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    • 专利摘要:
    The present invention provides a colored photosensitive resin composition containing a compound (F) having a coloring agent (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E) and a benzylidene skeleton; A method of forming a pattern by applying the colored photosensitive resin composition onto a substrate, removing the volatile component from the applied colored photosensitive resin composition layer, and then exposing and developing the layer from which the volatile component is removed from the colored photosensitive resin composition layer through a photomask. ; A color filter comprising a pattern formed by the method; And a liquid crystal display device equipped with the color filter.
    公开号:KR20040034512A
    申请号:KR1020030072487
    申请日:2003-10-17
    公开日:2004-04-28
    发明作者:이치카와고지
    申请人:스미또모 가가꾸 고교 가부시끼가이샤；
    IPC主号:
    专利说明:

    Colored photosensitive resin composition {A colored, photosensitive resin composition}
    [1] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to photosensitive resin compositions widely used in ultraviolet curable inks, photoresists, and the like, and particularly to resist coatings for forming colored images (hereinafter sometimes referred to as pixels) for use in color liquid crystal displays and imaging devices. It relates to a colored photosensitive resin composition suitable for the present invention.
    [2] The color filter in a color liquid crystal display device, an image pick-up element, etc. is normally manufactured by forming red, green, and blue three primary color pixels on board | substrates, such as glass and a silicon wafer. In addition, in order to shield between these pixels, a black matrix is usually provided. In order to form the pixels of each color, a resist coating containing a pigment corresponding to each color is uniformly applied by a spin coater on the substrate on which the black matrix is patterned, followed by heat drying (hereinafter, prebaking). And a method of exposing and developing such a coating film, and further heat curing (hereinafter sometimes referred to as post-baking) as necessary, is employed, and this operation is performed for each color required for the color filter. By repeating, images of each color are obtained. As such a resist, many compositions containing a photopolymerizable monomer and a photoinitiator together with a pigment and binder resin are used. Moreover, the resist containing a black pigment may be used also in formation of a black matrix.
    [3] Since the photoinitiator used for such a resist determines the characteristic and quality which are necessary for manufacturing a color filter, the thing with high sensitivity, the surface smoothness of a produced color filter, pattern shape, chemical resistance, and high reliability are examined, have. As such an example, a coloring photosensitive resin composition using a triazine compound, a mixture of a triazine compound and an imidazole compound, a mixture of a triazine compound, an imidazole compound, an aminoacetophenone compound, a benzophenone, or the like has been proposed (examples). For example, see Unexamined-Japanese-Patent No. 6-201913, Unexamined-Japanese-Patent No. 6-324484, Unexamined-Japanese-Patent No. 7-261014, etc.). In addition, with regard to high sensitivity, a mixture consisting of a polyfunctional thiol compound and at least one compound selected from biimidazole compounds, titanocene compounds, triazine compounds and oxadiazole compounds, 2-piperonyl-4,6-bis (Trichloromethyl) -s-triazine, or a mixture consisting of the above-described triazine compound, biimidazole-based compound, and hydrogen donor has been proposed (for example, JP 10-253815 A). , Japanese Unexamined Patent Publication No. 2000-221675 and the like). Although the color filter formed using the coloring photosensitive resin composition which has such a photoinitiator as a component has the said advantage, there existed a problem that the shape of the color pixel formed as a disadvantage worsens.
    [4] An object of the present invention is to provide a colored pixel pattern having a good shape and having good sensitivity to a colored photosensitive resin composition; A method of forming a colored pixel pattern having a good shape; A color filter comprising a colored pixel pattern having a good shape; And a color filter including a colored pixel pattern having a good shape.
    [5] The present invention provides a colored photosensitive resin composition containing a compound (F) having a coloring agent (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E) and a benzylidene skeleton; A method of forming a pattern by applying the colored photosensitive resin composition onto a substrate, removing the volatile component from the applied colored photosensitive resin composition layer, and then exposing and developing the layer from which the volatile component is removed from the colored photosensitive resin composition layer through a photomask. ; A color filter comprising a pattern formed by the method; And a liquid crystal display device equipped with the color filter.
    [6] The colored photosensitive resin composition of this invention is mainly used as a pigment dispersion resist, and a coloring agent (A) is normally disperse | distributed in a solvent (E), and also binder resin (B), a photopolymerizable compound (C), and a photoinitiator ( D) and the compound (F) having a benzylidene skeleton, and optionally other additives are dissolved or dispersed.
    [7] The colorant (A) usually consists of a pigment, and may be an organic pigment or an inorganic pigment commonly used in pigment dispersion resists. Examples of the inorganic pigments include metal compounds such as metal oxides and metal complex salts, and specific examples include metal oxides or composite metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. Can be mentioned. Moreover, as an organic pigment, the compound classified by Pigment can be mentioned specifically, in Color Index (The Society of Dyers and Colourists publication). More specifically, although the compound of the following color index (C.I.) numbers is mentioned, It is not limited to these.
    [8] Specific examples of the organic pigments and inorganic pigments include compounds classified as pigments in the color index (published by The Society of Dyers and Colourists). Specifically, for example, C.I. Pigment Yellow 1, C. I. Pigment Yellow 3, C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 15, C.I. Pigment Yellow 16, C.I. Pigment Yellow 17, C.I. Pigment Yellow 20, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 53, C.I. Pigment Yellow 83, C.I. Pigment Yellow 86, C.I. Pigment Yellow 93, C.I. Pigment Yellow 94, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 117, C.I. Pigment Yellow 125, C.I. Pigment Yellow 128, C.I. Pigment Yellow 137, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 147, C.I. Pigment Yellow 148, C.I. Pigment Yellow 150, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 166, C.I. Pigment Yellow 173, C.I. Pigment Yellow194, C.I. Yellow pigments such as pigment yellow 214;
    [9] C.I. Pigment Orange 13, C.I. Pigment Orange 31, C.I. Pigment Orange 36, C.I. Pigment Orange 38, C.I. Pigment Orange 40, C.I. Pigment Orange 42, C.I. Pigment Orange 43, C.I. Pigment Orange 51, C.I. Pigment Orange 55, C.I. Pigment Orange 59, C.I. Pigment Orange 61, C.I. Pigment Orange 64, C.I. Pigment Orange 65, C.I. Pigment Orange 71, C.I. Orange pigments such as pigment orange 73;
    [10] C.I. Pigment Red 9, C.I. Pigment Red 97, C.I. Pigment Red 105, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 144, C.I. Pigment Red 149, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 209, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 264, C.I. Red pigments such as pigment red 265;
    [11] C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Blue pigments such as pigment blue 60;
    [12] C.I. Pigment Violet 1, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment violet 32, C.I. Pigment Violet 36, C.I. Purple pigments such as pigment violet 38;
    [13] C.I. Pigment Green 7, C.I. Green pigments such as pigment green 36;
    [14] C.I. Pigment Brown 23, C.I. Brown pigments such as pigment brown 25;
    [15] C.I. Pigment Black 1, C.I. Black pigments, such as pigment black 7, etc. are mentioned, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Red 177, C.I. Pigment Red 209, C.I. Pigment Red 254, C.I. Pigment Red Violet 23, C.I. Pigment Blue 15: 6 and C.I. It preferably contains one or more pigments selected from pigment green 36.
    [16] These coloring agents (A) can be used individually or in combination of 2 types or more, respectively. The coloring agent (A) is usually used in the range of 5 to 60 mass%, preferably 10 to 55 mass%, based on the amount of solids in the colored photosensitive resin composition. When the content of the colorant (A) is in the range of 5 to 60 parts by mass based on the above criteria, even in the case of a thin film, the color density of the pixel is sufficient, and since the omission of the non-pixel portion does not decrease during development, no residue is generated. It tends to be preferable. In addition, in this invention, solid content amount in a coloring photosensitive resin composition means the total amount of the component except a solvent (E), and solid content of a coloring photosensitive resin composition consists of a component which removed the solvent (E) from the coloring photosensitive resin composition. Means.
    [17] As a binder resin (B) used in this invention, an acryl-type copolymer can be used, For example, the copolymer with a carboxyl group-containing monomer and the other monomer which can be copolymerized with this is mentioned.
    [18] As a carboxyl group-containing monomer, the unsaturated carboxylic acid which has one or more carboxyl groups in molecules, such as unsaturated polycarboxylic acid, such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and unsaturated tricarboxylic acid, is mentioned, for example. Here, as unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example. As unsaturated dicarboxylic acid, a maleic acid, a fumaric acid, itaconic acid, a citraconic acid, a mesaconic acid, etc. are mentioned, for example. The unsaturated polyvalent carboxylic acid may be an acid anhydride thereof, specifically maleic anhydride, itaconic anhydride, citraconic anhydride, or the like. Moreover, the unsaturated polyhydric carboxylic acid here also contains mono (2-methacryloyloxyalkyl) ester of polyhydric carboxylic acid, For example, mono succinate (2-acryloyloxyethyl) and mono succinate (2- Methacryloyl oxyethyl), mono phthalate (2-acryloyl oxyethyl), mono phthalate (2-methacryloyl oxyethyl), etc. are mentioned. In addition, the unsaturated polyhydric carboxylic acid includes, for example, -Carboxy polycaprolactone monoacrylate, -Carboxy polycaprolactone monomethacrylate, and the like. These carboxyl group-containing monomers can be used individually or in mixture of 2 or more types, respectively.
    [19] As another monomer copolymerizable with the said carboxyl group-containing monomer, For example, styrene, (alpha) -methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, p- chlor styrene, o-methoxy styrene, m-methoxy styrene, p-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether aromatic vinyl compounds such as p-vinylbenzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, secondary-butyl acrylate, secondary-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2- Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2 -Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxy Tyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate , 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, Methoxytriethylene glycol methacrylate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate Latex, dicyclopentadienyl acrylate, dicyclopentadiene Methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate unsaturated carboxylic acid esters and the like;
    [20] 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxylic acid amino such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate Alkyl esters;
    [21] Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate;
    [22] Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate;
    [23] Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether;
    [24] Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide;
    [25] Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide and N-2-hydroxyethyl methacrylamide;
    [26] Unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide;
    [27] Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene;
    [28] Polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate, having a monoacryloyl group or a monomethacryloyl group at the terminal of the polymer molecular chain of polysiloxane Macro monomers, etc. are mentioned. These monomers can be used individually or in mixture of 2 or more types, respectively.
    [29] Content of the carboxyl group-containing monomeric unit in the said copolymer is 10-50 mass% normally in a mass fraction, Preferably it is 15-40 mass%, Especially preferably, it is 25-40 mass%. When content of the said carboxyl group-containing monomeric unit is 10-50 mass%, solubility with respect to a developing solution is favorable and it exists in the tendency for the pattern to form correctly at the time of image development, and it is preferable.
    [30] As said acrylic polymer, a (meth) acrylic acid / methyl (meth) acrylate copolymer, a (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth, for example) ) Acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macro monomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethyl (meth) acrylate Macro monomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macro monomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macro monomer copolymer, (meth) Acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macro monomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / Benzyl (meth) acrylate / polymethyl (meth) acrylate macro monomer copolymer, (meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / mono succinate ( 2-acryloyloxyethyl) / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monosuccinate (2-acryloyloxyethyl) / styrene / allyl (meth) Acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / benzyl (meth) acrylate / N-phenylmaleimide / styrene / glycerol mono (meth) acrylate copolymer, etc. are mentioned. In addition, (meth) acrylate shows that it is an acrylate or a methacrylate.
    [31] Among these, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) Acrylic acid / methyl (meth) acrylate / styrene copolymer etc. are preferable.
    [32] In the acrylic polymer described above, the weight average molecular weight (polystyrene as a standard product, obtained by gel permeation chromatography) in terms of its polystyrene is usually 5,000 to 50,000, preferably 8,000 to 40,000, particularly preferably Is 10,000 to 35,000. When the molecular weight is 5,000 to 50,000, the coating film hardness is improved, the residual film ratio is also high, the solubility in the developer of the unexposed part is good, and the resolution tends to be improved, which is preferable.
    [33] In the acrylic polymer, the acid value thereof is usually 50 to 150, preferably 60 to 140, particularly preferably 80 to 135. When the acid value is 50 to 150, the solubility in the developing solution is improved, so that the unexposed portion is easily dissolved, and since the pattern is exposed to high sensitivity, the exposed portion tends to remain and the residual film ratio is improved. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can usually be obtained by titration using an aqueous potassium hydroxide solution.
    [34] The binder resin is usually contained in the range of 5 to 90% by mass, preferably 10 to 70% by mass, based on the amount of solids in the colored photosensitive resin composition of the present invention. When the binder resin (B) is 5 to 90% by mass based on the above criteria, the solubility in the developer is sufficient, the development residue is hardly generated on the substrate of the non-pixel portion, and the film reduction of the pixel portion of the exposed portion at the time of development It is hard to occur, and the omission of a non-pixel part becomes favorable, and it is preferable.
    [35] The photopolymerizable compound (C) contained in the coloring photosensitive resin composition of this invention is a compound which can superpose | polymerize by the action of light and the following photoinitiator, and may be bifunctional and other polyfunctional monomer other than a monofunctional monomer.
    [36] Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the like. Can be mentioned.
    [37] As specific examples of the bifunctional monomer, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, etc. are mentioned.
    [38] Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate etc. are mentioned. Among these, the bifunctional or more than polyfunctional monomer is used preferably.
    [39] A photopolymerizable compound (C) is 1-60 mass parts normally with respect to a total of 100 mass parts of binder resin (B) and a photopolymerizable compound (C) in a coloring photosensitive resin composition, Preferably it is the range of 5-50 mass parts It is contained. If content of a photopolymerizable compound (C) is the range of 1-60 mass parts on the said reference | standard, there exists a tendency for the intensity | strength and smoothness of a pixel part to become favorable, and it is preferable.
    [40] Next, it is preferable that the photoinitiator (D) contained in the coloring photosensitive resin composition of this invention contains a polyfunctional thiol compound and at least 1 compound chosen from the group which consists of a triazine compound, an acetophenone compound, and a biimidazole compound. Do. More preferably, a biimidazole compound and a polyfunctional thiol compound are included. The colored photosensitive resin composition containing said photoinitiator (D) becomes more sensitive, and the film | membrane formed using this becomes more favorable in intensity and surface smoothness of the pixel part. Moreover, the coloring photosensitive resin composition obtained by using together a photoinitiation start adjuvant becomes more highly sensitive, and since it is improved in the productivity at the time of forming a color filter using this, it is preferable.
    [41] Examples of the triazine compound included in the photopolymerization initiator (D) of the colored photosensitive resin composition of the present invention include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1, 3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 -[2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5- Triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, and the like.
    [42] Moreover, as an acetophenone compound contained in the photoinitiator (D) of the coloring photosensitive resin composition of this invention, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2 -Hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl ) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [ Oligomer of 4- (1-methylvinyl) phenyl] propan-1-one, etc. are mentioned.
    [43] Moreover, as a biimidazole compound contained in the photoinitiator (D) of the coloring photosensitive resin composition of this invention, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimi Dazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (for example, JP-A-6-75372 and Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'- Tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (for example, Japanese Patent Publication 48-38403 and JP-A 62-174204, etc.), imidazole compounds in which the phenyl group at the 4,4 ', 5,5'-position is substituted by a carboalkoxy group ( For example, work (See Japanese Patent Application Laid-Open No. Hei 7-10913, etc.), and the like, and preferably 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbi. Imidazole and 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole.
    [44] A polyfunctional thiol compound is a compound which has two or more thiol groups in a molecule | numerator, Especially the aliphatic polyfunctional thiol compound which has two or more thiol groups in an aliphatic group is preferable.
    [45] Examples of the aliphatic polyfunctional thiols used in the present invention include hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediolbisthiopropionate, butanediolbisthioglycolate, ethylene glycol bisthioglycolate, trimethylol Propane tristhioglycolate, butanediol bisthio propionate, trimethylol propane tristyropropionate, trimethylol propane tristhioglycolate, pentaerythritol tetrakistiopionate, pentaerythritol tetrakisthioglycolate, tris Hydroxyethyltristyoplopionate and other thioglycolates, thiopropionates of polyhydric hydroxy compounds, and the like, and trimethylolpropanetristyopiothionate, trimethylolpropane trithiothioglate, and the like. Pentaerythritol tetra And other examples thereof include cisthiopropionate, and particularly preferably pentaerythritol tetrakistiopionate.
    [46] Moreover, as long as it does not impair the effect of this invention, the photoinitiator etc. which are normally used in the said field can be used together, For example, a benzoin type, a benzophenone type, a thioxanthone type, anthracene type, and other initiators are used. Can be mentioned. More specifically, the following compounds are mentioned, These can be used individually or in combination of 2 or more types, respectively.
    [47] (a) Benzoin series
    [48] Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and the like.
    [49] (b) benzophenone series
    [50] Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone , 2,4,6-trimethylbenzophenone and the like.
    [51] (c) thioxanthones
    [52] 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxy city oxanthone, and the like.
    [53] (d) anthracene
    [54] 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene and the like.
    [55] (e) other
    [56] 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 10 -Butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound and the like.
    [57] Moreover, a photoinitiator can be used in combination with a photoinitiator. An amine compound, an alkoxy anthracene type compound, a thioxanthone type compound etc. are mentioned as a photoinitiation start adjuvant.
    [58] Examples of the amine compound include triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminoethyl benzoate. , 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively Michler's ketone), 4,4'-bis (diethylamino) benzo Phenone, 4,4'-bis (ethylmethylamino) benzophenone, etc. are mentioned, Among these, 4,4'-bis (diethylamino) benzophenone is preferable.
    [59] As an alkoxy anthracene type compound, 9, 10- dimethoxy anthracene, 2-ethyl-9, 10- dimethoxy anthracene, 9, 10- diethoxy anthracene, 2-ethyl-9, 10- diethoxy anthracene etc. Can be mentioned.
    [60] As a thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4 Propoxy city oxanthone etc. are mentioned.
    [61] The photopolymerization initiator may be used alone or in combination of many. Moreover, a commercially available thing can be used as a photoinitiator starting adjuvant. Examples of commercially available photopolymerization start adjuvant include trade name "EAB-F" (refer to Hodogaya Kagyo Kogyo Co., Ltd.).
    [62] As a combination of the photoinitiator and the photoinitiation adjuvant in the coloring photosensitive resin composition of this invention, diethoxy acetophenone / 4,4'-bis (diethylamino) benzophenone, 2-methyl- 2-morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one / 4,4'- Bis (diethylamino) benzophenone, benzyldimethyl ketal / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] Propan-1-one / 4,4'-bis (diethylamino) benzophenone, 1-hydroxycyclohexylphenyl ketone / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2 -methyl
    [63] Oligomer / 4,4'-bis (diethylamino) benzophenone of 2--1- [4- (1-methylvinyl) phenyl] propan-1-one, 2-benzyl-2-dimethylamino-1- (4- A combination of morpholinophenyl) butan-1-one / 4,4'-bis (diethylamino) benzophenone, and the like, and preferably 2-methyl-2-morpholino-1- (4- And combinations of methylthiophenyl) propane-1-one / 4,4'-bis (diethylamino) benzophenone.
    [64] In the photoinitiator (D), the total amount of the photopolymerization initiator (D) is usually 0.1 to 40 parts by mass, preferably 1 to 30 parts by mass based on 100 parts by mass of the total of the binder resin (B) and the photopolymerizable compound (C). The total amount of the photopolymerization start adjuvant is contained in the range of usually 0.1 to 50 parts by mass, preferably 1 to 40 parts by mass based on the above criteria.
    [65] If the total amount of photoinitiator (D) exists in the said range, a coloring photosensitive resin composition will become high sensitivity, and the intensity | strength of the pixel part formed using said coloring photosensitive resin composition and the smoothness in the surface of the said pixel will become favorable. It is preferable. In addition to the above, when the amount of the photopolymerization initiation aid is in the above range, the sensitivity of the obtained colored photosensitive resin composition is further increased, and the productivity of the color filter formed using the colored photosensitive resin composition tends to be improved, which is preferable. Do.
    [66] As the solvent (E), various solvents used in the art can be used. Specific examples of the solvent (E) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether;
    [67] Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether;
    [68] Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;
    [69] Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate;
    [70] Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene;
    [71] Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone;
    [72] Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin;
    [73] Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate;
    [74] Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned. Among these, Preferably, propylene glycol monomethyl ether acetate is mentioned.
    [75] These solvents (E) can be used individually or in mixture of 2 or more types, respectively.
    [76] The amount of the solvent (E) used is usually 60 to 90% by mass, preferably 70 to 85% by mass, with respect to the whole colored photosensitive resin composition including the same. If content of a solvent (E) is the range of 60-90 mass% on the said reference | standard, there exists a tendency for applicability | paintability to become favorable and it is preferable.
    [77] As a compound which has the (F) benzylidene frame | skeleton used by this invention, the compound which has a partial structure of General formula (1) is mentioned.
    [78]
    [79] Moreover, the compound of General formula (2) is mentioned as a compound which has a benzylidene frame | skeleton.
    [80]
    [81] In Formulas 1 and 2, Q 1 to Q 3 are each independently a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxyl group.
    [82] In formula (2), Q 4 is an alkyl group and X is a cyano group or an alkoxycarbonyl group. The alkyl group, alkoxyl group and alkoxycarbonyl group in these definitions may each have 1 to 6 carbon atoms. In addition, in the formula (2), when X is an alkoxycarbonyl group, the two ester moieties may be the same or different. In the unsaturated carboxylic ester compound of the formula (2), a compound in which X is a cyano group can be produced by the reaction of the corresponding benzaldehydes and cyanoacetic acid esters. In addition, the compound whose X is an alkoxycarbonyl group can be manufactured by reaction of corresponding benzaldehyde and malonic acid diester.
    [83] As a compound having a benzylidene skeleton suitable for use in the present invention, specifically, dialkyl benzylidene malonic acid dialkyl, 4-hydroxy-3-methoxybenzylidene malonic acid dialkyl, 4-hydroxybenzylidene malonic acid dialkyl, 2, 4- dihydroxy benzylidene malonic acid dialkyl, 2-cyano-3- (4-hydroxy-3- methoxyphenyl) propene acid alkyl, etc. are mentioned.
    [84] The usage-amount of the compound (F) which has a benzylidene frame | skeleton is 0.001-3 mass% normally in solid of the photosensitive resin composition, Preferably it is 0.01-2 mass%, More preferably, it is 0.1-1 mass%. When the usage-amount of the compound (F) which has a benzylidene frame | skeleton is 0.001-3 mass% on the said reference | standard, it exists in the tendency for a resolution and a missing property to become favorable, and it is preferable.
    [85] The coloring photosensitive resin composition of this invention can mix and use additives (G), such as a filler, another high molecular compound, a pigment dispersing agent, an adhesion promoter, antioxidant, a ultraviolet absorber, and an aggregation inhibitor, as needed.
    [86] As a filler, glass, silica, alumina, etc. can be used specifically as a high molecular compound, Polyvinyl alcohol, polyacrylic acid, a polyethyleneglycol monoalkyl ether, a polyfluoroalkyl acrylate, etc. can be used specifically ,.
    [87] Commercially available pigment dispersants may be used as the pigment dispersant, and examples thereof include silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants, and the like. It is used in combination of the above. Examples of the surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, and polyethylene imines. Et al., KP [Reference: Shin-Etsuka Furniture Co., Ltd.], Polyflow (Reference: Kyoeka Furniture Co., Ltd.), F-Top (Ref .: Tochem Products Co., Ltd.), Megafax [Reference: Dainihon Ink Car Furniture Co., Ltd.], Floride (Ref .: Sumitomos Reem Co., Ltd.), Asahi Guide (Res .: Asahigaras Co., Ltd.), Saffron (Res .: Asahigara's Co., Ltd.) Manufactured by Kaisha, Solfas, Inc. (manufactured by Genca Corp.), EFKA (manufactured by EFKA CHEMICALS), PB821 [manufactured by Ajinomoto Corp. ], And the like.
    [88] Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-. (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyl Trimethoxysilane etc. are mentioned.
    [89] Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, and the like.
    [90] Specific examples of the ultraviolet absorber include 2- (tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like.
    [91] Moreover, sodium polyacrylate etc. are mentioned specifically as a flocculant.
    [92] The coloring photosensitive resin composition of this invention can be manufactured as follows, for example. That is, the coloring agent (A) is previously mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the coloring material is about 0.2 µm or less. At this time, a pigment dispersant is used as needed, and some or all of binder resin (B) may be mix | blended. The remainder of the binder resin (B), the photopolymerizable compound (C) and the photopolymerization initiator (D), other components used as necessary, or additional solvent as needed in the obtained dispersion (hereinafter sometimes referred to as a mill base). (E) is added so as to become a predetermined concentration to obtain a target colored photosensitive resin composition.
    [93] The colored photosensitive resin composition of this invention manufactured in this way can be apply | coated on a base material as follows, for example, photocuring and developing, and it can be set as a black matrix or a colored image.
    [94] First, this composition is spin-coated on a board | substrate (usually glass), heat-dried (prebaking), a solvent is removed, and a smooth coating film is obtained. At this time, the thickness of a coating film is about 1-3 micrometers.
    [95] The ultraviolet-ray is irradiated to the coating film obtained in this way through the negative mask for forming an objective black matrix or an image. At this time, it is preferable to use a device such as a mask aligner such that the parallel light beam is uniformly irradiated on the entire exposed portion and the mask and the substrate are exactly aligned.
    [96] Then, a desired black matrix or image is obtained by bringing the coated film after curing into contact with a dilute alkali aqueous solution and dissolving and developing the non-exposed part. After development, you may perform post-curing (post baking) about 10 to 60 minutes at 150-230 degreeC as needed.
    [97] The developing solution used for image development after patterned exposure is the aqueous solution containing an alkaline compound and surfactant normally. The alkaline compound may be either an inorganic or organic alkaline compound.
    [98] Specific examples of the inorganic alkaline compounds include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium cinnamic acid, potassium cinnamic acid, sodium carbonate, potassium carbonate, hydrogen carbonate Sodium, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like.
    [99] In addition, specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoiso Propylamine, diisopropylamine, ethanolamine and the like. These inorganic and organic alkaline compounds can be used individually or in combination of 2 types or more, respectively. The preferable concentration of the alkaline compound in the alkaline developer is in the range of 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.
    [100] The surfactant in the alkaline developer may be any of nonionic surfactants, anionic surfactants or cationic surfactants.
    [101] Specific examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkylaryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, and polyoxy Ethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.
    [102] Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate or sodium oleyl alcohol sulfate, alkyl sulfate salts such as sodium lauryl sulfate or ammonium lauryl sulfate, sodium dodecylbenzenesulfonate or dode Alkyl aryl sulfonates, such as sodium cinnaphthalene sulfonate, etc. are mentioned.
    [103] Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, or quaternary ammonium salts.
    [104] These surfactant can be used individually or in combination of 2 or more types, respectively.
    [105] The concentration of the surfactant in the alkaline developer is usually in the range of 0.01 to 10% by mass, preferably 0.05 to 8% by mass, more preferably 0.1 to 5% by mass.
    [106] The pixel or black matrix corresponding to the color of the coloring material in the photosensitive resin composition is obtained through each operation such as the above application of the photosensitive resin liquid, drying, patterned exposure to the dried coating film obtained, and development. By repeating this operation by the number of colors necessary for the color filter, a color filter is obtained. That is, although the color filter normally arrange | positions the black matrix and the three primary color pixels of red, green, and blue on a board | substrate, by performing said operation using the coloring photosensitive resin composition of this invention containing the coloring material corresponding to a certain color. The black matrix and the three primary pixels can be arranged on a substrate by obtaining the black matrix or pixel of the color and performing the same operation using the colored photosensitive resin composition of the present invention containing a coloring material corresponding to a desired color for other colors. Can be. In addition, when the pixel or black matrix of a certain color is once arrange | positioned on a board | substrate, when processing the coloring photosensitive resin composition of another color, the coloring photosensitive resin composition of a separate color is carried out on the board | substrate with which the pixel or black matrix of the said certain color is arrange | positioned. After application | coating and drying, patterned exposure is normally performed in the position where the pixel or black matrix of a certain color is not arrange | positioned, and the pixel or black matrix of the said other color is arrange | positioned at the exposed position. Of course, it is also possible to apply the coloring photosensitive resin composition of this invention only to any 1 type, 2 types, or 3 types of a black matrix and three primary colors. In addition, since the black matrix which is a light shielding layer may be formed with a chromium layer etc., in this case, of course, it is not necessary to use the coloring photosensitive resin composition of this invention for formation of a black matrix.
    [107] And the color filter manufactured using the photosensitive liquid of this invention has a small difference in the film thickness inside surface, For example, in the film thickness of 1-3 micrometers, the film thickness difference inside surface is 0.15 micrometer or less, or 0.05 It can be set to micrometer or less. Therefore, the color filter obtained in this way is excellent in smoothness and transparency, and the liquid crystal panel of the outstanding quality can be manufactured with a high yield by inserting this in a color liquid crystal display device.
    [108] In the above, although embodiment of this invention was described, embodiment of this invention described above is an illustration to the last, and the scope of the present invention is not limited to such embodiment. The scope of the invention is indicated by the claims, and includes all modifications within the meaning and range equivalent to the description of the claims. EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. In the examples,% and parts indicating content to amount of use are based on mass unless otherwise specified.
    [109] The component used by a present Example is as follows, and may abbreviate | omit it and display it below.
    [110] (a-1) C.I. Pigment Blue 15: 6
    [111] (a-2) C.I. Pigment Violet 23
    [112] (b-1) Binder resin: copolymer of methacrylic acid and benzyl methacrylate [the ratio of methacrylic acid unit and benzyl methacrylate unit is 30:70 by mass ratio (molar ratio), the acid value is 113 , Polystyrene equivalent weight average molecular weight is 25,000]
    [113] (c-1) Photopolymerizable compound: dipentaerythritol hexaacrylate (reference: KAYARAD DPHA manufactured by Nihon Kayaku Co., Ltd.)
    [114] (c-2) Photopolymerizable compound: Dimethylol tricyclodecane diacrylate [Reference: KAYARAD R-684 manufactured by Nihon Kayaku Co., Ltd.]
    [115] (d-1) Photoinitiator: 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one
    [116] (d-2) Photoinitiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one
    [117] (d-3) Photoinitiator: 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole (Ref .: Kuroganeka Co., Ltd. make)
    [118] (d-4) Photoinitiator: pentaerythritol tetraquistiopionate
    [119] (g-1) Photopolymerization start adjuvant: 2,4-diethyl thioxanthone
    [120] (g-2) Photopolymerization Initiation Aid: 4,4'-bis (diethylamino) benzophenone
    [121] (h) Epoxy compound [orthocresol novolak-type epoxy resin, "Sumiepoxy ESCN-195XL-80" (reference: Sumitomoka furniture Co., Ltd. product)]
    [122] (f) 4-hydroxy-3-methoxybenzylidene malonic acid diethyl
    [123] Solvent (E): Propylene Glycol Monomethyl Ether Acetate
    [124] Example 1
    [125] Preparation of colored photosensitive resin composition
    [126] (a-1) 6.869 mass parts, (a-2) 0.105 mass parts, 2.094 mass parts of polyester pigment dispersants, (b-1) 6.242 mass parts, (c-1) 4.162 mass parts, (d-3) 0.832 parts by mass, (d-4) 0.208 parts by mass, (g-2) 0.416 parts by mass, (h) 1.040 parts by mass, (f) 0.022 parts by mass, and (e) 78.000 parts by mass to form a colored photosensitive resin composition (1 ).
    [127] Corning's # 1737 glass substrate, each 2 inches in length, was washed sequentially with neutral detergent, water and alcohol and then dried. The above photosensitive resin composition 1 is spin-coated on this glass substrate, and then prebaked for 3 minutes at 100 ° C. during clean open. After cooling, such a resist coated substrate and a quartz glass photomask [hotomask 1 having a pattern for changing the transmittance stepwise in the range of 1 to 100% and a line / space pattern of 1 to 50 microns, and a line width Photomasks for forming linear colored patterns of 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm and 100 μm ( 2)] and 100 micrometers, and it irradiates light at 50mJ / cm <2> or 150mJ / cm <2> exposure amount in air | atmosphere using the ultra-high pressure mercury lamp by Ushio Denki Co., Ltd. make. Subsequently, the coating film is immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 80 seconds, and then washed with water and post-baked at 220 ° C. for 20 minutes.
    [128] evaluation
    [129] The sensitivity which can form a pattern using the photomask 1 is 2 mJ / cm <2>, and in the photomask 2, both 50 mJ / cm <2> exposure and 150 mJ / cm <2> exposure are pure taper.
    [130] Example 2
    [131] Preparation of colored photosensitive resin composition
    [132] (a-1) 6.869 mass parts, (a-2) 0.105 mass parts, 2.094 mass parts of polyester pigment dispersants, (b-1) 6.731 mass parts, (c-1) 2.244 mass parts, (c-2) 1.122 parts by mass, (d-3) 0.897 parts by mass, (d-4) 0.337 parts by mass, (g-2) 0.449 parts by mass, (h) 1.122 parts by mass, (f) 0.022 parts by mass and (e) 78.000 parts by mass The parts are mixed to obtain a colored photosensitive resin composition (2).
    [133] evaluation
    [134] A pattern is formed like Example 1 except using the coloring photosensitive resin composition (2). The sensitivity which can form a pattern using the photomask 1 is 3 mJ / cm <2>, and in the photomask 2, both 50 mJ / cm <2> exposure and 150 mJ / cm <2> exposure are forward taper.
    [135] Comparative Example 1
    [136] Preparation of colored photosensitive resin composition
    [137] (a-1) 6.869 mass parts, (a-2) 0.105 mass parts, 2.094 mass parts of polyester pigment dispersants, (b-1) 4.644 mass parts, (c-1) 5.452 mass parts, (d-1) 1.212 mass parts, (g-1) 0.606 mass part, (h) 1.010 mass part, and (e) 78.000 mass part are mixed, and the coloring photosensitive resin composition (3) is obtained.
    [138] evaluation
    [139] A pattern is formed like Example 1 except using the coloring photosensitive resin composition (3). Although the sensitivity which can form a pattern using the photomask 1 is 50 mJ / cm <2>, the pattern does not remain in 50 mJ / cm <2> exposure in the photomask 2. As shown in FIG. Although the pattern is formed in 150mJ / cm <2> exposure, it is an angled taper.
    [140] Comparative Example 2
    [141] Preparation of colored photosensitive resin composition
    [142] (a-1) 6.869 parts by mass, (a-2) 0.105 parts by mass, 2.094 parts by mass of polyester pigment dispersant, (b-1) 6.264 parts by mass, (c-1) 4.162 parts by mass, (d-3) 0.832 mass part, (d-4) 0.208 mass part, (g-2) 0.416 mass part, (h) 1.040 mass part, and (e) 78.000 mass part are mixed, and the coloring photosensitive resin composition (4) is obtained.
    [143] evaluation
    [144] A pattern is formed like Example 1 except using the coloring photosensitive resin composition (4). The sensitivity at which the pattern can be formed using the photomask 1 is 2 mJ / cm 2, and in the photomask 2, the pattern is not missed for both the 50 mJ / cm 2 exposure and the 150 mJ / cm 2 exposure.
    [145] Comparative Example 3
    [146] Preparation of colored photosensitive resin composition
    [147] (a-1) 6.869 mass parts, (a-2) 0.105 mass parts, 2.094 mass parts of polyester pigment dispersants, (b-1) 6.753 mass parts, (c-1) 2.244 mass parts, (c-2) 1.122 mass parts, (d-3) 0.897 mass part, (d-4) 0.337 mass part, (g-2) 0.449 mass part, (h) 1.122 mass part, and (e) 78.000 mass part, mixing and coloring photosensitive resin composition (5) is obtained.
    [148] evaluation
    [149] A pattern is formed like Example 1 except using the coloring photosensitive resin composition (5). The sensitivity at which the pattern can be formed using the photomask 1 is 5 mJ / cm 2, while the photomask 2 is a forward taper at 50 mJ / cm 2 exposure, but the pattern is not missed at 150 mJ / cm 2 exposure.
    [150] The coloring photosensitive resin composition of this invention is excellent in a sensitivity. Moreover, the colored pixel obtained using the colored photosensitive resin composition of this invention is excellent in pattern shape. Therefore, when a color filter is produced using the colored photosensitive resin composition of this invention as a pigment dispersion resist, it is possible to obtain a color filter having excellent productivity and high quality.
    权利要求:
    Claims (12)
    [1" claim-type="Currently amended] The coloring photosensitive resin composition containing the compound (F) which has a coloring agent (A), binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), a solvent (E), and a benzylidene frame | skeleton.
    [2" claim-type="Currently amended] The coloring photosensitive resin composition of Claim 1 whose compound (F) which has a benzylidene frame | skeleton is a compound which has a partial structure of General formula (1).
    Formula 1

    In Formula 1 above,
    Q 1 to Q 3 are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxyl group having 1 to 6 carbon atoms.
    [3" claim-type="Currently amended] The coloring photosensitive resin composition of Claim 1 or 2 whose compound (F) which has a benzylidene frame | skeleton is an unsaturated carboxylic ester compound of Formula (2).
    Formula 2

    In Formula 2 above,
    Q 1 to Q 3 are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxyl group having 1 to 6 carbon atoms,
    Q 4 is an alkyl group having 1 to 6 carbon atoms,
    X is a cyano group or an alkoxycarbonyl group having 1 to 6 carbon atoms.
    [4" claim-type="Currently amended] The coloring photosensitive resin composition of Claim 3 whose X is a C1-C6 alkoxycarbonyl group.
    [5" claim-type="Currently amended] The coloring photosensitive resin composition of Claim 1 whose compound (F) which has a benzylidene frame | skeleton is 4-hydroxy-3- methoxybenzylidene malonic acid diethyl.
    [6" claim-type="Currently amended] The coloring photosensitive resin composition of any one of Claims 1-5 which contains 0.01-3 mass% of compound (F) which has a benzylidene frame | skeleton in 100 mass parts of solid content in a coloring photosensitive resin composition.
    [7" claim-type="Currently amended] The photosensitive initiator according to any one of claims 1 to 6, wherein the photopolymerization initiator (D) comprises a polyfunctional thiol compound and at least one compound selected from the group consisting of a triazine compound, an acetophenone compound and a biimidazole compound. Resin composition.
    [8" claim-type="Currently amended] The coloring photosensitive resin composition of Claim 7 in which a photoinitiator (D) contains a biimidazole compound and a polyfunctional thiol compound.
    [9" claim-type="Currently amended] The coloring photosensitive resin composition of any one of Claims 1-8 which further contains a photoinitiation start adjuvant.
    [10" claim-type="Currently amended] The colored photosensitive resin composition of any one of Claims 1-9 is apply | coated on a board | substrate, the volatile component is removed from the applied colored photosensitive resin composition layer, and a volatile component is removed from the said colored photosensitive resin composition layer through a photomask. The pattern formation method which exposes and develops the layer which removed.
    [11" claim-type="Currently amended] A color filter comprising a pattern formed by the method according to claim 10.
    [12" claim-type="Currently amended] A liquid crystal display device comprising the color filter according to claim 11.
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    同族专利:
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    JP4161677B2|2008-10-08|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2002-10-21|Priority to JPJP-P-2002-00305546
    2002-10-21|Priority to JP2002305546A
    2003-10-17|Application filed by 스미또모 가가꾸 고교 가부시끼가이샤
    2004-04-28|Publication of KR20040034512A
    优先权:
    申请号 | 申请日 | 专利标题
    JPJP-P-2002-00305546|2002-10-21|
    JP2002305546A|JP4161677B2|2002-10-21|2002-10-21|Colored photosensitive resin composition|
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