TWI303350B - Colored photosensitive resin composition - Google Patents

Description

1303350 发明, DESCRIPTION OF THE INVENTION [Technical Field to Which the Invention Is Ascribed] The present invention relates to a colored photosensitive resin composition. The colored photosensitive resin composition is a photosensitive resin composition containing a colorant and is used as a material for forming a colored pattern constituting a color filter. Here, the term "filter color" refers to an optical element which is used to colorize a display image of a liquid crystal display device and to color an image developed by a solid developing device. The coloring pattern ' is a color pixel such as red, green, or blue, or a color matrix (8), and may be a line shape or a puzzle shape. [Prior Art] When a film is formed by using a colored photosensitive resin composition on a substrate to be coated such as a wafer to form a film, the color photosensitive resin composition is dropped from the vicinity of the center portion of the substrate to be coated by the nozzle, or from the crack. After the (slh) nozzle is dropped onto the coated substrate, the colored photosensitive resin composition is dropped, and the substrate is rotated at a speed of 1000 Å to disperse the solvent and the photosensitive resin composition which is excessively dropped onto the substrate. The spin COMM is used to make a flat coating (4). However, if a spin coater is used, it is moved (4): the colored photosensitive resin composition on the substrate is dispersed so that it is not formed yet = the photosensitive resin layer is discarded and the wave is f乂 乂 乂 乂 习 习 习 习 lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm The liquid-saving applicator is not a %-transfer applicator, as it is recorded in the Japanese Tai Chi 4, 丨 4 士, and Japanese Patent Special Open 200 pp 62370. 3] 4902 5 1303350 "In the case of a coloring device which is applied to a photosensitive resin composition by a conventional spin coater, it is not easy to obtain a flat: 2 (4) flat after coating: : In terms of the spin coater, it is necessary to have a considerable degree of flatness. 'Because of the rotation, it can be cut by heating, etc.; the solvent has been removed by rotation, and the amount of solvent removed inside is small. The flatness of the layer is not greatly affected. In the case of non-rotating applicators, it will not be rotated by two:: Therefore, the state after coating has determined most of the flatness, and The amount of solvent removal due to heating or the like is significantly higher than that of the spin coater. Therefore, the material is also inclined from the already formed layer + m. n "One note deteriorates to 疋, and the conventional colored photosensitive resin composition (4) There is a method of adding a polymer additive such as a leveling agent. The solid component of the coloring photosensitive resin composition is colored such that it is made to have a surface amount of $, such as a polymer additive to which a leveling agent or the like is added, and coated. Undried coating film of photosensitive resin composition The frame edge portion formed at the peripheral portion of the substrate immediately after the coating is applied (the thick film portion of the undried coating film moves toward the center of the substrate to affect the in-plane uniformity. The purpose of the present invention is to provide a colored photosensitive resin composition which is excellent in coatability even when a liquid-absorbent applicator such as a non-rotating applicator is used. The present inventors have developed a non-rotating applicator or the like. ]49〇2 6 1303350 The liquid-saving photoresist coating element or the black-colored color-sensitive photosensitive can still form a uniform color-coated surfactant n-form and concentrate on the knot* and find that it contains a special r ,... '"The surface tension in a certain range of color-sensitive photosensitive trees, and the objects, in addition to the inferior m, such as cloth crying, can also be used in non-rotating coating Erzhier cloth The present invention has finally been completed. (4), that is, the present invention provides a coloring photosensitive resin composition containing: a human color agent' (8) a binder polymer, a (yttrium) photopolymerizable compound , (9) initiator, (8) solvent, and (F) selected from anthrone-based surface activity a mouse-based surfactant and a fluorenone-based surfactant having a fluorine atom, which is a colored photosensitive resin composed of a surfactant in a private group, and characterized by a surface tension of 25.5 mN/ a method of adjusting a surface tension of a colored photosensitive resin composition, a method of adjusting a surface tension of a colored photosensitive resin composition, and a method of forming a layer formed by coloring a photosensitive resin, using the above-mentioned method The colored photosensitive resin composition: a method of forming a pattern, a color filter containing a pattern formed by the above method, and a liquid crystal display device having the color filter as described above. [Embodiment] The colored photosensitive resin composition of the present invention is Containing: (A) a colorant, (B) a binder polymer, (c) a photopolymerizable compound, (D) a photopolymerization starting sword, (E) a solvent, and (F) an anthrone-based surfactant A colored photosensitive resin composition comprising a fluorine-based surfactant and a surfactant having a fluorine atom-based ketone-based surfactant, wherein the surface tension is 25.5 mN/m. Above 29mN The range of /m or less is in the range of 26 mN/m or more and 28.2 mN/m or less. For example, if the surface is 3) 4902 1303350, the force can be used to form a layer with good flatness and a resin composition: the uneven color of the photosensitive color is used for the non-coagulation applicator. . The colored photosensitive resin composition of the present invention is an organic pigment of an organic substance, and the coloring agent can be an inorganic pigment of an inorganic substance. A is more commonly used because of the heat resistance of organic pigments and excellent color rendering properties: among them, organic pigments and inorganic pigments, and specific examples are: in the dyes 〇 〇 l〇i Index 'title ' dyes and color The designer learns to publish, a compound classified as a pigment. C I. (Colorimetric Index) Pigment, 1, CI·Pig Yellow-3, CJ·Pigment Yellow_12, CI•Pigment Yellow c? Yellow 14, C丄 Pigment Yellow 15, CI Pigment Yellow 16, CI• Pigment Yellow 1? Yan CI Pigment Yellow 20, C丄 Pigment 24, CI•Pigment Yellow 31, C丄 Pigment Yellow μ, CI Pigment Yellow 83, C丄 Pigment Yellow%, CI. Pigment Yellow%, ci Pigment 94, CI Pigment Yellow 109, CI Pigment Yellow 11〇, c丨 Pigment Yellow ιΐ7, Kernel, Pigment Yellow 125, CI Pigment Yellow 128, CI Pigment Yellow 137, C] [Pigment ^ 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI • Pigment yellow ci pigment yellow 150, c 丄 pigment yellow 153, CI pigment yellow i54', c, yellow (6), CL pigment yellow 173, CI • pigment yellow i94'c i • pigment pu = yellow pigment; ' 4 C.1·Pigment Orange 13, CI·Pigment Orange 31, CI Pigment Orange, CI Lai Orange 36, C丄 Pigment Orange 38, αι. Pigment Orange. ·Pigment Orange 42, ^ Pigment Orange 43, CI Pigment Orange 51, c·!•Pigment Orange 55, CI. Pigment Orange μ, · ci Pigment Orange 61, c丄 Pigment Orange 64, c丄 Pigment Orange 65, c i. Pigment 柢71, CI pigment orange 73 and other orange pigments; CI·颔料红9, CI·Pigment Red 97'c·]·Pigment Red]〇5, 314902 8 1303350 Pigment Red 122, CI·Pigment Red 123, CI Pigment Red 144, CI Pigment Red 149, CI·Pigment Red 166, CI Pigment Red 168, CI Pigment Red 176, CI·Pigment Red 177, CI·Pigment Red 180, CI·Pigment Red 192, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 224, Red pigments such as CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 264, CI Pigment Red 265, etc.; CI·Pigment Blue 15, CI Pigment Blue 15 ·· 3, CI Pigment Blue 15 : 4, CI Pigment Blue 15 · · 6, blue pigment such as CI Pigment Blue 60; CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI·Pigment Violet 32, CI Pigment Violet 36, CI·Pigment Violet 38, etc. Purple pigment; CI pigment green 7, CI pigment green 36 and other green pigment; CI · pigment brown 23, CI pigment brown 25 and other brown pigment; CI · pigment black 1, CI pigment black 7 and other black pigment, and Jiawei contains from CI·Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Red 177, CI·Yan Red 209, C.I Pigment Red 254, C.I pigment red violet 23, C.I · Pigment Blue 15: 6 Pigment Green 36 and at least one pigment. These organic pigments and inorganic pigments may be used alone or in combination of two or more. It is preferred to contain, for example, CI Pigment Red 209 and CI Pigment Yellow 139 when forming a red pixel, and to contain green pixels. One of the groups selected from the group consisting of CI Pigment Green 36, CI Pigment Yellow 150, and CI Pigment Yellow 138, contains CI Pigment Blue 15: 6 〇 9 314902 1303350 when forming a blue pixel, The organic pigment can be subjected to rosin treatment when needed, and the surface treatment of the pigment derivative having an acidic group or a basic group, the graft treatment of the surface of the pigment by the molecular compound, and the granulation treatment by the sulfuric acid microparticle method Or an organic solvent or water for removing impurities: washing treatment, removal of ionic impurities by ion exchange method, etc. (0) Coloring agent used in the coloring photosensitive resin composition of the present invention, amount, The solid content in the colored photosensitive resin composition is divided by mass: 'usually 8 mass% or more and 6 mass% or less, preferably enamel...55 mass or less, more preferably 25 mass%. The above 5" parts are as long as the content of the (4) coloring agent is 8 parts by mass or more and 6 parts by mass or less, = the color concentration when the coloring device is formed is sufficient and the composition may contain a viscosity; It is suitable to form a figure with sufficient mechanical strength. Here, the colored light component of the present invention means the sum of the components of the solvent removed.曰,, 'The solid in the composition is a colored photosensitive resin composition obtained in the present invention, and the coloring agent is preferably a particle size of the uniform sentence. In order to make the pigment a particle size of a uniform sentence, the group (F) which is described below is selected from the group consisting of an anthrone-based surfactant, a t-agent, and a gas atom-containing surfactant. > A surfactant other than the surfactant is used as a pigment dispersant to feed the dispersion. In the case of the above-mentioned pigment dispersing agent, the surface activity of the cationic nonionic type, amphoteric or the like can be exemplified: ^ J Μ Early alone or in combination 2 groups 3] 4902 10 1303350 or more. The amount of the pigment dispersant to be used is usually 0. 0.001 parts by mass or more and 1 part by mass or less, preferably 0 〇 5 parts by mass or more and 0.5 parts by mass or less per 1 part by mass of the coloring agent. For the (B) binder polymer used in the present invention, it is possible to use a propylene group. The compound may, for example, be a copolymer of a monomer containing a slow group and another monomer copolymerizable therewith. The monomer having a carboxyl group may, for example, be one having at least one carboxyl group in a molecule such as an unsaturated monobasic acid or an unsaturated polycarboxylic acid such as an unsaturated dicarboxylic acid or an unsaturated tricarboxylic acid. Unsaturated carboxylic acid. Here, as the unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid or the like can be exemplified. The unsaturated dicarboxylic acid may, for example, be a maleic acid, a horse acid, an itaconic acid, a citraconic acid or a mesaconic acid. The anhydride of the unsaturated polycarboxylic acid, specifically [may be maleic anhydride, itaconic anhydride, citrate anhydride, and the like. Further, the unsaturated polycarboxylic acid may be mono(2-methylpropenyloxyalkyl)S, which may be, for example, succinic acid mono(2-propenyloxyethyl ester), glassy acid acrylate oxyethylene Vinegar), phthalic acid mono (2-methylpropanol-) but benzene-formic acid (2-propene oxime), phthalic acid mono (2_: propyl acesulfame). Unsaturated The both ends of the acid-lowering acid may be the early (meth)acrylic acid vinegar of the two-reactive di-dimers, which may be, for example, a slow-polymerized poly-caprolactone lactic acid ester, a | Polycaprolactone monomethacrylate, etc. These carboxyl group-containing monomers can be used alone or in combination of two or more kinds.

In the above-mentioned other monomers capable of early copolymerization of sulfhydryl groups, styrene, 'r*benthene ethylene, o-vinyltoluene, and methylene-ethylene can be exemplified. ] 3] 4902 1303350 based toluene, p-vinyl toluene, p-chlorostyrene, o-methoxy styrene, m-decyloxystyrene, p-nonyloxystyrene, o-vinylbenzyl oxime ether, m-vinyl An aromatic vinyl compound such as benzyl methyl ether, p-vinylbenzyl anthracene ether, o-vinyl anthracene glycidol, m-vinyl decyl glycidol, p-vinyl fluorenyl glycidyl ether, hydrazine or the like; Mercapto acrylate, decyl methacrylate, ethyl acrylate, ethyl thioglycolate, n-propyl acrylate, n-propyl decyl acrylate, isopropyl propyl acid , mercaptopropyl isopropyl acrylate, n-butyl acrylate, decyl butyl acrylate, isobutyl acrylate, isobutyl methacrylate, second butyl acrylate, sulfhydryl Dibutyl acrylate, tert-butyl propyl phthalate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, mercapto acrylate 2 - benzyl ethyl ester, 2-propenyl propyl phthalate, 2- propyl propyl methacrylate, 3- propyl propyl acrylate, 3- propyl propyl acrylate 2 - butyl butyl acrylate, thiol propan acid 2 - butyl ketone, 3 - butyl butyl acrylate, mercapto acrylate 3 - butyl butyl, 4 - thiol Butyl acrylate®, 4-hydroxybutyl methacrylate, allyl acrylate, propyl decyl acrylate, decyl acrylate, methacrylate methacrylate, cyclohexyl acrylate , cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, < 2-decyloxyethyl acrylate, methoxyethyl methacrylate, 2 • phenoxyethyl propionic acid Ester, 2-phenyloxyethyl methacrylate, decyloxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxy-B'-propionic acid Vinegar, mercaptopropyl sulphide sulphate triethylene glycol vinegar, methoxy propylene glycol acrylate, decyl decyl acrylate propylene glycol ester, decyloxy dipropylene glycol propyl acrylate, hydrazino acrylate Oxydipropylene glycol cool, different ice 12 314902 1303350 acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2-hydroxyphenoxypropyl acrylate, 2-hydroxyl methacrylate -3 - phenoxypropyl ester, glycerin monoacrylic acid ester, methyl acrylate monoglyceride, etc.; 2 -aminoethyl acrylate, methyl acrylate 2 · Aminoethyl acetoacetate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-mercapto-acrylic acid 2-amino group C-, 2-dimethylaminopropyl propyl acrylate, 2-dimercaptopropyl propyl methacrylate, 3-aminopropyl propyl benzoate, methyl endo acid 3-amino group Propyl ester, 3-dimercaptopropyl propyl acrylate, 3-dimethylaminopropyl methacrylate, etc., and acid-labile amine-based esters; glycidyl acrylate, glycidyl methacrylate Such as unsaturated unsaturated glycidol g-type; vinyl acetate, vinyl propionate, butyric acid ethylene, benzoic acid ethylene and other vinyl acetates; vinyl ether ether, vinyl ether, An unsaturated group such as propyl glycidyl ether; a cyanoethylene compound such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile or dicyanethylene; acrylamide, mercapto acrylamide, J _ chloropropene An unsaturated amide such as guanamine, hydrazine-2-hydroxyethyl acrylamide or hydroxyethyl methacrylamide; & maleic amine, N•'phenyl maleimide, N-ring An unsaturated decylamine such as hexylmethaneamine; 3] 4902 1303350 an aliphatic conjugated diene such as 1,3-butadiene, isoprene or chloroprene; polystyrene, polymethyl Acrylic vinegar, polymethyl methacrylate, polybutyl acrylate vinegar, polybutyl methacrylate, having a monopropyl sulfhydryl group or a single at the end of the molecular chain of the polyoxyalkylene dimer Methyl-propyl-based macromonomer (10) (10) monomer). These monomers may be used alone or in combination of two or more. The content of the monomer unit containing a carboxyl group in the above copolymer is usually 10 to 50% by mass, preferably 15 to 4% by mass, particularly preferably 25 to 4% by mass, based on the mass fraction. The monomer containing (4) as described above: The content of cerium is from 10 to 50% by mass, and the solubility in the developing solution is good, and it is preferable to form a pattern when developing. The above-mentioned acrylic acid copolymer may, for example, be a (meth)acrylic acid/methyl(meth)acrylate copolymer or a fluorene (meth)acrylic acid/benzyl(fluorenyl)propene.酉 酉 共聚物 共聚物 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Methyl(meth)acrylic acid/methyl(indenyl)acrylic acid styrene macromonomer copolymer, (meth)acrylic acid/methyl (methylpropionic acid western L7 polymethyl(methyl)propyl Dilute acid giant monomer copolymer, (I I) acrylic acid / mercapto (mercapto) acrylate / " 夂 13th / difficult ethylene giant monomer copolymer, (meth) acrylic acid / sulfhydryl ) Bingjia J yoke / polymethyl (meth) acrylate 巨大 huge huge body copolymer, (meth) propyl, knee) acrylic acid/2-hydroxyethyl (fluorenyl) acrylic acid

S曰/mercapto (meth) acrylate/poly 芏 7 PI olefin huge monomer copolymer, (methyl meth) acrylate/2-hydroxyethyl (methyl) propyl " city I 3 曰 / fluorenyl ( Methyl)acrylate / I methyl (meth) acrylate giant single A early copolymer, (mercapto) acrylic acid / benzene 3] 4902 14 1303350 Ethylene / benzyl (meth) acrylate - benzene Kamalylamine copolymer, (meth)acrylic acid/succinic acid mono(2-anthracene, knee-to-tablet, premature (2 propylene oxime)/styrene/τ-based (methyl) propyl hydrazine (4) Phenylmaline amine copolymer, (meth)acrylic acid/succinic acid monoterpene, decyloxyethyl phenethyl/allyl (meth)acrylic acid lysine-phenyl hydrazine I "Do not (meth)acrylic acid / benzyl (hydrazino) acrylate / Ν phenyl male malic amine / styrene / glycerol mono (meth) acrylic acid vinegar copolymer, etc.. Diluted acid is a meaning of acrylic acid or methacrylic acid vinegar. Among them, (mercapto)acrylic acid/benzyl (meth) acrylate copolymer, (mercapto) acrylic acid / benzyl group is preferred. (fluorenyl) acrylate/styrene copolymerization , (meth)acrylic acid 7 methyl (meth)acrylic acid copolymer, (fluorenyl) acrylic acid / mercapto (mercapto) acrylate / styrene copolymer, etc. Ethylene-equivalent weight average molecular weight (using polyethylene as a standard, the value obtained by gel permeation chromatography is usually 5,000 to 50, 〇〇〇, preferably 8, 〇〇〇 to 4 〇, 〇〇 The range of 〇, particularly preferably 10,000 to 35, 〇〇〇. If the molecular weight of the propylene polymer is (10) to 50,000, the hardness of the coating film is increased, and the residual film rate is also high, and the dissolution of the selected image liquid in the unexposed portion is obtained. The acidity is usually from 50 to 丨5〇, preferably from 60 to U0, and particularly preferably from 8〇 to 135. The acid value is from 5〇 to 15〇, as described above. Therefore, the solubility in the developing solution is improved, the unexposed portion is more easily dissolved, and the sensitivity is high, and the pattern of the exposed portion remains in the image of the same as the image of the exposed portion, and the residual film ratio tends to be improved. Here, the acid value is determined as the amount (mg) of potassium oxychloride required to neutralize the propylene polymer 丨g. The value is usually determined by titration with an aqueous solution of potassium hydroxide. / 15 314902 1303350 The (B) binder polymer described above is based on the mass fraction of the solid component of the colored photosensitive resin composition. 5 mass% or more and 40 mass% or less, preferably 10% by mass or more and 35 mass% or less, and particularly preferably used in the range of i 5 mass% or more and 26 mass% / 〇 or less. When the content is 5% by mass or more and 26% by mass or less, the pattern can be formed and the resolution and the residual film ratio are improved. The (C) photopolymerizable compound used in the present invention can be irradiated with light. The compound polymerized by a living radical, an acid or the like which is generated by a photopolymerization initiator may, for example, be a compound having a polymerizable carbon-carbon unsaturated bond, etc. 0 used in the color-sensitive photosensitive resin composition of the present invention ( c) photopolymerization, a ruthenium compound which can be produced by photopolymerization initiator from light irradiation; a compound which is polymerized by a base, an acid or the like, may be exemplified by a polymerizable property: carbon-carbon A compound that saturates the bond. The photopolymerizable compound is preferably a light having three or more functional groups: a conjugate compound. A trifunctional or higher polyfunctional photopolymerizable property is used. 'Can be exemplified by: pentaerythritol triacrylate, tridecyl acrylonitrile tetraol brewing, pentaerythritol tetraacrylic acid vinegar, tetramethyl isopropyl acid isoindole four, hydrazine, monoisodecyl alcohol Propane, pentamethyl propylene diisopentaerythritol cool = tetraol hexaacrylate vinegar, hexamethyl propyl bisulphate vinegar and the like. :::: Synergistic, the compound may be used singly or in combination of two or more kinds, and the solid component of the composition of the 3:-pair color-sensitive photosensitive resin is 5 mass by mass. ...5 quality. In the following, it is preferably “35 mass% or less, particularly preferably 15 mass% or more and 26 mass% J6 314902 1303350 denier. The content of the photopolymerizable compound is 5 mass% or more. When 45 is less than %%, it can be sufficiently hardened to improve the tendency of the undercut in the second layer to be less likely to cause undercut and improve the adhesion. Stupid. (9) Photopolymerization initiator used in the present invention Preferably, the compound containing a styrene-indole compound is exemplified by diethoxyethyl benzene,

Methylmorpholino-1-('曱AT basic guaia)propan-1-one, 2-hydroxyindolyl[4_(2_di\^+:decyldidecyl ketal, 2·hydroxyl_ Oligomerization of 2-methyl-1-2-perfluoromethyl ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone And not W 2-mercapto-2-morpholino-1-(4-methyl humyl)propane ~ 1-ketone. In addition, it is also possible to combine a plurality of acetaminophens. The light other than the benzene-based benzene system*, and he "starts to produce active free beauty m. exemplified by the generation of light by the base = free radical generator, sensitizer, etc. The activity is self-generating." The benzoin compound and the thioxanthone-based compound "Do not be a 甲 糸 、 、, a diterpenoid compound, etc. may be mentioned. The present intrinsic compound and t m 7 3 may, for example, be benzoin, benzoin methyl ether, quinine diethyl ether, 1 lithium, singular isopropyl ether or benzoin isobutyl ether. In the case of the cage-benzamide, the compound can be exemplified by benzophenone, methyl benzoate, methyl 4-methyl hydrazine, phenanthrene, and benzyl ketone. Μ, - 曱基二笨美炉, 3,3,-4,4, four (second Dingmei - Toguay „ —— butyl perhydroxycarbonyl) benzophenone, 2,46_

Monomethyl benzophenone and the like. , H, D 314902 17 1303350 The thioxanthone compound can be exemplified by 2: isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2 , 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. The triterpenoid compound may, for example, be 2,4-bis(trichloroindenyl)-6-(4-mercaptophenyl)-1,3,5-three tillage, 2,4-bis ( Trichloromethyl)-6-(indolylnaphthalenyl)-1,3,5-trin, 2,4-bis(trichloroindenyl)-6-(4-decyloxystyryl) -1,3,5-triterpene, 2,4-bis(trichloroindolyl)-6-[2-(5-fluorenylfuran-2-yl)vinyl]-1,3,5-three tillage , 2,4-bis(trichloroindenyl)-6-[2-(furan-2-yl)vinyl]trimium, 2,4-bis(trichloroindenyl)-6-[2-(furan) -2-yl)vinyl]-1,3,5-three tillage, 2,4-bis[trichloroindenyl]-6-[2-(4-diethylamino-2-mercaptophenyl) ) Vinyl three-pill, 2〆-bis(trichloroindenyl)-6-[2-(3, geninoquinoneoxy) vinyl]-1,3,5-triterpene and the like. As the living radical generating agent, for example, 2 5 4 5 6 -trimercaptophenylphosphonium diphenylphosphine oxide, 2,2'-bis(o-chlorophenyl)-454'55, 55-four can be used. Phenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethyl hydrazine, benzyl-9,10-phenanthrenequinone, camphorquinone, phenylglyoxylic acid An oxime ester, a titanocene compound, and the like. The acid generator may, for example, be 4-hydroxyphenyldifluorenylsulfonium-p-toluenesulfonate, 4-hydroxyphenyldifluorenylsulfonium hexafluoroantimonate or 4-ethenyloxybenzene. Dimethyl sulfonate p-toluenesulfonate, 4-acetoxyphenylmethylbenzyl yellow iron hexafluoroantimonate, diphenyl ferrous iron p-benzoate, triphenyl sulphate a key salt such as hexafluoroantimonate, diphenyliodonium p-toluenesulfonate or diphenyliodonium hexafluoroantimonate, or nitroguanidino-p-benzenesulfonate or benzoin Benzene sulfonate and the like. Further, as the active radical generating agent, among the above compounds, 18 314902 l3 〇 335 〇

Invited, 壬A 八:... A compound which produces an acid at the same time, for example, a triterpene photopolymerizable α-alkaline agent can also be used as an acid generator. The content of (D) photopolymerization initiation = used in the coloring photosensitive resin composition of the present invention is 0 (100 parts by weight) of the (Β) binder polymer and (C) photopolymerizable compound. Usually, it is preferably 1 part by mass or more and 15 parts by mass or less in terms of 5% by mass or more. When the amount of the photopolymerization initiator is from 0.1 part by weight to not more than 25 parts by mass, it is suitable for high sensitivity and shortening of the exposure time to improve productivity and maintain high resolution. In the present invention, a photopolymerization initiation aid can also be used. The photopolymerization starting aid can be used in combination with a photopolymerization initiator to promote the polymerization of the photopolymerizable compound initiated by the photopolymerization initiator. The photopolymerization initiation aid may, for example, be a narcotic compound, an alkoxy fluorene compound or a thioxanthone compound. The amine compound may, for example, be triethanolamine, mercaptodiethanolamine, triisopropanolamine, methyl 4-didecylaminobenzoate, ethyl dinonylaminobenzoate, 4- Isoamyl dimercaptoacetate benzoate, 2-mercaptoaminoethyl benzoate, ethylhexyl 4-didecylamine benzoate, N,N-fluorenyl hydrazine, 4 , 4'-bis(didecylamino)dibenzophenone (commonly known as Michlei-'s Ketone), 4,4'-bis(diethylamino)benzaldehyde g, 4,4-bis(ethyl-decylamino)diphenyl fluorenone, bis(ethylmethylamino)dibenzophenone, etc., of which 4,4, bis(diethylamino) are preferred The benzophenone oxime compound can be exemplified as: 9, 〇-dimethoxy grass, 314902 19 1303350 2-ethyl-9,10-dimethoxy fluorene, 9510-diethoxy Base, 2_ethyl_9, 1 decyl diethoxy hydrazine, and the like. The peptidone compound may, for example, be isopropylthiazinone, isopropyl thioxanthone, 2, diethyl thioxanthone, 2,4-dichlorothioxanthone or chloroform. -4-propoxythioxanthone and the like. The photopolymerization initiator may be used singly or in combination of plural kinds. In addition, a commercially available photopolymerization start-up aid may be used, and the commercially available photopolymerization start-up aid may, for example, be a product name rEAB_F" (manufactured by Hodogaya Chemical Industry Co., Ltd.). ', a combination of a photopolymerization initiator and a photopolymerization starter in the color-sensitive photosensitive resin composition of the present invention may, for example, be diethoxyethyl hydrazine, bis(diethylamine) Benzophenone, 2-methyl-2-bromomorpho-methylsulfonyl)propan-1-one/4,4, bis(diethylamino)benzophenone, hydroxyl one Methyl phenyl propyl ketone / 4, 4, bis (diethylamino) diphenyl H via hydrazino 1 [4 (2-decyl ethoxy) phenyl] propyl ketone 4. Bis(diethylamino)benzophenone, hydroxycyclohexyl phenyl ketone/4,4, bis(diethylamido)benzophenone, 2_trans-base_2-methyl [4_〇_曱基乙基基)Benzene-propanone-μ oligomers/4,4,_bis(diethylamino)benzophenone, 2_mercapto-2-methyl Combination of fe-morpholino-phenyl)butane "-ketone-muthium, hetero-amino) benzophenone, etc., pregnancy is 2 mercapto-2-morpholino _! ·Μ-methylbenzene Thio)propane q•ketone/4, hydrazine (a 1f violent female base) _ a combination of fluorenone 0, and its use amount is preferably 0.01 mA or more for each mole light. 5 Use of such light Aggregate When the auxiliary agent is used, the polymerization initiator is usually 314902 20 1303350 or less in the range of 10 mol or less. The solvent (E) used in the invention may, for example, be an ether, an aromatic hydrocarbon, a ketone or an alcohol. , esters, guanamines, etc. Examples of the ethers: tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol single Propyl ether, ethylene glycol monobutyl ether, diethylene glycol monoterpene ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dioxime ether, diethylene glycol diethyl ether, diethyl Diol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monoterpene ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether ethanol ester, fluorenyl fibrin acetate, ethyl fibrinolysin Acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol oxime ether acetate, decyloxybutyl acetate, decyloxypentyl acetate vinegar, fennel® Anisol), phenetol, fluorenyl anisole, etc. The aromatic hydrocarbons may, for example, be benzene, toluene, diphenylbenzene or trimethylbenzene. · Acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-mercapto-2-pentanone, cyclopentanone, cyclohexanone, etc. Examples: sterol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, etc. Examples of the esters include ethyl acetate, n-butyl acetate, and isobutyl acetate. Amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, decyl lactate, ethyl lactate, cesium glycolate Ester, ethyl hydroxyacetate, butyl hydroxyacetate, decyl methoxyacetate, ethyl decyloxyacetate, butyl oxyacetate, ethyl 2] 314902 1303350 oxyacetic acid ruthenium, ethyl ethoxyacetate , · 3-hydroxypropionate, 3-hydroxypropionate, 3-methoxypropionate, 3-methoxypropionic acid ethyl ester, 3-methoxypropionic acid methanol, 3-B Ethyl oxypropionate, decyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, decyl 2-methoxypropionate, 2-methoxypropionic acid , 2-propoxypropionic acid propyl ester, 2-ethoxypropyl propionate, 2-ethoxy Ethyl propyl propionate, methyl 2-oxomethyl propyl propionate, ethyl 2-oxo-2-mercaptopropionate, decyl 2-methoxymercaptopropionate, 2-ethoxylated _2 - mercaptopropionate, propane S, decyl acetate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, 2 - oxobutyrate, 2-oxo Ethyl acetate, 3-decyloxybutyl acetate, 3-mercaptomethoxybutyl acetate, ^-butyrolactone, and the like. The amine may, for example, be a team of dimethylformamide, N,N-dimercaptoacetamide or the like. The other solvent may, for example, be decyl pyrrolidone or dimethyl sulfoxide. · Ethyl 3-ethoxypropionate, propylene glycol monoterpene Among the above solvents, ether acetate is suitable. The above solvents may be used alone or in combination of two or more. (E) The content of the solution in the colored photosensitive resin composition of the present invention. From

314902 22 1303350 At least one type of surfactant (hereinafter referred to as (F) component) in a group of surfactants. The surfactant may, for example, be a surfactant having a polyoxymethylene. Specifically, it can be mentioned: Torayone DC; 3PA, with SH7PA, with DC11PA, with SH21PA, with SH28PA, with SH29PA, with SH30PA, polyether modified Shishi oil SH84〇0 (trade name: Donglixone) )), Kp321, ΚΡ3 22, ΚΡ3 23, ΚΡ324, ΚΡ3 26, ΚΡ3 40, ΚΡ3 41 (Shin-Etsushishi), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (Gee Toshiba ketone (shares) and so on. The Dun surfactant is exemplified by a surfactant having a fluorinated fluorocarbon chain as a hydrophobic group. Specifically, it can be exemplified by Fluroline (registered trademark Khan 0:430, Tong? (2431 (Sumitomo 3)\4 (share) system), Mejiafake (registered trademark) F1420, same as F171, with F172, Same as F173, with F177, with F183, with R30 (made by Otsuka Ink Chemical Industry Co., Ltd.), Effluent (registered trademark) EF301, with EF3〇3, with EFMl, with EF352 (New Akita Chemicals Co., Ltd.) )) Shaflon (registered trademark) S381, with S382, with SCl〇1, with SC 105 (Asahi Glass Co., Ltd., E5844 (share) Taijin Precision Chemicals Research Institute, hexadecane fluorene Base) 丄2-epoxypropane), BM-1 000, bm-HOO (all trade names: manufactured by bm Chemicals Co., Ltd.), etc. Examples of the surfactants having a fluorine atom are exemplified by An anthrone-based surfactant having a fluorinated fluorocarbon chain as a hydrophobic group. Specifically, it can be exemplified by Megarfax (registered trademark) R〇8, same as BL9〇, the same F475, and the same F477. F443 (manufactured by Otsuka Ink Chemical Industry Co., Ltd.) 314902 23 1303350, etc. The above surfactants may be used alone or in combination of two or more. The content of the colored photosensitive resin is usually 0.0005 parts by mass or more and 66 parts by mass or less, preferably 〇〇〇1 parts by mass or more and 0.5 parts by mass or less, such as (F) component. When the content is 0.0005 parts by mass or more and 6 parts by mass or less, the flatness of the obtained coating film tends to be gradually improved, and the composition of the colored photosensitive resin composition of the present invention is prepared by mixing components other than the component (F). 'Adding (F) component to adjust the surface sheet: can be carried out in a range of 25.5 mN/m or more and 29 mN/m or less. Alternatively, the components can be mixed and the surface tension of the obtained composition can be measured. The amount of the component (F) is increased or decreased in the form of a woman (for example, if the enthalpy value is too large, and the measured value is decreased when the measured value is too small), the coloring photosensitive resin composition may also contain a filler and a viscous ultraviolet ray. Additives such as an absorbent, an adhesion promoter, an antioxidant, and the like. The organic acid, the organic amine compound, and the curing filler may, for example, be granules such as a granule, a binder, or a oxidized slag. The high-molecular-weight vinyl alcohol and the polypropylene _ ^ f compound other than the material may, for example, be a poly-N-acid or a polyethylene glycol ester, etc. Early olefin ether, polyfluoroalkyl acrylate 4 σ promoter In other words, an alkenyl triethoxy sulphate, an ethyltrimethoxy decane, a bis(2-aminoethyl hydrazine, a gluten (2, methoxyethoxy) decane, a cold base Propylmercaptodimethoxydecane, aminoethyl 314902 24 1303350 base) 3-aminopropyltrimethoxysecond burn, 3-aminopropyltriethoxylate, glyceroloxypropyltrimethoxysilane Xishou, 3' glycidoxymethyl monomethoxy decane, 2-(3,4-cyclochlorojol^ clothing hexyl)ethyltrimethoxy decane, 3-chloropropyl decyl ruthenium Gas 々石、@,2 β ^ 夕心3·虱propyltrimethoxydecane, 3-methylpropoxyloxypropyl r:Apreparation|Doping soil N soil-f-decyl decane, Hongyingji Propyltrimethoxydecane, and the like. The ruthenium oxidizing agent may, for example, be 4,4, _ thiobis (6-t-butyl-3-3-methyl hydrazine), 2,6-di-t-butylmethyl hydrazine or the like. The external and external absorbents may, for example, be a benzotriazole-based or 1-hydroxyoctyl-based diphenyl group such as 2-(2-hydroxy-tert-butylphenyl)-phenylbenzotriazole. a benzoate such as a benzophenone or a benzoate such as 2,4-di-t-butylphenyl-3,5-di-tert-butylhydroxybenzoate or a 2-(4,6- Three tillage systems such as diphenyl-1,3,5-triD-2-yl)-5-hexylhydroxyphenol. The anti-coagulant can be exemplified by sodium polyacrylate or the like. The organic acid may, for example, be an aliphatic monocarboxylic acid such as capric acid, acetic acid, propionic acid, butyric acid, valeric acid, tridecyl acetic acid, caproic acid, diethyl acetic acid, heptanoic acid or octanoic acid; Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, malic acid, mercaptomalonic acid, ethylmalonic acid, dimercapto Aliphatic dicarboxylic acids of malonic acid, mercapto succinic acid, tetradecyl succinic acid, cyclohexane dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid, etc. Aromatic tri-acids such as propylene tricarboxylic acid, aconitic acid, and decomposed camphoric acid; aromatics such as benzoic acid, phthalic acid, cuminic acid, dinonyl phenyl acid, mesitylenic acid, etc. Group of monocarboxylic acids; aromatics of o-dicarboxylic acid, isophthalic acid, terephthalic acid, etc. 25 314902 1303350 •- group dicarboxylic acids; trimellitic acid, trimesic acid, benzene An aromatic polycarboxylic acid such as citric acid or benzoic acid. The organic amine compound may, for example, be n-propylamine, isopropylamine, n-butylamine, isobutylamine, second butylamine, third butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, or Monoamines such as decylamine, n-decylamine, n-undecylamine, n-dodecylamine; cyclohexylamine, 2-nonylcyclohexylamine, 3-mercaptocyclohexylamine, 4-fluorenyl ring One of the cycloalkylamines such as hexylamine; mercaptoethylamine, diethylamine, mercapto-n-propylamine, ethyl-n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, a dialkylamine such as a second butylamine, a di-tert-butylamine, a di-n-pentylamine or a di-n-hexylamine; a monovalent alkyl mono-cycloalkylamine such as a nonylcyclohexylamine or an ethylcyclohexylamine; a cycloalkylamine such as cyclohexylamine; dimercaptoethylamine, decyldiethylamine, triethylamine, dimercapto-n-propylamine, diethyl-n-propylamine, decyldi-n-propylamine, ethyldi-n-butyl a trialkylamine such as propylamine, tri-n-propylamine, 'triisopropylamine, tri-n-butylamine, triisobutylamine, tri-second butanamine, tri-tert-butylamine, tri-n-pentylamine or tri-n-hexylamine; Cyclohexylamine, ® diethyl ring a dialkyl monohaloalkylamine such as an amine; a monoalkyldicycloalkylamine such as methyl dicyclohexylamine, ethyl dicyclohexylamine or tricyclohexylamine; 2-aminoethanol, 3-amine Mono-1-alkanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-p-pentanol, 6-amino-1-hexanol Alcoholamines; one-membered cycloalkanolamines such as 4-amino-cyclohexanol; diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, two a dialkyl alkanolamine such as n-pentanolamine or di-n-hexanolamine; a dicycloalkanolamine such as bis(4-cyclohexanol)amine; triethanolamine, tri-n-propanolamine, triisopropanolamine a trialkanolamine such as tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine or tri-n-hexanolamine; 3 3,4902 1303350; tricycloalkane such as tris(4-cyclohexanol)amine > clothes ~ know amines; 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amine]. Female suspension - anthracene, 2-butanediol, 4-amino-1,3-diethylamino-1,2-propanol, 2-diethylamino 4,3-propanediol Chain-burning glycols; 4-amino-anthracene, 2-amino-cyclohexanol-based amine ring;): complete glycols; butanediol, 3-dimethylamino-1,2- Amine-containing groups such as propylene glycol, diol, 2-didecylamino q, 3-propanol, 4-amino-1, 3-aminocyclopentanone decyl alcohol, 4-aminocyclopentanone sterol Ring, p and makeup 丞 兀 A 兀 曱 ; ;; 1 - aminocyclohexanone methanol ' 4 - aminocyclohexanone methanol, 4 - dimethyl amino ring oxime methanol, heart diethyl Amino-containing cycloalkanols such as aminocyclopentane decyl alcohol, 4-dimethylaminocyclohexane decyl alcohol, and decarboxyethyl cyclohexane decyl alcohol; alanine and 2-amine Butyric acid '3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisoacetic acid, 3-aminoisoacetic acid, 2-aminopentanoic acid, 5-aminopentanoic acid, 6-amino group An aminocarboxylic acid such as caproic acid, acetocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid or 4-aminocyclohexanecarboxylic acid; streptoamine, o-methylaniline, m-decylaniline, P-nonylaniline, p-ethylbenzene , p-propyl aniline, p-isopropylaniline, p-n-butyl amide, p-tert-butylaniline, 丨-naphthylamine, naphthylamine, N,N-dimercaptoamine, N,N-di Aromatic amines such as ethyl aniline, p-fluorenyl-ν, fluorenyl-diphenyl aniline; o-amino benzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-didecylamino benzyl alcohol, Aminobenzyl alcohols such as p-diethylamino benzyl alcohol; o-amino benzene S, m-amino phenol, p-amino benzene g, p-didecyl phenyl age, p-diethyl Aminophenols such as aminophenol; m-aminobenzoic acid, p-aminobenzoic acid, p-didecylaminobenzoic acid, p-diethylaminobenzoic acid, and the like. The curing agent may, for example, be a compound which reacts with a carboxyl group of 3] 4902 1303350 in a binder polymer to carry out a binder polymer by heating: a compound which can be recombined by itself. It is also possible to exemplify a compound which can be polymerized as in the above-mentioned compound to form a compound which is cured in a pattern. Things and so on. The oxetane compound epoxy compound may, for example, be a double-test A-based epoxy resin, a cone-A epoxy resin, or a hydrogenated bismuth and an age-old F-based epoxy resin. An oxyresin or a novolac. Type production? · T, gasified bisphenol F-based cycloaliphatic epoxy resin, tree: oil vinegar resin such as glycidylamine wax, epoxidized oil, desertification derivative of resin, epoxy resin and Or an epoxy group, an alicyclic or aromatic epoxy compound, an epoxide of a fat other than a biological organism, a (co)polymerization of a isoprene, a polymer oil base (methyl) Acrylic brewing compound, shrinking water, etc. - 鲕 甘油 甘油 异 异 异 氧 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 ^ ^ ^ ^ ^ ^ ^ ^ Ester dioxane, equivalent. ^ hexane red dicarboxylic acid dioxetane ^ Γ 之 之 之 之 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 含有 含有 含有 含有 θ θ θ θ θ θ θ θ θ θ θ θ θ θ θ A compound which is an oxetane calcined compound of an epoxy oxime-based oxime-based or oxetane compound. The above compound and >, 3 % 々" are exemplified by a polycarboxylic acid singular carboxylic acid anhydride, an acid generator, and the like. For the buccal and polycarboxylic acids, it can be exemplified as: 邻 二 二 Τ 七 七 4 4 4 314 314 314 314 314 314 314 314 314 314 314 314 314 314 314 314 314 314 314 314 314 314 314 314 314 314 314 314 314 314 314 314 An aromatic polycarboxylic acid such as benzoic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3,4,4, diphenylfluorene 1 and tetracarboxylic acid; succinic acid, glutaric acid, Aliphatic polycarboxylic acids such as adipic acid, i, 2,3,4-butane tetracarboxylic acid, maleic acid, fumaric acid, itaconic acid, etc., hexahydrophthalic acid, 3,4·dimethyl Tetrahydrophthalic acid, hexahydroisophthalic acid, hexahydro-p-benzoic acid, cyclopentane tricarboxylic acid, hydrazine hexane tricarboxylic acid, cyclopentane tetracarboxylic acid, ^, VII, An alicyclic polybasic acid such as cyclohexanetetracarboxylic acid. For example, it can be exemplified by itaconic anhydride, isophthalic acid tetras, 3,3 fluorene, 4, benzophenone tetracarboxylic dianhydride, etc., acetoic anhydride, citraconic anhydride, polycarboxylic acid anhydride, phthalic anhydride , stupid Sanchaic acid Xuan, aromatic polybasic acid anhydride; 12-carbon succinate, white acid Xuan, propylene tricarboxylic acid needle, stomach acid needle, Dingyuan four slow acid two with: Rong > zhizhi Fatty polycarboxylic anhydrides; hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic acid, ...-cyclopentazone three rebellious anhydride 1,2,4_hexahexane Carboxylic anhydride, cyclopentane tetracarboxylic dianhydride, l52,4,5_ " /Himic anhydride, naic anhydride, 夕日一,,, Xuan class; ethylene glycol di-p-trimellitic anhydride, glycerol hydrazine, / / this dicarboxylic anhydride and other ester-containing phthalic anhydride. For the carboxy phthalic anhydride, a commercially available epoxy resin curing agent can also be used.环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂(Nippon Chemical and Chemical Co., Ltd.) - ()), etc., quotation MH_7〇〇" (New Japan Physicochemical Co., Ltd.) The two curing agents can be used alone or 314902 29 1303350 to use the colored photosensitive resin of the present invention. In the method of forming a pattern, the coloring photosensitive resin composition of the present invention is applied to a colored photosensitive resin composition layer coated with a coating agent to remove a solvent, etc., by a mask. After exposure of the layer from which the volatile component is removed, the method of developing the film is carried out. The substrate 5 may, for example, be a glass substrate, a ruthenium substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, or a polyamide. a substrate having a flat surface such as an amine substrate, an imine substrate, an A1 (aluminum) substrate, or a (gallium arsenide) substrate, etc. These substrates may be treated by a plasma treatment with a decane coupling agent or the like, and ion-electrophoresis treatment. , splash clock treatment, gas phase reaction treatment, For example, when a substrate or the like is used as the substrate, a charge coupled device (ccd), a thin film transistor (TFT), or the like may be formed on the surface of the substrate. When the photosensitive resin composition is colored, a conventional spin or a liquid-saving coating is used, and particularly, it is applied onto a substrate or the like using a non-rotating applicator, and then, a volatile component such as a solvent is volatilized by heating. In this manner, the layer can be formed on the substrate or the like in such a manner that the solid content of the colored photosensitive resin composition is good in flatness. Next, a layer formed of a solid component of the colored photosensitive resin composition (hereinafter, simply colored photosensitive resin) The solid content layer of the composition is exposed to light. For example, the light is irradiated through the mask. For the light, ultraviolet rays called g line (wavelength of 4 6 nm) and i line (wavelength of 365 nm) are usually used.丨The illuminator is irradiated by the reticle, and the reticle here is attached to the surface of the glass plate & a light shielding layer for shielding light is provided. The portion of the glass plate not provided with the light shielding layer 314902 30 1303350 The amount of light, the amount of the monomer, the content, the type of the initiator, or the content of the initiator, which are the unexposed areas of the colored photosensitive resin group, are appropriately selected. The layer is exposed, and the irradiation of the light and the irradiated light is the amount of the light-compatible compound of the viewpoint mixture polymer, and the photopolymerization start-up agent produces a non-irradiated area according to the pattern of the light-transmitting portion. The weight average molecular weight, the type or content, the type or content of the photopolymerization, etc., are developed after calendering. For example, the exposed photosensitive resin composition layer after exposure is contacted with the developing solution, specifically In other words, the substrate in a state in which the colored photosensitive resin composition layer is formed on the surface thereof may be immersed in the developing liquid. The developing solution may, for example, be an aqueous solution of a basic compound such as sodium carbonate, carbonic acid clock, sodium oxychloride or potassium hydroxide, tetrakisyl ammonium hydroxide. The unirradiated areas in the photosensitive resin composition layer which are not irradiated with light by the development are removed. On the other hand, the light-irradiated area remains as it is to form a pattern. After the image is developed, it is usually washed with water and dried to obtain the desired pattern. It can also be heated after drying. It can be cured by heating of the pattern, and its mechanical strength tends to be strong. For example, if the composition containing the colored photosensitive resin is used as a curing agent, the mechanical strength can be further improved. The heating temperature is usually i 8 以上 or more, preferably 200 ° C or more, and usually 25 〇 ° C or less. On the substrate on which the colored pattern is formed in this way, a layer formed of a colored photosensitive resin composition colored with different colors and colored with different colors is formed, and the layer is exposed and developed to be colored again. pattern. Further, by using the colored photosensitive resin composition colored in different colors and repeatedly performing the above operation, 3) 4902 1303350, a colored pattern can be sequentially formed to produce a desired color filter state. That is, the color filter is usually one in which a black matrix and three primary color patterns of red, green, and blue are disposed on a substrate, and the colored photosensitive resin composition of the present invention containing a colored enamel corresponding to a certain color is used, and the above operation is performed. A black matrix or a colored pattern of the color can be obtained, and a colored photosensitive resin composition of the present invention containing a coloring agent corresponding to a desired color can be used for other colors, and the same operation can be performed to arrange a black matrix and three primary colors on the substrate. Coloring the pattern. Here, if the coloring pattern or the black matrix of a certain color is disposed on the substrate, and then the coloring photosensitive resin composition of the color is disposed on the substrate, the substrate having the colored pattern or the black matrix of the certain color is disposed. Applying a color-colored resin composition of another color, after drying, (4) patterning and exposing a position where the color pattern or the black matrix of the color is not disposed, the force is that the other portion is disposed at the exposed position The color is more than the same 4-shouldered pattern or black background. Of course, the cups of the black matrix and the three primary colors are inserted, and the "coloring resin composition" of the present invention is applied to only one, two or three kinds.萁冰,巴巴, because it is a black matrix of the light-shielding layer, sometimes it is used, for example, from a chrome layer to form a smear + from t ^ ^, and the invention is used, and it is not necessary to use the invention for the formation of a black matrix. The colored photosensitive resin composition. Color:: The color filter obtained by the method is a pattern, and the above is set. In the above, the liquid crystal display device of the present invention is described in the above description, and the present invention is related to the present invention. It is only an exemplified person, and the invention of the present invention does not have to be implemented in the absence of July. The scope of the present invention is not limited by the patent application, but also includes the description of the scope of the patent, and the description of the scope of the patent is equivalent to 314902 1303350 and all the changers within the scope. In the following, the present invention will be further described in detail by way of examples, but the invention is not limited thereto. The components used in this example are as follows. 'The following may be omitted. 0 (H) Colorant: CI·Pigment Red 254 (A-2) Colorant: ci·Pigment Yellow 139 (B) Adhesive Polymer : a copolymer of mercaptoacrylic acid and mercaptodecyl acrylate [the ratio of methyl methacrylate unit to mercaptomethyl acrylate unit is 27: 73 by mass ratio (mole ratio), acid The value was 83, the polystyrene conversion weight 1 average molecular weight was 18, and the measurement of the weight average molecular weight f of the mixture polymer was carried out by the GPC method under the following conditions. Device: HLC-8120GPC (manufactured by Tosoh Co., Ltd.) Column: TSK-GELG2000 Hx L Column temperature: 40 °C Solvent: THF (tetrahydrofuran)

Polystyrene standard··polystyrene (manufactured by Tosoh Corporation, Mw: 9100) Flow rate: 1. 〇ml/min Injection amount: 50 // 1 Detector: RI (C) Photopolymerizable compound: Diisopentaerythritol hexaacrylate (D-1) photopolymerization initiator: 2_methyl-2-morpholino-1-(4-mercaptophenylthio) propylene-less-1 - s Same as (D-2) photopolymerization initiator: 2,4-bis(trichloroindenyl)-6-piperonyl-1:3,5 - 314902 1303350 Three-plowed (G-1) photopolymerization starter · 2,4-diethyl hydrazine.顿一同(E-1) Solvent: propylene glycol monoterpene ether acetate (E-2) Solvent: 3-ethoxypropionate oxime Example [Production of colored photosensitive resin composition] (A-1) (A-2) Dispersant (B) (C) (D-1) (D-2) (G-1) (E>1) (E - 2) 4.070 parts by mass of 0.955 parts by mass, 1.507 parts by mass of 3.229 mass 3.947 parts by mass of 0.431 parts by mass of 0.431 parts by mass of 0.431 parts by mass of 76.502 parts by mass of 8.500 parts by mass of loach to prepare a mixture 1. For mixing, as a (F) surfactant, F475 (manufactured by Otsuka Ink Chemical Industry Co., Ltd., containing a perfluoroalkyl fluorenone oligomer) of 0·0 10 parts by mass to obtain coloring Photosensitive resin composition. [Surface tension evaluation] The front end of a glass tube with a direct control of 1 mm can be made into a vertical pattern/again/before square, colored photosensitive resin composition, and the rise from the impregnation portion of the colored photosensitive resin composition The result of the surface tension is 314902 34 1303350 28.2 mN/m 〇 [Formation of coating film] When the colored photosensitive resin composition is dropped from a micro-syringe and is called a glass substrate, the diffusion is rounded to a diameter of 7 mm. : Wide coverage of stripes, and flatness is good. There is no dry [Evaluation when using a non-rotating applicator] to make the non-rotating applicator a film with uneven spots. When the obtained colored photosensitive resin composition was formed into a coating film, the flatness was improved, and the F475 (manufactured by Dainippon Ink Chemicals Co., Ltd.) of the component (7) was changed to 0. 050 parts by mass. Share) /, you will manufacture colored photosensitive resin composition 2 according to the formula 1. n ^ square [surface tension evaluation] The surface tension of the colored photosensitive resin composition 2 was determined by the surface-like ST-like method, and the result was 26.5 mN/m. Name [Formation of Coating Film] When the colored photosensitive resin composition was dropped from the micro-syringe to the glass substrate, it was diffused into a diameter of 7 powers, and the flatness was good. No dryness was observed [Evaluation when using a non-rotating applicator] When the obtained colored photosensitive resin was formed into a coating film, the flatness Example 3 was obtained, and the product was excellent in non-rotation coating and had no uneven spots. Coating film. The F475 (manufactured by Otsuka Ink Chemicals Co., Ltd., 314902 35 1303350 ·) of the Example (F) was changed to 0.075 parts by mass, and the others were colored in the same manner as in the Example. Resin sister product 3. [Evaluation of Surface Tension] The surface tension of the colored photosensitive resin composition 3 was determined in the same manner as in Example i, and as a result, it was 26.0 mN/m.乂[Formation of coating film] The dripping of the colored photosensitive resin composition 3 from a micro-syringe is carried out. (1) When it is called on a broken glass substrate, it spreads to a round shape of 71 ships, and no interference fringes appear, but the flatness is [Evaluation when using a non-rotating applicator], coloring the photosensitive resin composition 3, using a non-rotating applicator to form a film with good flatness and no uneven spots {Example Industrial Co., Ltd. 1 In the same way, the F475 (Daily Ink Chemical Chemical Coating) of the component (F) of Example 1 is further reduced to 10,000 parts by mass, and the rest is in accordance with the examples. The colored photosensitive resin composition 4 was obtained in the following manner. [Surface tension evaluation] The surface tension of the colored photosensitive resin composition 4 was determined in the same manner as in Example 1 and found to be 26.5 mN/m. [Formation of Coating Film] 攸When the main component of the coloring photosensitive resin composition 4 drops the drop (^: owed) square on the broken glass substrate, it spreads to a circular shape of diameter 7_, no interference fringes appear, and the flatness is good. [When using a non-rotating applicator, 36 314902 1303350 will color the photosensitive resin group When a non-rotating applicator was used to form a coating film, a coating film having good flatness and no unevenness was obtained. Comparative Example _1 F475i of the component (F) of Example 1 was made into a large Japanese ink chemistry. In the same manner as in the Example, the comparative colored photosensitive resin composition 1 was produced in the same manner as in the Example. [Evaluation of Surface Tension] The surface tension of the comparative colored photosensitive resin composition 1 was determined in the same manner as in the embodiment, and as a result, it was 29 9 mN/m. [Formation of Coating Film] The comparatively colored photosensitive resin composition i was dropped from a micro syringe. When the droplet (10) was called on a glass substrate, it was diffused into a circular shape having a diameter of 8 mm, and interference fringes were formed, and flatness was poor. [Evaluation when using a non-rotating applicator] The colored photosensitive resin composition 1 will be compared, using a non-rotating applicator

When a coating film is formed, a coating film having a ten-faced defect and having uneven spots is prepared. Example 2: F475 (Daily Ink Chemical Industry Co., Ltd.) of the component (F) of Example 1 was changed to 〇·200 parts by mass, and the others were colored in the same manner as in the example. Photosensitive resin composition 2. [Evaluation of Surface Tension] VIII. Example 1 The surface tension of the comparative colored photosensitive resin composition 2 was determined in the same manner. As a result, it was 23 8 mN/m. [Formation of Coating Film] 314902 1303350 When a drop (10 // L) of the comparative photosensitive resin composition 2 was dropped from a micro-syringe onto a glass substrate, it was diffused into a circular shape having a diameter of 81ΉΠ1, and interference fringes appeared, and flatness was observed. For the bad. [Evaluation when using a non-rotating applicator] When the colored photosensitive resin composition 2 was compared and a non-rotating applicator was used to form a coating film, a coating film having poor flatness and uneven spots was obtained. Example 5

F475 (Daily Ink Chemical Industry Co., Ltd.) of the component (F) of Example 1 was changed to polyether modified eucalyptus SH8400 (trade name · Toray ketone (share) phantom 0.0H) by mass In the same manner as in Example ι, the colored photosensitive resin composition 5 was produced. [Surface tension evaluation] /, Bega example 1 and the same method were used to determine the surface tension of the colored photosensitive resin, and the result was 27.4 mN/m. Table 5 [Formation of coating film] Composition 5 drops 1 drop of 〇〇 7 mm round, no dryness from the micro-syringe to color the photosensitive resin # L) on the glass substrate, the diffusion into a diameter-dependent stripe, and flat Sex is good. [Evaluation when using a non-rotating applicator] To form, "coloring the photosensitive resin composition 5, when using a non-rotating coating plate, a coating film having good flatness and no smearing is obtained. I 6 changed the F475 (large system) of the component (F) of Example 1 into a polymer...^_(Product 3] 4902 38 1303350 In the same manner, the manufacture of ') 0·〇5〇 parts by mass, the bean bell Private t > /, Yu Zhizhi: Coated with the example of the coloring photosensitive resin composition 6. [Surface tension evaluation]. Table 6 was obtained in the same manner as in Example i to determine the surface tension of the colored photosensitive resin composition, and the result was 26.5. mN/m [Formation of coating film] When a syringe is used to form a colored photosensitive resin (AL) on a glass substrate, it diffuses into a diameter-dependent stripe, and the flatness is good. 7 mm round, 1 drop (1 0 No dryness was observed [Evaluation when using a non-rotating applicator] The colored photosensitive resin was composed of 4, and when a non-rotating applicator was used to coat the film, a coating film having good flatness and no uneven spots was obtained. Example 3 The F475 (manufactured by Otsuka Ink Chemical Industry Co., Ltd.) of the component (F) of Example i was changed. For the comparison test, the modified Shishi oil SH84 〇〇 (trade name: Toray (four) (share) clothing) 0 · 1 0 0 Berry, except for the same manner as in Example i, the comparative colored photosensitive resin composition 3 [Evaluation of Surface Tension] The surface tension of the comparative colored photosensitive resin composition 3 was determined in the same manner as in Example 1, and the result was 25.2 mN/m. [Formation of Coating Film] From the injection of comet to compare the colored photosensitive resin The composition 3 drops] When the droplet (1 0 // L) is on the glass substrate, the diffusion is rounded to a diameter of 8rnm, and interference fringes appear, and the flatness is poor. 314902 39 1303350 蝎"[Use non-rotation Evaluation at the time of the applicator] 胄Compared with the colored photosensitive resin composition 3, and formed by using non-rotation coating to form a coating film, a coating film having poor flatness and uneven unevenness was obtained. (F) component F475 (Otsuka ink chemical industry (share) ^), changed to polyether modified eucalyptus oil SH8400 (trade name: Toray ketone (share)) mussel injury, the rest is implemented Example 1 was fabricated in the same manner. • Comparison of the colored photosensitive resin composition 4. [Surface tension evaluation The surface tension of the comparative colored photosensitive resin composition 4 was determined in the same manner as in Example 1, and the result was 24 5 mN/m. [Formation of Coating Film] k U i Zhuang Ai will compare the colored photosensitive resin composition 4 When 1 drop (1 0 // L) is dropped on the glass substrate, the diffusion is rounded in diameter, and _ interference fringes appear, and the flatness is poor. [Evaluation when using a non-rotating applicator] When the photosensitive resin composition 4 was colored, a coating film was formed by using a non-rotating applicator, and a coating film having poor flatness and unevenness was obtained. • The colored photosensitive resin composition of the present invention can produce a coating film which does not cause interference fringes and has good flatness even if it is dropped on a substrate, and forms a coating film on the substrate even if a non-rotating applicator is used. A coating film having good flatness can be obtained. 40 314902

Claims (1)

1303350 ; - * 4 M 112. The patent application No. 92120759 (96 years, 1 month, 25 pm) Pickup, patent application scope: 1 · The color of the photosensitive resin composition' is characterized by: (a a coloring agent, (B) a binder acrylic copolymer, (c) a compound having a polymerizable carbon-carbon unsaturated bond, (D) a photopolymerization initiator, (£) a solvent, and (F) selected from the group consisting of a colored photosensitive resin composition comprising at least one surfactant selected from the group consisting of an anthrone-based surfactant, a fluorine-based surfactant, and an anthrone-based surfactant having a gas atom; wherein The content of the coloring agent is 8% by mass to 6% by mass based on the mass fraction of the coloring photosensitive resin composition; (B) the content of the binder acrylic copolymer is relative The solid content of the colored photosensitive resin composition is 5% by mass to 4 Å by mass fraction, and (C) the content of the compound having a polymerizable carbon-carbon unsaturated bond is relative to the above colored photosensitive resin. The solid content of the composition is 5 mass by mass fraction. % to 45% by mass; (D) The photopolymerization initiator contains a total amount of the compound (B) binder acrylic copolymer and (c) polymerizable carbon-carbon unsaturated bond. The ι mass parts are from 0.1 part by mass to 25 parts by mass; (E) the solvent is contained in an amount of from 7 to 5% by mass to 95% by mass based on the coloring photosensitive resin composition; and (F) the surfactant is contained The amount is 0.0005 parts by mass to 0.6 parts by mass based on 1 to 0 parts by mass of the colored photosensitive resin composition, and the surface tension of the photosensitive resin composition is 25.5 mN/m or more and 29 mN/m or less. 2. The color-sensitive photosensitive resin composition of claim 1, wherein (D) the photopolymerization initiator contains an styrene-based compound, and the 41,314,902, revised patent application No. 92120759 (96) October 25th ') Species application patent range No. 1 or 2 of the color-sensitive photosensitive resin composition eight manufacturing method' includes the inclusion of (A) colorant, (B) binder polymerization, (C) light The polymerizable compound, (D) photopolymerization initiator, and (E ^ 丨 曰 'Add (F) are selected from the group consisting of a nicotinic surfactant, a fluorine-based surfactant, and an anthrone-based surface having a fluorine atom. The active agent and at least one surfactant in the human group; wherein, the (A) colorant has a ratio of 8% by mass to 60% relative to the solid content of the colored photosensitive resin composition. (B) The content of the binder propionic acid-based copolymer is 5% by mass to 4 Å by mass based on the solid content of the colored photosensitive resin composition. ", the content of a compound having a carbon-carbon unsaturated bond of one nature is relative to the above coloring photosensitive The solid content of the resin composition is 5% by mass to 45% by mass based on the mass fraction; (D) the content of the photopolymerization initiator is relative to the above (B) binder acrylic copolymer and the above (C) The total amount of the compound having a polymerizable carbon-carbon unsaturated bond is 1 part by mass to 2 parts by mass to 25 parts by mass; (E) the solvent is 70% by mass based on the coloring photosensitive resin composition. To the content of 95% by mass; (F) the content of the surfactant is 0.0005 parts by mass to 0.6 parts by mass relative to the mass fraction of the colored photosensitive resin composition. The method for producing a resin composition includes mixing (A) a colorant, (B) a binder acrylic copolymer, (C) a compound having a polymerizable carbon-carbon unsaturated bond, and (D) photopolymerization. Starting agent, (E) solvent, and an anthrone-based surfactant, a fluorine-based surfactant, and an anthrone having a fluorine atom, Table 314902, Revision No. 42 1303350, Patent Application No. 92120759 (96, 1st, 25th, 1996) At least 1 in the group of surfactants In the case of a surfactant, the (F) is selected from the group consisting of an anthrone-based surfactant, a fluorine-based surfactant, and a fluorene-based surfactant having a fluorine atom. The amount of the agent added; wherein the content of the '(4) coloring agent is 8 mass=0/. to 60 mass% by mass fraction with respect to the solid content of the upper f-colored photosensitive resin composition. (B) Adhesive The solid content of the acrylic copolymer is 5% by mass to 4% by mass based on the solid content of the colored photosensitive resin composition; (c) a compound having a polymerizable carbon-unsaturated bond The content of the solid content relative to the coloring photosensitive resin composition is 5% by mass to 45% by mass based on the mass fraction; (D) the content of the photopolymerization initiator is relative to the above (b) binder olefin The total amount of the acid-based copolymer and the (C) polymerizable carbon-carbon-free compound and the bond is 100 parts by mass to 25 parts by mass; (E) the solvent is composed of the above-mentioned colored photosensitive resin. The content of the substance is 70% by mass to 95% by mass, and (F) the surface is live Containing an amount of the agent with respect to the parts by mass Shu thousand and the colored photosensitive resin composition by mass to 0005 parts by square-square-6 mass. The method for adjusting the surface tension of the colored photosensitive resin composition is a horse mixed (Α) coloring agent, a (Β) binder acrylic copolymer, (c) a compound having a polymerizable carbon-carbon unsaturated bond, (D) a photopolymerization creping agent, a (Ε) solvent, and (F) a group selected from the group consisting of a nicotinic surfactant, a gas-based surface susceptor, and a ruthenium surfactant having a gas atom. In at least one surfactant, the (F) is selected from the group consisting of an anthrone-based surfactant, a fluorine-based surfactant, and a fluorene-based surface having a fluorine atom. 43 314902 Rev. 1303350 Patent Application No. 92120759 (96) 1〇月25曰) \片J is a group of at least 丨胄 surfactant added to form a surface tension of 25.5mN / m or more and 29mN / m or less; where '(4) colorant content The amount of the solid content of the colored photosensitive resin composition is 8% by mass to 3% by mass. The content of the acryl-based copolymer is a solid content relative to the colored photosensitive resin composition. 5 parts by mass based on mass fraction 4〇贝里%, (the content of the compound having a polymerizable carbon-carbon unsaturated bond is 5% by mass to 45 f% by mass based on the solid content of the colored photosensitive resin composition; (D) The content of the photopolymerization initiator is a total amount 100 of the compound of the (B) binder propylene (tetra) copolymer and the (C) oxime having a poly-amplitude carbon-carbon unsaturated bond. 〇" parts by mass to 25 parts by mass; (8) solvent: the content of the above-mentioned colored photosensitive resin composition is 7 〇 mass% to % 篁%, and (F) the content of the surfactant is relative to the above coloring The photosensitive resin composition is a mass fraction of G·Cai 5 f parts to G 6 parts. 6. The method of forming a layer is a composition of the photosensitive resin which is applied by the patent scope or the item An applicator other than the spin coater forms a layer composed of a colored green resin composition on the substrate. 7. - A method for forming a pattern" is a colored photosensitive resin of the first or second application of the patent application. The composition is coated on the substrate by the coated (four) color photosensitive tree The composition layer removes the volatile component, exposes the layer by a photomask, and develops the image. D 8. - A coloring device, which is included in the method of patent application 帛 7 314902 revision 44 1303350 92120759 No. Patent application (October 25, 1996). A liquid crystal display device, which is equipped with a color filter of claim 8 of the patent application. 45 314902 revision