, and a nitrided silicon film may be sputtered.

In the method of manufacturing a photosensitive material according to an embodiment of the present application, the step b) is a step of exposing and developing the applied photosensitive resin composition.

More specifically, the prebaked coating film can be patterned by irradiating ultraviolet rays through a predetermined pattern mask and developing it with an aqueous alkaline solution to remove unnecessary portions. At this time, as a developing method, a dipping method, a shower method, and the like can be applied without limitation. The developing time is usually about 30 to 180 seconds. Examples of the developer include aqueous alkaline solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, sodium metasilicate and ammonia; Primary amines such as ethylamine and N-propylamine; Secondary amines such as diethylamine and di-n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine and dimethylethylamine; Tertiary alcohol amines such as dimethylethanolamine, methyldiethanolamine and triethanolamine; Diazabicyclo [4.3.0] hept-2-ene, 1,1-diazabicyclo [5.4.0] Cyclic tertiary amines such as cyclohexane-5-nonene; Aromatic tertiary amines such as pyridine, coridine, lutidine and quinoline; An aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide can be used.

After the development, washing with water for about 30 to 90 seconds and drying with air or nitrogen can be carried out. This pattern can be obtained through a post-bake using a heating device such as a hot plate or an oven. At this time, it is preferable to heat post-baking at 150 to 230 DEG C for 10 to 90 minutes.

Examples of the light source for curing the photosensitive resin composition according to one embodiment of the present application include mercury vapor arc, carbon arc, Xe arc, etc., which emit light having a wavelength of 250 to 450 nm, .

The light-sensitive material according to one embodiment of the present application has an excellent surface-defect free property, developability, light-shielding property, and insulation, and is excellent in adhesion with a substrate and has an excellent impact resistance after a substrate adhesion process, a liquid crystal injection process, have.

The photosensitive material according to one embodiment of the present application may be a pigment-dispersed photosensitive material for manufacturing 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, a photosensitive material for a column spacer, But it can also be used for photocurable paint, photocurable ink, photocurable adhesive, printing plate, photosensitive material for printed wiring board, other transparent photosensitive material, and PDP, I do not.

In particular, since the photosensitive resin composition according to one embodiment of the present application contains the antioxidant represented by the above formula (1), it has an excellent processability, excellent chemical resistance, and is capable of forming a precise hole pattern.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

<Examples>

&Lt; Example 1 >

2 g of B15: 6 / V23 as a colorant, 0.002 g of an AO60 compound as an antioxidant, 0.9 g of an alkali-soluble binder resin (LGC EM40) as shown in the following structural formula, 0.8 g of dipentaerythritol hexaacrylate as a polyfunctional monomer, , 0.06 g of TF-1740 as a surfactant, 0.08 g of PBG305 as an oxime ester indicator as a high-sensitivity photoinitiator, 3 g of PGMEA and 2.5 g of PBM3057 as organic solvents, and 2.5 g of 3-MBA were mixed for 3 hours using a shaker, To prepare a resin composition.

&Lt; Example 2 >

A photosensitive resin composition was prepared in the same manner as in Example 1, except that AO00 was used in place of AO60 as an antioxidant in Example 1.

&Lt; Comparative Example 1 &

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the antioxidant was removed in Example 1 and 0.04 g of I907, 0.07 g of I369 and 0.006 g of EMK were used instead of the high-sensitivity photoinitiator as the photoinitiator .

&Lt; Comparative Example 2 &

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the antioxidant was removed in Example 1.

&Lt; Experimental Example 1 >

The photosensitive resin composition prepared in Example 1 and Comparative Examples 1 and 2 was spin-coated on a glass substrate and heat-treated at about 100 캜 for 80 seconds to form an even film having a thickness of about 2.2 탆. Then, After exposure at 40 mJ / cm ^{2 with a} mask, development was carried out with 0.043% KOH solution at 25 ° C for 60 seconds, and the shape and size of the hole pattern were observed through SEM to evaluate the possibility of forming fine hole patterns. The results are shown in Figs. 1 to 3 below. The hole referred to herein is a square shape, and as the hole shape is maintained, it can be said that the implementation of the fine hole pattern is excellent.

&Lt; Experimental Example 2 >

The photosensitive resin compositions prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were spin-coated on a glass substrate and heat-treated at about 100 캜 for 80 seconds to form an equivalent film having a thickness of about 2.2 탆, 40 mJ / cm ^2, followed by baking in an oven at 230 ° C for 20 minutes, and chemical resistance was evaluated using NMP (N-methyl-2-pyrrolidone) solvent. The results are shown in Fig.

As described above, the photosensitive resin composition according to the present invention includes the antioxidant represented by Formula 1, and thus has excellent processability, excellent chemical resistance, and is capable of forming a precise hole pattern.

Claims (8)

1) an alkali-soluble binder resin,
2) Multifunctional monomers,
3) photoinitiator,
4) colorant,
5) solvent, and
6) An antioxidant comprising a compound represented by the following formula
: &Lt; EMI ID =
[Chemical Formula 1]

In Formula 1,
R 1 to R 4 are the same or different and each independently represents a linear or branched alkylene group having 1 to 10 carbon atoms,
R5 to R12 are the same or different and each independently is a straight or branched alkyl group having 1 to 10 carbon atoms. The photosensitive resin composition according to claim 1, wherein the content of the antioxidant is 0.01 to 5% by weight based on the total weight of the photosensitive resin composition. The photosensitive resin composition according to claim 1, wherein the formula (1) is represented by the following formula (2)
(2)

[2] The composition according to claim 1, wherein the polyfunctional monomer is at least one selected from the group consisting of pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa Wherein the photosensitive resin composition contains at least one selected from the group consisting of a polyvinyl alcohol and a polyvinyl alcohol. The photosensitive resin composition according to claim 1, wherein the content of the alkali-soluble binder resin is 1 to 10 wt%, the content of the polyfunctional monomer is 1 to 10 wt%, the content of the photoinitiator is 0.5 to 5 wt% By weight, the content of the solvent is 65 to 90% by weight, and the content of the colorant is 5 to 20% by weight. The photosensitive resin composition for a black matrix according to claim 1, wherein the photosensitive resin composition further comprises at least one member selected from the group consisting of a dispersant, an adhesion promoter, an ultraviolet absorber, a thermal polymerization inhibitor, and a leveling agent. A photosensitive material formed using the photosensitive resin composition of any one of claims 1 to 6. a) applying the photosensitive resin composition of any one of claims 1 to 6 onto a substrate, and
b) exposing and developing the applied photosensitive resin composition
Wherein the photosensitive material is a photosensitive material.

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