TW201136955A - Black-colored photosensitive resin composition, black matrix prepared by using thereof and color filter comprising the black matrix - Google Patents

Abstract

A black photosensitive resin composition, a black matrix manufactured therefrom, and a color filter including the black matrix are provided to secure the excellent storage stability of the resin composition, and to reduce the optical density difference when forming a micro-pattern. A black photosensitive resin composition contains an alkali-developable resin obtained by polymerizing a monomer including compounds marked with chemical formula 1 and 2. In the chemical formula 1, n is an integer of 2~4. In the chemical formula 2, m is the integer of 0-2. 10-40 parts of compound marked with the chemical formula 1 by weight, is mixed with the total amount of the monomer.

Description

201136955 VI. Description of the Invention: [Technical Field] [0001] The present invention relates to a black photosensitive resin composition, a black matrix manufactured using the same, and a color filter having the black matrix Specifically, the color filter is excellent in adhesion to the substrate and storage stability, and the heat flow property during the post-exposure baking treatment is reduced while maintaining the sensitivity, thereby improving the formation of the fine pattern. A black photosensitive resin composition having a difference in optical density due to the position, a black matrix produced using the same, and a color filter light sheet having the black matrix. [Prior Art]

[0002] In a color filter of a liquid crystal display, a black matrix is a color that shields light that is uncontrolled outside the transparent small electrode, thereby improving contrast, and is made of chrome or resin. In the case of chromium, although the film has excellent light-shielding properties and pattern straightness, the resin-based black matrix is preferable in consideration of environmental problems, high reflectance, and high cost of the engineering surface. [0003] However, in the photosensitive resin composition for producing a resin black matrix, since a black pigment having a significant hindrance to photosensitivity is formed, it is impossible to form photocrosslinking with high efficiency, that is, a so-called "undercut". The developer is excessively corroded, and there are problems such as insufficient stability and decreased light sensitivity. The invention disclosed in the Korean Patent Application No. 1995-700231 3 uses a sensitized resin composition for a black matrix in order to enhance the sensitivity, but its large molecular structure causes a decrease in adhesion. . In particular, in the case of a black matrix, in order to achieve the desired optical density of 100108441, the form number A0101, page 3 of 37, 1003179628-0, 201136955 degrees, the content of the black pigment is increased, so that the adhesion is drastically lowered. In this regard, the Korean Patent Application No. 2000-0055255 discloses a cadmium-based resin and a decane-based coupling agent which are copolymerized with various monomers, but has poor storage stability and is subjected to post-exposure baking treatment. When the heat flow forms a fine pattern, there is a problem of a difference in optical density due to the position. SUMMARY OF THE INVENTION [0007] [0008] [0008] [Problems to be Solved by the Invention] An object of the present invention is to provide an excellent adhesion to a substrate and storage stability. By reducing the thermal fluidity during the post-exposure treatment while maintaining the sensitivity, it is possible to improve the black photosensitive resin composition having a difference in optical density due to the position during formation of the fine pattern, and the black matrix produced using the same. A color filter having the black matrix. <Technical means for solving the problem> In order to achieve the above object, a black photosensitive resin composition comprising an alkali-soluble resin (B) obtained by polymerization of a monomer containing a compound of the following Chemical Formula 1 is provided. (Chemical Formula 1)

(In Chemical Formula 1, η represents a constant of 2 to 4). The monomer may further contain a compound described in the following Chemical Formula 2. (Chemical Formula 2) 100108441 Form No. Α0101 Page 4 of 37 1003179628-0 201136955

[0009] [0012] [Chemical Formula 2, which represents a constant of 〇~2). The compound which has been planted in the formula 1 may contain a 〇 to 4 〇 weight portion with respect to the monomer. The compound (4) recorded in Chemical Formula 2 may contain 10 to β of the monomer. The soluble resin (8) may contain 25 parts by weight relative to the solid content of the composition. Further, it comprises a (meth)acrylic acid sl compound, an aromatic compound 1 acid vinyl vinegar compound, a vinyl cyanide compound = a quinone imine compound, a acetyl acid, a compound, an unsaturated gas propane carboxylate. An acid ester compound, a monocarboxylic acid compound, a compound of _ ^ ^ ± a ^ , a compound of a sulfhydryl compound having a mercapto group and a hydroxyl group at the wood end of the compound or a plurality of compounds. The selected photosensitive composition of the fresh-keeping group may further comprise a mixture of the individual selected from the "green compound (C), photopolymerization initiator (D) agent (Α) light-concentrating group) In order to achieve the other object of the present invention, the present invention is linked to a black matrix in which the black photosensitive resin composition of the present invention is coated and exposed, and obtained by development. In order to achieve still another object of the present invention, the present invention provides a color filter provided with the black matrix of the 100108441 form nickname A0101, page 5 / page 37, 201136955. [0015] <Effect of the Invention> The black photosensitive resin composition of the present invention is excellent in sensitivity not only in adhesion to a substrate, but also in a fine pattern. [0016] The black photosensitive resin composition of the present invention does not have a decrease in sensitivity. At the same time, the thermal fluidity during the post-exposure baking treatment is reduced, and the optical density difference due to the position during the formation of the fine pattern can be improved, thereby producing a black matrix which can uniformly shield the strong backlight. 0017] Black of the invention The photosensitive resin composition is excellent in storage stability and does not change in physical properties during storage. [Embodiment] Hereinafter, the present invention will be described in detail so that the related art can easily carry out the present invention. The black photosensitive resin composition of the present invention contains an alkali-soluble resin (B) obtained by a polymerization reaction with a monomer. The monomer contains a compound described in the following Chemical Formula 1. [0020] (Chemical Formula 1)

In the chemical formula 1, η represents a constant of 2 to 4. [0021] The black photosensitive resin composition of the present invention contains a polymer containing a monomer of the compound described in the following Chemical Formula 1, and the adhesion to the substrate can be improved, and the polymer is non-reactive. Therefore, the storage stability can be improved without a change in line width due to storage. In addition, by 100108441 Form No. 1010101 Page 6 of 37 1003179628-0 201136955 [0022]

[0023] [0024] When the post-exposure baking treatment is performed, the thermal fluidity is small, and the difference in optical density due to the position can be improved, so that a black matrix capable of uniformly shielding the backlight can be manufactured. Specifically, the compound described in Chemical Formula 1 may be acryloyloxyethyl succinic acid or the like, and is preferably used from 4-(2-(acryloyloxy)ethoxy)-4-acetyl. a group consisting of acetic acid, 5-(2-(acryloyloxy)ethoxy)-5-levulinic acid and 6-(2-(acryloyloxy)ethoxy)-6-oxohexanoic acid A single or multiple mixture selected, but not limited thereto. The compound described in Chemical Formula 1 may contain 10 to 40 parts by weight based on the monomer. In other words, a weight of 10 to 40 parts by weight is added to the total amount of the monomers charged for the polymerization of the alkali-soluble resin (B) to be polymerized. When the compound described in the chemical formula 1 contains less than 10 parts by weight, when the pattern is formed, the effect of reducing the thermal fluidity during the post-exposure baking treatment is insignificant, and when the pattern is formed, the residue is formed. The formation of a film may result in poor straightness. In the case of more than 40 parts by weight, when the pattern is formed, problems such as straightening and film uniformity occur due to the sinking phenomenon. The monomer may further contain a compound described in the following Chemical Formula 2. (Chemical Formula 2)

In the chemical formula 2, m represents a constant of 0 to 2. Further, the formula 100108441, Form No. A0101, Page 7 of 37, 1003179628-0, 201136955, contains the compound as a monomer, because the chemical formula and the monomer of the formula are contained in the polymerization. When combined, the thermal fluidity is further reduced by the post-exposure baking treatment, and the difference in optical density due to the positional difference can be reduced when the fine pattern is formed. [0029] Specifically, as the compound described in Chemical Formula 2, isobornyl methacrylate can be used, and it is preferred to use 17 7-trimethylbicyclo[2. ???hept-2-yl methacrylate, 7,7-didecyl y-propyl bicyclo[2.2.1]hept-2-ylmercaptopropionate, 1-ethyl-γ, γ_ Selected from the group consisting of methylbicyclo[2.2.1]hept-2-ylmercapto acrylate and ethylethyl-7,7-indenylbicyclo[2_2.1]heptan-2-yldecyl acrylate Mixtures of singly or plural, but not limited to them. The compound described in Chemical Formula 2 may contain 1 to 40 parts by weight based on the monomer. When the pattern is formed, the adhesion is weak, and when it is more than 40 parts by weight, the developability is lowered and the adhesion to the substrate is increased, and the fine pattern is formed. There will be difficulties in terms of formation. Additionally, the monomer may further contain a compound having an unsaturated bond which can be copolymerized with the compound described in the above Chemical Formula 1 or Chemical Formula 2. In other words, the monomer other than the compound described in the above Chemical Formula 1 or Chemical Formula 2 is additionally supplied and copolymerized to produce the soluble resin (Β) of the present invention. Specifically, it may further comprise a (meth) acrylate-based compound (the (meth) acrylate has both a mercaptopropionate and a propionate), an aromatic vinyl compound, and a slow Ethyl acetate compound, gasified ethylene compound, maleic amine compound 'vinyl carboxylate compound' unsaturated propylene oxide carboxylate 100108441 Form No. 1010101 Page 8 of 37 1003179628- 0 201136955

The compound, the monocarboxylic acid compound, the dicarboxylic acid compound, and the mixture of the compound having a carboxyl group and a hydroxyl group at the two terminals may be selected as a single or plural mixture, but not limited thereto. Specifically, the (fluorenyl) acrylate-based compound is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, or 2-hydroxyethyl (meth) acrylate. a non-substituted or substituted alkyl ester compound of an unsaturated carboxylic acid such as (mercapto) benzyl acrylate or decyl (meth) acrylate; an unsaturated carboxylic acid glycidyl ester compound such as glycidyl methacrylate or The monocarboxylic acid glycol ester compound such as methyl methacrylate oligoethylene glycol monoalkyl ester is not limited thereto. Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, and vinyltoluene, but are not limited thereto. Specific examples of the vinyl carboxylic acid ester compound include vinyl acetate or vinyl propionate, but are not limited thereto. Specific examples of the vinyl cyanide compound include acrylonitrile, mercapto acrylonitrile or α-apopropanonitrile, but are not limited thereto. Specific examples of the maleimide compound include anthracene-cyclohexylmaleimide or anthracene-stupyl maleimide.

But not limited to this. Specific examples of the compound of the ethyl ruthenium sulphate include vinyl acetate or acetal propionate, but are not limited thereto. Specific examples of the unsaturated epoxy-propionic acid ester compound include 3-methyl-3-propenyloxydecyl propylene oxide and 3-methyl-3-isobutenyloxymethyl propylene oxide. 3-ethyl-3-propenyloxymethyl propylene oxide, 3-ethyl-3-isobutenyloxymethyl propylene oxide, 3-methyl-3-acryloyloxyethyl propylene oxide, 3 - mercapto-3-isobutoxyethyl propylene oxide, 3-mercapto-3-acryloyloxyethyl propylene oxide or 3-mercapto-3-isobutenyloxyethyl propylene oxide, etc. Without being limited thereto, "specific examples of the monocarboxylic acid compound" are acrylic acid, methacrylic acid or crotonic acid, but not 100108441 Form No. 1010101 Page 9 of 37 pages 1003179628-0 201136955 limit. Specific examples of the dicarboxylic acid compound include fumaric acid, mesaconic acid or itaconic acid, but are not limited thereto. Specific examples of the compound having a carboxyl group and a hydroxyl group at the two terminals include 〇-carboxypolycaprolactone polyol mono(meth)acrylate, etc., but are not limited thereto. The alkali-soluble resin (B) may contain 4 to 25 parts by weight, preferably 5 to 2 parts by weight, based on the solid content of the composition. When the alkali-soluble resin (B) contains less than 4 to 25 parts by weight, the solubility in the developer is sufficient, so that pattern formation is facilitated, and film formation in the exposed portion can be prevented from being reduced during development. Therefore, the integrity of the pixel portion becomes better. [0031] The black photosensitive resin composition may further comprise a separate group selected from the group consisting of a coloring agent (A), a photopolymerizable compound (c), a photopolymerization initiator (]), and a solvent (E). Or a mixture of plural species. [_ The coloring agent (A) contains a black pigment (A1) and an organic pigment (A2). [0033] The black pigment (A1) is not particularly limited as long as it has a light-shielding pigment, but specific For the purpose, aniline black, ruthenium black, titanium black, carbon black or the like can be used. [0034] The organic pigment (A2) functions as a color correcting agent, and a pigment known in the art such as printing ink or inkjet ink can be used without limitation, and specifically, a water-soluble azo pigment can be used. Insoluble azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline quinone pigment, isoindoline pigment, anthraquinone pigment, cyclic ketone pigment, dioxazine pigment, anthraquinone pigment, diterpene pigment, Alizarin pyrimidine pigment, 蒽 蒽 100108441 Form No. A0101 Page 10 / Total 37 pages 1003179628-0 201136955 (anthanthrone) pigment, indanthrone pigment, buddy 1 pigment, 芘蒽鲖 (Pyranthrone) pigment, Diketopyrrolopyrene pigments, etc. 'but not limited to this. [0037] The colorant (A) is contained in a solid content of 2 to 7 Å, preferably 3 to 65 parts by weight, relative to the solid content of the composition. When the colorant (A) contains 20 to 70 parts by weight, when the film is formed, the optical density is sufficiently 'developed, and the occurrence of residue in the pixel portion is reduced. Here, the "solid-opening tool J, the meaning means the total amount of the remaining components after removing the solvent from the black photosensitive resin composition. The photopolymerizable compound (C) can be started by photopolymerization. A compound which is polymerized by the action of the agent (D) may be a monofunctional monomer, a difunctional early or a polyfunctional monomer, and a difunctional or higher polyfunctional monomer may preferably be used. Specific examples are decyl phenol carbitol vinegar, 2-hydroxy-3-phenoxy propyl acrylate, 2-ethylhexyl propylene propylene diacetate, acrylic acid 2-carboxylate Ethyl ester or N-ethylene group, but not limited thereto. As a specific example of the difunctional monomer, there is 1,6-hexanediol di(meth)acrylate, B. Diol (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether or 3 _mercapto diol di(meth) acrylate, etc., but not limited thereto. As a specific example of the polyuterine monomer, trimethylolpropane tris(methyl) Acrylate, ethoxylated trimethylolpropane tris(indenyl) propylene 100108441 Form No. A0101 Page 11 of 37 1003179628-0 [0039] 201136955 Acidate, propoxylated trihydroxydecylpropane Tris(mercapto) acrylate, pentaerythritol di(meth) acrylate vinegar, pentaerythritol tetrakis(meth) acrylate, pentaerythritol penta(indenyl) acrylate, ethoxylated dipentaerythritol hexa Acrylate, propoxylated dipentaerythritol hexa(meth) acrylate or dipentaerythritol hexa(meth) acrylate, etc., but not limited thereto. [0040] The photopolymerizable compound (C) is relatively The solid content of the composition may be 3 to 40 parts by weight, preferably 5 to 30 parts by weight. When the photopolymerizable compound (C) contains 3 to 40 parts by weight, the strength and smoothness of the exposed portion are obtained. The photopolymerization initiator (D) is not limited, and a photopolymerization initiator known in the related art can be used. Specifically, a triazine compound, a acetophenone compound, or a diimidazole can be used. Compound and bismuth compound A single or a plurality of selected mixtures are selected. Specifically, the triazine compound is 2,4-bis(trimethylmethyl)-6-(4-methoxyphenyl)-1,3. , 5-triazine, 2, 4-bis(trimethyl)-6-(4-decyloxynaphthalene)-1,3,5-triazine, 2,4-bis(trimethyl)- 6-Pepperyl-1,3,5-triazine, 2,4-bis(tris-methyl)-6_(4-decyloxystyrene)-1,3,5-triazine, 2, 4- Bis(trimethylsulfonyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(triseodecyl)-6 -[2_(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trimethylsulfonyl)-6-[2-(4-diethylamino-2- Methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trimethylsulfonyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]- 1,3,5 _三嘻, etc.' but not limited to this. 100108441 Form No. A0101 Page 12 of 37 1003179628-0 201136955 [0044] Specifically, the acetophenone-based compound is diethoxyacetophenone, 2-hydroxy-2-methyl- 1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropanone, 1-hydroxyl Cyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-phenylmorphopropan-1-one, 2-benzyl-2-didecylamino-(4_ Oligomers of morpholinyl phenyl ketone, butan-1-one, 2-hydroxy-2-mercapto-1-[4-(dimethylvinyl)phenyl]propan-1-one, etc. limit. Further, the acetophenone-based compound may be a compound described in the following Chemical Formula 3 (Chemical Formula 3)

[0045] In the chemical formula 3, 1^~1?4 represents a separate hydrogen atom, a functional atom, a hydroxyl group, a stupid group which may be substituted by an alkyl group having 1 to 12 carbon atoms, and may have a carbon number of 1 to 12 The alkyl group is substituted with a benzyl group or a naphthyl group which may be substituted with a C 1 to 12 alkyl group. Specific examples of the compound described in Chemical Formula 3 are 2-methyl-2-amino(4-morphinyl)ethyl-1-one and 2-ethyl-amino (4-morpholinyl). Phenyl)ethan-1-one, 2-propyl-2-amino(4-morpholinylphenyl)ethyl-butanone 2-butyl-2-amino(4-morpholinylphenyl)- 1-keto, .2-mercapto-2-amino(4-pipelinylphenyl)propan-1-amine, 2-methyl-2-amino(4-morpholinylphenyl)butan-1-one , 2-ethyl-2-amino(4-mercapto basic) propan-1-steel, 2-ethyl-2-amino(4-cylinylphenyl)butan-1-one, 2-mercapto 2-nonylamino (4-morphinylphenyl) propan-buxoton, 2-mercapto-2-diindolyl (4-morpholinylphenyl)propan-1-one, 2-anthracene Alkyl-2-diethylamino(4-cylinylphenyl)propan-1-one 100108441 Form No. A0101 Page 13 of 37 1003179628-0 201136955 etc., but not limited thereto. [0048] Specifically, the diimidazole compound is 2, 2'~雔(2chlorophenyl)-4,4,5,5'-tetraphenyldiimidazole, 2, 2,-bis(23-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2 2,bis(2,3-diphenyl)-4'4,5 , 5'-tetraphenyldiimidazole, 22,_bis (2-phenylphenyl 4'4', 5'5'-tetrakis(sodium pyrene)diimidazole, 2,2,-bis(2- Chlorophenyl)-4,4,55, _tetrakis(trisethoxyphenyl)diimidazole, 17 m salic compound substituted by alkoxycarbonyl group at the 4,4',5,5 position Etc., preferably, 2,2,-bis(2-hydroxyphenyl)-4,4',5,5,-tetraphenyldiimidazole, 2,2,-bis(2'3-diphenylbenzene) can be used. _4, 4', 5, 5'-tetraphenyldiimidazole, etc., but not limited thereto. The x s s may be described in any one of the following Chemical Formulas 4 to 6, for example. Compound (Chemical Formula 4) 100108441 [0049]

(Chemical Formula 6) Form No. _丨 Page 14 of 37 1003179628-0 [0050] 201136955

[0051]

In addition to the above-mentioned photopolymerization initiator, other photopolymerization initiators and the like which are generally used in the technical field can be added as long as the effects of the present invention are not impaired. Examples of the other photopolymerization initiator include a benzoin compound, a scleroside compound, a sedative compound, a spermidine compound, and a poly-functional thiol compound. A suitable compound may be used singly or in combination of two or more. Specifically, the benzoin-based compound is benzoin, benzoin decyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl or the like, but is not limited thereto. Examples of the benzophenone-based compound include benzophenone, 0-benzoylbenzoic acid methyl ' 4-phenylbenzophenone, 4-benzyl aceta-4, -methyldiphenyl sulfide, 3, 3', 4, 4' - tetra (tert-butyl peroxycarbonate) benzophenone, 2, 4, 6-trimethylbenzophenone and the like. Specifically, the thioxanthone compound is 2-isopropyl thioxanthone, 2, 4-diethyl thioxanthone, 2, 4-dithioxanthone, and b-butyl-4-propoxy Base thioxanthone, etc., but not limited to this. Specifically, the spermidine compound is a 9, 10-dimethoxyanthracene, 2-ethyl-9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 2-ethyl -9, 10-diethoxy hydrazine, etc., but not limited to this. Specifically, the polyoxyl thiol compound is tris-(3-mercaptopropionic acid)-ethyl-isocyanuric acid, trishydroxypropylpropane tris- 3 -mercaptopropionic acid, pentaerythritol tetra-3 - mercaptopropionic acid, dipentaerythritol tetra_3_mercaptopropionic acid, etc., but not as 100108441

limit. Form No. 1010101 Page 15 of 37 I 1003179628-0 201136955 [0055] [0056] In addition, 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide can be used. , 1 〇 丫疋 、 、 , 2 - 蒽 蒽 、 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , use. The photopolymerization initiator (D) may contain 20 parts by weight, preferably 0.5 to 10 parts by weight, based on the solid content of the composition. When the photopolymerization: the starter (D) contains a 〇··~ 〇 weight portion, the sensitivity of the black photosensitive resin composition is excellent, and the exposure time is shortened, and the productivity is known: while being maintained, it can be maintained Since the fineness is high, the strength and smoothness of the exposed portion are good, which is preferable. In the photopolymerization initiator (D), a photopolymerization initiator (Dq) can be used in combination. When a photopolymerization initiator (D-1) is used in combination with the photopolymerization initiator (D), a black photosensitive resin composition containing these photopolymerization initiators can be made higher in sensitivity and form a black matrix or black column interval (Black). The productivity of Column Spacer) is improved. As the photopolymerization initiator (D-1), a single or a mixture of a plurality of selected ones selected from the group consisting of an amine compound and a carboxylic acid compound can be used. Specifically, the amine compound is an aliphatic amine compound such as triethanolamine, mercaptoethanolamine or triisopropanolamine; or an alkyl group of 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4 -Isoamyl dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-didecylaminoethyl benzoate, N,N-dimethyl-p-nonylamine, 4 , 4'-bis(dimethylamino)benzoquinone_ (commonly known as Michler'sketone), 4,4'-bis(diethylamino)benzophenone, etc. Preferably, 100108441 Form No. A0101 Page 16 of 37 1003179628-0 201136955 Aromatic amine compounds are used, but not limited thereto. Specifically, the carboxylic acid compound is phenylthioacetate, methylphenylthioacetate, ethylphenylthioacetate, mercaptoethylphenylthioacetate, dimethyl Phenyl phenyl thioacetate, methoxyphenyl thioacetate, dimethoxyphenyl thioacetate, chlorophenyl thio 6 acid salt, dichlorophenyl thioacetate, hydrazine-phenylamino An aromatic heteroacetate such as acetic acid, phenoxyacetic acid, naphthylthioacetate, hydrazine-naphthylaminoacetic acid or naphthyloxyacetate, but not limited thereto. The photopolymerization initiator (D-1) may have a weight of 0.01 to 10 parts, preferably 0.01 to 5 parts by weight, relative to the solid content of the composition. When the photopolymerization initiator (D-1) contains 0.1 to 10 parts by weight, the sensitivity of the black photosensitive resin composition increases, and the strength and smoothness of the colored layer formed by the addition are increased, and the color is increased. The productivity of the filter is also improved. Ο The solvent (Ε) is not limited, and a solvent known in the related art can be used. Specifically, ethylene glycol monodecyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl can be used. Ethylene glycol monoalkyl ethers such as ether and ethylene glycol monobutyl ether; diethylene glycol didecyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol II Diethylene glycol dialkyl ethers such as butyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate; propylene glycol oxime ether acetate, propylene glycol monoethyl Alkenyl glycol alkyl ether acetates such as ether acetate, propylene glycol monopropyl ether acetate; alkoxyalkyl acetates such as methoxybutane acetate and methoxypentan acetate; Aromatic hydrocarbons such as benzene, toluene, diphenylbenzene, and trimethylbenzene; methyl ethyl ketone, acetone, decylpentanone ketone, decyl isobutylene 100108441 Form No. 101 0101 Page / Total 37 Page 1003179628-0 201136955 曱_, cyclohexanone, etc. 曱 _ p _ class, ethanol, propanol, butanol, hexanol, cyclohexyl, ethylene glycol, and _ 1 Bu Qiao 2, etc. Alcohols; 3-ethoxy phenylpyruvate ethyl [0060] [0063] oxy-type benzyl acid such as methyl; and τ-τ /,, a mixture of individual or plural selected from the group. It is preferably used from 9ηΛ. I consider the properties of cloth and dryness, organic solvents with a boiling point of 1 00~c, _ _ better use of ene glycol alkyl ether acetate, 曱1, 3~;?> « Milk A mixture of two or more selected from the group consisting of ethylpyruvate ethyl and 3-methoxypropiophenone·, :, and the like may be propylene glycol monodecyl ether acetic acid, propylene glycol monoethyl ^ A mixture of a single or a plurality of selected ones of the acid group '1, 3, ethoxyphenylpyruvate ethyl and 3' methoxy acyl-acid methyl groups. The δ' sizing agent (E) contains 6 〇 to 90 parts by weight, preferably 7 〇 to 88 parts by weight, based on the black photosensitive resin composition. When the solvent (ε) contains a weight of 60 to 9 Torr, a roll coater, a rotary coater, a slit and a rotary coater, a slit coater (die coater, Die Coater), When the coating apparatus is applied, the coating property is good. In addition to the above-described components, the black photosensitive resin composition of the present invention can be used in combination with a filler, other polymer compound, a hardener, a pigment, and a densely packed one, without departing from the object of the present invention. An additive F such as an accelerator, an oxidation preventive, an ultraviolet absorber, or an aggregation inhibitor. Specifically, the filler may be glass, ruthenium, alumina, or the like, but is not limited to 100108441 Form No. A0101, page 18 of 37, 1003179628-0, 201136955. Specifically, as the other polymer compound, a curable resin such as an epoxy resin or a maleimide resin, polyethylene glycol, polyacrylic acid, polyethylene glycol monoalkyl ether, or perfluoroalkyl acrylate may be used. , thermoplastic resins such as polyester and polyurethane, etc., but not limited to this. [0065] The curing agent is used to improve core hardening and mechanical strength, and specifically, an epoxy compound, a poly-isocyanate compound, or an epoxy compound can be used.

Ο melamine compounds, propylene oxide compounds, etc., but not limited to this. Specifically, as the epoxy compound, a bisphenol fluorene epoxy resin, a hydrogenated bisphenol fluorene epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol F epoxy resin, a phenolic epoxy resin, or the like can be used. Aromatic epoxy resin, cycloaliphatic epoxy resin, glycidyl ester resin, glycidylamine resin or brominated derivative of this type of epoxy resin, epoxy resin and its desertified derivative Aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co)polymer epoxides, isoprene (co)polymer epoxides, glycidyl (meth) acrylates ) Polymer, triglycidyl isocyanate, etc. 'but not limited thereto. Specifically, the propylene oxide compound may use carbonate dipropylene oxide, xylene dipropylene oxide, adipic acid dipropylene oxide, p-dibenzoate dipropylene oxide, cyclohexane dicarboxylic acid double Propylene oxide, etc., but not limited to this. The curing agent may be used in combination as a hardening auxiliary compound which can ring-open the polymerization of a curing agent with an epoxy group of an epoxy compound or a propylene-fired skeleton of a propylene oxide compound. Specifically, as the hardening auxiliary compound, a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydrate, an acid generator or the like can be used. The carboxylic acid anhydride can be used as a resin hardener for a commercially available product. For example, as a 100108441, the form number A0101, the 19th page, and the 37th page, 1003179628-0, 201136955, the product name (adeka HARDENER EH-700) (made by ADEKA AG), and the product name (RIKACID) HH) (manufactured by Shin-Nippon Chemical and Chemical Co., Ltd.), trade name (MH-700) (manufactured by Shin-Sakamoto Rika Co., Ltd.), etc. The curing agent and the hardening auxiliary compound may be used singly or in combination of two or more. [0068] The pigment dispersant may be a commercially available surfactant, and specifically, a group of surfactants such as Shixia, fluorine, ester, cationic, anionic, nonionic, and amphoteric may be used. A mixture of individual or plural selected. More specifically, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitol fatty acid vinegars, fatty acid-modified polyesters, and tertiary amine-modified polyurethanes can be used. For the product name, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), ρ- can be used.

Top (manufactured by T0KEM Products Co., Ltd.), MEGAFAC (manufactured by Dainippon Ink and Chemicals, Inc.), Fluor ad (manufactured by Sumitomo 3M), ASAHI CURD, and Surf Ion (above, manufactured by Asahi Glass Co., Ltd.)

Solsperse (made by Lubrizol), EFKA (made by EFKA CHEMICALS), 'PB821 (made by Ajinomoto Co., Ltd.), Disperbyk-series (BYK-chemi), etc. [0069] Specifically, the adhesion promoter may use vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-decyloxyethoxy) decane, N-(2-amino group Ethyl)-3-aminopropyl-decyldimethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxy sulphur[3] - glycidyl ether propyl trimethyl sulphate, 100108441 Form No. A0101 Page 20 of 37 1003179628-0 201136955 [0070] ζ) [0071] [0073]

3-Glycidyl bond propyl tridecyldimethoxy sulphate, 2-(3,4-epoxycyclohexyl)ethyltrimethylsulfonyl sulphate, 3-chloropropylmethyl dimethyl Oxycarbonyl, 3-cyclopropyltrimethoxydecane, 3-methacryloxypropyltrimethoxysulfonate, 3~thylpropyltrimethoxycarbazide, 3-isocyanatepropyldimethoxylate A mixture of individual or plural selected from the group consisting of Xishou and 3-isocyanate propyl triethoxylate. 05〜2重量部。 The adhesion promoter may be contained in a weight ratio of the composition of the composition. Specifically, 'the oxidation inhibitor may be 2, 2,-thiobis(4-methyl-6-t-butyl phenol), 2,6_:_t_butyl-4-methylphenol, etc., but Not limited to this. Specifically, the ultraviolet absorber may be 2-(3-tert-butyl-2-hydroxy-5-mercaptophenyl)-5-chlorobenzotriazole, decyloxybenzazole or the like, but not This is limited to this. Specifically, the aggregation inhibitor may be used, but not limited to sodium polyacrylate or the like. The black photosensitive resin composition of the present invention can be produced by the method described below. The coloring agent (A) was previously mixed with the solvent (E), and the average particle diameter of the coloring agent was lowered to about 0.2/zm, and dispersed in a bead mill to obtain a dispersion. At this time, a pigment dispersant may be used as needed, and it is also possible to test that the soluble resin (B) may be partially synthesized or all synthesized. In the obtained dispersion (hereinafter, in the case of a polishing base), the residual of the alkali-soluble resin (B), the photopolymerizable compound (C), and the photopolymerization initiator (D) are required to be added, and after the addition, the additive F is added. 100108441 Form No. A0101 Page 21 of 37 1003179628-0 201136955 It is necessary to add an additional solvent to a black photosensitive resin composition represented by θ as a target. [0079] [0079] The color filter related to the present invention will be described below. In the private color light-receiving sheet of the present invention, the black photosensitive resin composition according to the present invention described above is applied to the upper portion of the substrate, and the black matrix or the black column interval can be obtained by exposure and development in a predetermined pattern. Further, a method of forming a pattern of a black matrix or a black column interval using a black photosensitive resin composition according to the present invention includes a coating step of coating the black photosensitive resin composition on a substrate, and selecting An exposure step of exposing a part of the black photosensitive resin composition to an exposure step and a development step of removing the exposure region or the exposure region of the black photosensitive resin composition. In the coating step, a black photosensitive resin composition of the present invention is applied onto a substrate and preliminarily dried to remove a volatile component such as a solvent to obtain a smooth coating film. 5〜5#m。 At this time, the thickness of the coating film is about 0. 5~5#m. The substrate may be a plate of a plastic substrate such as glass, tantalum wafer or polysulfonate (pES: P〇lyethersuifone) or polycarbonate (pc: p〇lycarb〇n_ate), but there is nothing special about its kind. limit. This exposure step is a step of irradiating the ultraviolet rays in a specific field through a mask in order to obtain a pattern represented by the object on the coating film obtained in the foregoing process. At this time, the parallel light is uniformly irradiated on the entire exposed portion, and a device such as a mask aligner or a stepper is preferably used in order to accurately align the position with the substrate. 100108441 Form No. A0101 Page 22 of 37 1003179628-0 201136955 [0082] The development step is performed by using a coating film which is hardened in the foregoing process. The step of contacting the aqueous solution of the developer to dissolve the non-exposed field and performing development can produce a pattern representative of the object. After development, it may be dried at 150 to 230 ° C for about 1 to 6 minutes. The developer used in the developing step is usually an aqueous solution containing a basic compound and a surfactant. As the basic compound, an inorganic or organic basic compound can be used. Specifically, the inorganic basic compound can be sodium oxychloride, hydrazine hydroxide, dihydrogen hydride, sodium dihydrogen citrate, diammonium citrate or citric acid. Ammonium hydroxide, potassium dihydrogen citrate, sodium citrate, ruthenium sulphate, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, rotten acid clock, ammonia, and the like. In addition, specifically, the organic basic compound may be exemplified by tetrakilyl gas oxidation, 2-phenylethyltrimethyl hydroxide, monoammine, dimethylamine, tridecylamine, and monoethyl Alkylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, and the like. The weight of the inorganic and organic compounds can be singly or in combination of two or more. The preferred concentration of the bismuth compound is in the range of from 〇1 to 1 0. In the developer, the surfactant may be a mixture of a single or a plurality of selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant. Specifically, 'the nonionic surfactant may be a polyoxyethylene alkyl ether, a hydroxy ether, a polyoxyethylene alkyl aromatic hydroxy ether, a derivative, an oxyethylene/oxypropylene block copolymer ester, or a polyoxyethylene sorbent. Alcohol fatty acid esters, glycerol fatty acid polyoxyethylene aromatic other polyoxyethylene, sorbitan fatty acid exhaust, polyoxyl 100108441 Form No. A0101 Page 23 of 37 201136955 Ethylene fatty acid ester, polyoxyethylene alkylamine Wait. Specifically, the anionic surfactant may be a higher alcohol sulfate salt such as sodium lauryl sulfate or oleyl sulfate, a sodium lauryl sulfate, a lauryl sulfate or the like, a decyl sulfate or a dodecyl group. An alkyl propylene sulfonate such as sodium phenyl sulfonate or sodium lauryl sulfone sulfonate. Specifically, as the cationic surfactant, an amine salt such as stearylamine hydrochloride, lauryl trimethyl gasification or a fourth-order ammonium salt or the like can be used. The surfactants may be used singly or in combination of two or more. The weight of the surfactant is 0.1 to 10 parts by weight, preferably 0. 05 to 8 parts by weight, more preferably 〇. 1 to 5 parts by weight. [0085] Through the foregoing process, a black matrix or black column interval can be obtained. The configuration and manufacturing method of the color filter are known in the art to which the present invention pertains, and detailed description thereof will be omitted. According to the present invention, a liquid crystal display device including the above color filter is also included in the scope of application. The liquid crystal display device of the present invention includes a known configuration in addition to the color filter described above in the technical field of the present invention. That is, a liquid crystal display device to which the color filter of the present invention is applicable is included in the present invention. An example of an electrode substrate including a thin film transistor (TFT element), a pixel electrode, and an alignment layer is provided so as to face each other at a predetermined interval, and a liquid crystal material is injected into the gap portion as a liquid crystal layer. Transmissive liquid crystal display device. Further, there is also a reflective liquid crystal display device in which a reflective layer is provided between a substrate of a color filter and a coloring layer. 100108441 Form No. A0101 Page 24 of 37 1003179628-0 201136955 [0086] Further, as another example, a TFT (Thin Film Transistor) substrate including a transparent electrode bonded to a color filter may be cited; And a liquid crystal display device of a backlight fixed at a position where the TFT substrate overlaps the color filter. The TFT substrate may include an outer frame composed of a light-preventing resin surrounding a peripheral surface of the color filter, and a liquid crystal layer composed of nematic liquid crystal supplied to the outer frame; a plurality of pixel electrodes in each field of the liquid crystal layer; a transparent glass substrate composed of the pixel electrodes; and a polarizing plate formed on the exposed surface of the transparent glass substrate.偏 [0087] The polarizing plate has a polarizing direction that is vertically transmitted, and is composed of the same organic material as polyethylene glycol. The plurality of pixel electrodes are connected to a plurality of thin film transistors respectively formed on the glass substrate of the TFT substrate. If a predetermined potential difference is applied to a specific pixel electrode, a predetermined voltage can be applied between the pixel electrode and the transparent electrode. Therefore, the electric field formed corresponding to the voltage can change the alignment of the field corresponding to the specific pixel electrode of the liquid crystal layer. The present invention will be described in more detail by way of examples and comparative examples. These examples are only intended to illustrate the invention and are not intended to limit the scope of the invention. [Production Example> Production of Pigment Dispersion Liquid 〕] Carbon black 2 〇 g, AJISPER ΡΒ 821 (manufactured by Ajinomoto Fine-Techmo Co., Ltd.) as a dispersing agent, 6 g of propylene glycol oxime ether as a solvent 74 g of acetic acid vinegar was mixed and dispersed by a bead mill for 12 hours to produce a pigment dispersion liquid. 100108441 Form No. 1010101 Page 25 of 37 1003179628-0 201136955 [<Synthesis Example 1 to 20 > Synthesis of Alkali Soluble Resin] Agitator, thermometer, reflux cooling tube, dropping funnel and nitrogen introduction In a 1 000 ml flask of the tube, propylene glycol methyl ether acetate (PGMA), AIBN, 2-acryloyloxyethyl succinate (Bl), N-stupyl horse were charged according to the amounts shown in Table 2 and Table 3 below. The imine, stupid ethylene, methacrylic acid, and isobornyl methacrylate (B-2) were subjected to nitrogen substitution (the units of the following Tables 2 and 3 are g). Thereafter, the temperature of the reaction liquid was raised to 100 ° C while stirring, and then the reaction was further carried out for 7 hours. The final solid content of the alkali-soluble resin thus synthesized, the acid value of the solid component, and the weight average molecular weight measured by GPC are shown in Tables 2 and 3 below. (B-1) and (B-2) used in the respective synthesis examples are the same as in the following Table 1 [0091] [Table 1] Synthesis Example acryloyloxyethyl succinate Ο1) Isoborn A Acrylic acid SS (B-2) 1 3- (2-(nonenoyloxy)ethoxy)-3-oxopropionic acid 1,7,7-trimethylbicyclo[2.2.1]heptane- 2-Based methacrylate 2 3·(2-(acryloyloxy)ethenyl)-3-oxopropionic acid V?-dimethyl-1-propylbicyclo[2.11]heptan-2-yl Methylpropionic acid® 3 4-(2-(acryloyl)ethoxy)*4-acetoacetic acid 1,7/7-trimethyl-sodium (2.2,]]hept-2-ylmethyl Acrylate 4 (2-(Propyloxy)ethoxy)acetoacetate 1-hexyl-7,7-dimethylbicyclo[2.2.1]hept-2-ylmethacrylate 5 4- (2- (acryloyloxy)ethoxy)4-acetoacetic acid 7,7·dimethyl propyl bicyclo[2.2.1]hept-2-yl methacrylic acid _ 6 4- (2-(propylene oxyfluoride) Ethyl)) acetoacetate dimethyl-1_phenylbicyclo[2.2.1]hept-2-ylmethyldecenoic acid S 7 4-(2-(acryloyloxy)decyloxy) Acetylacetic acid 1,7,7·trimethylbicyclo[2.2.1]hept-2-ylmethylpropane Benzene male 8 9 4- (2-(2-enoyloxy)ethoxy) hexanoyl acetic acid 7,7-dimethyl-hydrazine-ft-bicyclo[2.2.1]hept-2-ylmethyl Acrylic acid into 4-(2-(acryloyloxy)ethoxy) acetoacetic acid 1,7,7-trimethylbicyclo[2.2.1]hept-2-ylmethacrylic acid® 10 5. (2 (二灿政氡)Ethoxy)-5-acetylpropionate 1,7,7-trimethylbicyclo(2.2.1)hept-2-ylmethacrylic acid S Π 5- (2-(two Ethylenyloxy)ethoxy)acetylpropanol 1-ethyl-7,7·dimethylbicyclo[2.2.1]hept-2-ylmethacrylic acid chisel 12 5- 〇(3⁄4 跌 跌 oxy) Ethoxy)-5-levulinic acid 7,7-dimercapto-1-propylbicyclo[2.2.1]hept-2-ylmethacrylic acid S 13 5-(2-(dienyloxy) Ethoxy)-5-levulinic acid 7>Dimethyl small stupidylbicyclo[2.2.1]hept-2-ylmethyl methacrylate 14 S-C2-(acryloyloxy)ethylidene) 1,7,7-tridecylbicyclo[2.2,1]heptan-2-yl methacrylic acid SS 15 S-(2-(dienyloxy)hexyloxy) oxo hexa Ethyl-7,7-dimethylbicyclo[2.2.1]hept-2-yl methacrylate 16 fi_[2-(acryloyloxy) Alkoxy)7,7-dimethyl-l-diylbicyclo[O.sub.2-9 hept-2-yl methacrylic acid S 17 i (propanoloxy)ethoxy) 1,7,7-trimethylbicyclo[2.2.1]heptan-2-ylf- acrylate 18 Fi·C2-(nonenoyloxy)ethenyl)oxohexanoic acid 1 ,7,7·trimethylbicyclo[2.2.1]hept-2-ylmethacrylate 19 R- ΠC-dienoyl-rolling) hexyl) oxo-octyl 1/7,7-three Methyl bicyclo [2.2.1] hept-2-yl methacrylate hydrazine 20 4- (2-(3⁄4 enoyl hydrazino) ethoxy) 4· 乙乙乙睃----- [0092] [Table 2] 100108441 Form No. A0101 Page 26/37 Page 1003179628-0 201136955 Composition Synthesis Example I Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 Synthesis Example 9 Synthesis Example 10 PGMA 400 400 400 400 400 400 400 400 400 400 MBN 7 7 7 7 7 7 7 7 7 7 3-1 45 45 45 45 45 1 45 15 15 85 45 M· Stupid Malay “Bowlamine 58 58 58 58 58 58 65 65 15 58 20 20 20 20 20 20 30 30 8 20 Methacrylic acid 40 40 40 40 40 40 55 55 10 40 B-2 20 20 20 20 20 20 15 15 90 20 Reaction time 7 7 7 7 7 7 7 7 7 7 B forming fraction (wt%) 31.00 30.79 30.90 31.00 31.00 30.90 30.70 30.85 33.87 31.00 Acid price 123 120 125 127 120 128 135 133 100 127 Molecular Dong 12000 13100 13000 13000 13100 9000 8500 9000 15000 [Table 3] Composition Synthesis Example 11 Synthesis Example 12 Synthesis Example 13 Synthesis Example 14 Synthesis Example 15 Synthesis Example 16 Synthesis Example 17 Synthesis Example 18 Synthesis Example 19 Synthesis Example 20 PGMA 400 400 400 400 400 400 400 400 400 400 «ΒΝ 7 7 7 7 7 7 7 7 7 7 3-1 45 45 45 45 45 45 15 85 45 45 Stupid base maleate 58 58 58 58 58 58 65 15 58 58 Stupid vinyl 20 20 20 20 20 20 30 8 20 20 Methacrylic acid 40 40 40 40 40 40 55 10 40 40 B-2 20 20 20 20 20 20 15 90 20 • During the reaction "7 7 7 7 7 7 7 7 7 7 Cluster formation (Wt °/P) 31.05 31.20 31.00 30.88 31.00 30.90 30.85 33.87 31.20 29.3 *Reimbursement 123 122 126 125 123 120 130 100 130 132 Molecular weight 13100 13100 10000 12800 12800 12500 10000 14000 8500 9800 [Example 1 to 1 7 > Manufacture of black photosensitive resin composition] 组成The composition of the following list 4 and 5 'use Guan methods well known in the industry for producing a black photosensitive resin composition. The units of the following Tables 4 and 5 are g » [0095] [Table 4] 100108441 Form No. A0101 Page 27 of 37 1003179628-0 201136955 [Table 5] Composition Example 10 η 12 13 14 15 16 17 Pigment Dispersion Μ 50 50 50 50 50 50 50 50 Synthesis Example 7 9.5 Synthesis Example 8 9.5 Synthesis Example 9 9.5 Synthesis Example 9.5 Synthesis Example 18 9.5 Synthesis Example 20 9.5 Synthesis Example 6 9.5 Synthesis Example 13 9.5 Photopolymerizable Compound υ 1.98 1.98 1.98 1.98 1.98 1.98 1.98 1.98 Igacure 3692) 0.2] 0.21 0.21 0.21 0.21 0.21 0.21 0.21 [gracure 〇XE013) 0.4 0.4 0,4 0.4 0.4 0.4 0.4 0.4 Egracure OXE024) 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Photopolymerization initiator 5:1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 PGMA 37.41 37.41 37.41 37.41 37.41 37.41 37.41 37.41 [0097] Ingredient Example 1 2 3 4 5 6 7 8 9 Pigment Dispersion Μ 50 50 50 50 50 50 50 50 50 Synthesis Example 3 9.5 Synthesis Example 4 9.5 Synthesis Example 5 9.5 Synthesis Example 10 9.5 Synthesis Example 11 9.5 Synthesis Example 12 9.5 Synthesis Example 14 9 .5 Synthesis Example 15 9.5 Synthesis Example 16 9.5 Photopolymerizable Compound 1.98 1.98 1.98 1.98 1.98 1.98 1.98 1.98 Ϊ.98 [gacure 3692) 0.21 0.21 0.21 0.21 0.21 0.21 0.21 0.21 0.21 0.21 [gracure OXE013) 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 [gracurc 〇XE024) 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Photopolymerization initiator 51 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 PGMA 37.41 37.41 37.41 37.41 37.41 37.41 37.41 37.41 37.41 1 ) KAYARAD DPHA (made by Sakamoto Pharmaceutical Co., Ltd.) 2) Ciba Specialty Chemical 3) Ciba Specialty Chemical 4) Ciba Specialty Chemical 100108441 Form No. A0101 Page 28 of 37 1003179628-0 201136955 5) 4,4'-Di(N,N'-Dimercaptoamino) - benzophenone (manufactured by Hodogaya Chemical Co., Ltd.) [<Comparative Example 1 to 4 > Production of Black Photosensitive Resin Composition] The composition of the following Table 6 was produced in the same manner as in the above Example. A photosensitive resin composition. The unit of the following list 6 is g. [Table 6] Composition comparison 1 Comparison example 2 Comparative Example 3 Comparative Example 4 Pigment dispersion Μ 50 50 Synthesis Example 1 9, 5 Synthesis Example 2 9.5 Synthesis Example 19 9.5 Cadmium Resin η 9.5 Photopolymerizable Compound 2) 1.98 1.98 1.98 1.98 Igacure3693) 0.21 0.21 0.21 0.21 IgracureOXE014) 0.4 0.4 0.4 0.4 IgracureOXE025) 0.4 0.4 0.4 0.4 Photopolymerization starter δ) 0.1 0.1 0.1 0.1 PGMA 37.41 37.41 37.41 37.41 [0100] 1 ) WR-101 ADEKA 2 ) KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 3) Ciba Specialty Chemical 4) Ciba Specialty Chemical 5) Ciba Specialty Chemical 6) 4,4'-bis(N,N'-didecylamino)-benzophenone (Evaluation of Thermal Fluidity) [Electrical Example 1> Evaluation of Thermal Fluidity] The black photosensitive resin compositions produced in the above Examples 1 to 17 and Comparative Examples 1 to 4 were rotated. The coating method was applied to a glass substrate, and then placed on a hot plate at a temperature of 100 ° C for 2 minutes to form a film. 100108441 Form No. A0101 Page 29 of 37 1003179628-0 201136955 Next, a pattern having a transmittance ranging from 1 to 100% in a stepwise manner is placed on the film; and Ι/zm Measure the mask of the pattern of ~50#m line width/line spacing, and set the interval between the test mask and the setting mask to 50 0 // m for ultraviolet irradiation. At this time, the ultraviolet light source was irradiated with an illuminance of 50 mJ/cm 2 using a high-pressure mercury lamp of 1 kW containing all of the g, h, and i lines, and no special optical filter was used. The film irradiated with the above ultraviolet rays was immersed in a KOH aqueous solution developing solution of ρ. 5 for 2 minutes to develop a film. The glass plate to which the film was attached was washed with distilled water, then blown with nitrogen, dried, and heated in a heating oven at 230 ° C for 20 minutes to produce a color filter. 0微米。 The film thickness of the film is 1. 0 μ m. For the 20 gm map of the exposed portion remaining after development, the film thickness of the film was measured before and after the post-exposure baking treatment, and the thermal fluidity was measured in the same manner as the following, and the results were evaluated according to the following criteria. , listed in Table 7. * (film thickness after post-exposure treatment / film thickness before post-baking treatment) X 100 〇: 97% or more, Δ: 95 to 97%, X: 950 / 〇 or less [0103] [Table 7 〕

ί "Example Comparative Example No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 1 2 3 4 Heat flow system 〇〇〇〇〇〇〇〇〇 Δ 〇 Δ 〇〇 △ 〇 X Δ XX

As shown in the above Table 7, it was found that the black photosensitive resin composition of the examples had a small heat flow system and did not largely change in film thickness before and after the post-exposure baking treatment. On the other hand, when the black photosensitive resin composition of the comparative example is known, the thermal fluidity is large, and after the exposure, the baking process is 100108441. Form No. A0101, page 30/37 pages, 1003179628-0, 201136955, before and after, A difference in film thickness is produced. Further, the compounding amount of the chemical formula and the chemical formula 2 was a small amount of the composition of Example 1, and the effect of lowering the thermal fluidity was not improved to the same extent as the other examples. [Experimental Example 2> Evaluation of Storage Stability] The black photosensitive resin composition for light shielding manufactured in the above-described Examples 1 to 17 and Comparative Ships ~ 4 was placed under the muscles, and placed 5 separately. The composition of the day, the 3rd day, the ι day; and the composition produced by the model before the experiment of the pattern corresponding to the respective composition of the Yi Zhaobiao Shenjie ^bei #', was applied by spin coating After being placed on the glass substrate, it is placed on a hot plate at a temperature just after. In c, it was maintained for 2 minutes to form a film. A test reticle having a pattern of 2 - was implanted and set at a distance of 5 〇 _ from the test reticle for ultraviolet ray irradiation. At this time, the feed line diaphragm was irradiated with a high-pressure mercury lamp containing all of the g, h, and i lines (10), and the illuminance of the milk-2 was used, and no special optical filter was used. Jiang Zhao shot & 丄 用 用 用 照射 照射 照射 照射 照射 照射 照射 照射 照射 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线After the nitrogen is blown into the crucible, it is dried, and then heated in a heating oven of Gossip, C., and heated for 20 knives to produce a color filter. In the color grading sheet produced in the foregoing process, the line width of the pattern formed on the mask having a width of 2 〇 _ is measured, and the CCD of the line width variation caused by the placement time is The measurement was carried out, and the results are shown in the following table [0106] ΔCD The line width of the pattern evaluated by the resin composition manufactured by Tian Tian - the pattern evaluated by the regular temperature (4) lipid composition Line width 〇: △ CD: 0. 5 The following 100108441 Form number A0101 Page 31 of 37 1〇〇3179628-0 201136955 Δ : ACD = 0.5~1.0//m χ : ACD = 1. 0 ym or more [ 0107] [Table 8]

EXAMPLES Comparative Example No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 1 2 3 4 5 days Place 〇〇〇〇〇〇〇〇〇 XX 〇X 〇〇XX Δ XXX 3 days 〇〇〇〇〇〇〇〇〇Δ Δ 〇Δ 〇〇△ Δ Δ Δ Δ X 1 day placement 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 X

As shown in the above Table 8, the black photosensitive resin composition of the example did not cause a difference in pattern line width at room temperature based on the standing time of the composition, but the composition of the comparative example was self-placed 3 In the future, the change in the line width of the pattern is started. [<Experimental Example 3> Evaluation of fineness and sensitivity] The composition of the above examples and comparative examples was applied onto a glass substrate by a spin coating method, and then placed on a hot plate at a temperature of l〇〇. In °C, it was maintained for 2 minutes to form a film. A test mask having a pattern of 20 was placed and placed at a distance of 50 μm from the test mask to perform ultraviolet irradiation. At this time, the ultraviolet light source was irradiated with an illuminance of 50 mJ/cm 2 using a high-pressure mercury lamp of 1 kW containing all of the g, h, and i lines, and no special optical filter was used. The film irradiated with the above ultraviolet rays was immersed in a KOH aqueous solution developing solution of pH 10.5 for 2 minutes to carry out development. The glass plate to which the film was attached was washed with distilled water, and then observed with an optical microscope until a few / m pattern was observed, and is shown in Table 9 below. [Table 9] 100108441 Form No. A0101 Page 32 of 37 1003179628-0 201136955 Example Comparative Example No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 1 2 3 4 Type ffl (sensitivity) 4 4 4 4 4 4 4 4 4 6 8 6 8 6 4 4 4 8 10 10 4 [0111] As shown in the above Table 9, the composition of the example can be known, because 8/zm Since the pattern remains, the sensitivity is excellent, and the composition of the comparative example remains after the pattern of 8 //m, so the sensitivity is good. In the case of Examples 10, 11 and 13 in which the content of the monomer of Chemical Formula 1 or Chemical Formula 2 was small, the adhesion and the degree of sensitivity were somewhat reduced. Further, in the case of Examples 12 and 14 in which the content of the monomer of Chemical Formula 1 or Chemical Formula 2 is high, it is revealed that as the adhesion increases, the connection of the residual film occurs between the fine patterns, and the sensitivity is further reduced. tendency. [Experimental Example 4 > Evaluation of Adhesiveness] After performing the development process in the same manner as in Experimental Examples 1 to 3, the ultrahigh pressure washing process (2 MPa) was carried out for 30 seconds using distilled water. After that, an optical microscope was used to observe the pattern of several patterns, and it was shown in Table 10. [Table 10] Example Comparative Example No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 1 2 3 4 Adhesion ring type 4 6 4 6 4 6 6 6 6 10 10 6 8 6 6 8 8 16 16 10 6 [0114] According to the above Table 10, the composition of the examples can be known, and compared with the composition of the comparative example, there is no washing phenomenon until the fine pattern There is also no connection between the graphics. As described above, the black photosensitive resin containing the alkali-soluble resin produced by polymerizing the single 100108441 Form No. A0101, page 33/37 pages, containing the compound of Chemical Formula 1 of the present invention, is contained. The composition is excellent not only in adhesion to the substrate, sensitivity, and storage stability, but also has a low heat flow property during the post-exposure baking treatment, and can reduce the pattern downflow phenomenon, thereby providing an optical density average map. Type and Black Matrix 〇 [Simple Description] [0116] No [Main Component Symbol Description] [0117] None 100108441 Form No. A0101 Page 34 of 37 1003179628-0

Claims (1)

201136955 VII. Patent application scope: 1. A black photosensitive resin composition comprising a polymer obtained by polymerizing one of the compounds described in the following Chemical Formula 1 to obtain a soluble resin (B). Black photosensitive resin composition, (Chemical Formula 1) (In Chemical Formula 1, η represents a constant of 2 to 4). ^2. The black photosensitive resin composition according to claim 1, wherein the oxime monomer further comprises a compound described in the following Chemical Formula 2, (Chemical Formula 2) (In Chemical Formula 2, m represents a constant of 0 to 2). 3. The black photosensitive resin composition according to claim 1, wherein The compound of Chemical Formula 1 contains 10 to 40 parts by weight based on the monomer. 4. The black photosensitive resin composition according to claim 2, wherein the compound of the chemical formula 2 contains 10 to 40 parts by weight based on the monomer. 5. The black photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (B) contains 4 to 25 parts by weight relative to the solid content of the composition. 6. The black photosensitive resin composition as described in claim 1, the 100108441 Form No. A0101, page 35/37, 1003179628-0, 201136955 The single system further comprises a (meth) acrylate compound, aroma Group vinyl compound, acidified ethyl vinegar compound, vinyl cyanide compound, maleic imine compound, ethylene retinoic acid compound, unsaturated epoxidized acid ester compound, single trehalic acid compound a mixture of two or a plurality of selected ones of the group consisting of a compound of a tetrandic acid compound and a compound having a carboxyl group and a hydroxyl group at the two terminals. 7. The black photosensitive resin composition according to claim 1, wherein the black photosensitive resin composition further comprises a coloring agent (A), a photopolymerizable compound (C), and a photopolymerization initiator (D). And a mixture of individual or plural selected from the group consisting of solvent (e). The black matrix is obtained by coating, exposing and developing the black photosensitive resin composition according to any one of the above claims. 9. A color filter having a black matrix as described in claim 8 of the patent application. 100108441 Form No. A0101 Page 36 of 37 1003179628-0