TW200815918A - Photo-curable colored composition and color filter formed by using the same - Google Patents

Abstract

The invention provides a photo-curable composition comprising: a photopolymerization initiator having a specific chemical structure; a black pigment comprising at least one selected from the group consisting of (A) a carbon black having a specific surface area of 110 m<SP>2</SP>/g or less and a pH of 2 to 9, (B) a carbon black coated with silica, and (C) a carbon black coated with a resin; and an addition-polymerizable compound having an ethylenic unsaturated group. The invention further provides a color filter comprising a colored pattern formed using the photo-curable composition.

Description

[Technical Field] The present invention relates to a photocurable coloring composition and a color filter obtained by using the same, which is used for forming a liquid crystal display element ( A color filter such as a liquid crystal display (LCD) or a solid-state imaging device (Charge Coupled Device (CCD), Complementary Metal Oxide Semiconductor (CMOS) or the like) is useful. [Prior Art] In recent years, displays of various types of devices such as televisions, personal computers, and mobile phones have been required to have high image quality and high color. In particular, displays for televisions are also required to be screened. At present, in the mainstream liquid crystal display system of the display, in order to achieve the above-described high image quality, high colorization, and large screen, the color filter technology used in this mode becomes very important. Specifically, a technique for manufacturing a color filter and a photohardenable coloring composition suitable for the color filter become important. In order to refine the color filter, in order to refine the line width of the pattern formed by the color filter, it is necessary to form a pattern with good precision for pattern exposure and subsequent development. Further, in order to increase the coloration, the hue adjustment and the high concentration of the colorant are necessary. However, the use of the curable composition obtained by dispersing the previous pigments causes problems such as uneven color due to the coarser particles of the pigment. Therefore, it is difficult to further improve the resolution by using the curable composition. Therefore, the curable composition is not suitable for applications in which a solid pattern is required for a solid-state image sensor. Therefore, there is a proposal (for example, refer to Japanese Laid-Open Patent Publication No. Hei No. No. Hei No. Hei No. Hei. No. Hei. No. Hei. When a dye is used or a pigment is used as a coloring agent, the content of the coloring agent of the colored curable composition for producing a color filter must be increased, but on the other hand, it is used to harden the colored curable composition. The content of the photopolymerization initiator and the photopolymerizable monomer which are essential components is limited, or the exposure wavelength light to be hardened is likely to be caused to interfere with the interface of the glass support, so that the high sensitivity of the curable coloring composition is high. Modification or high adhesion to the support becomes necessary. Moreover, in recent years, as the size of the substrate has expanded, the manufacture of a large-area color filter has become indispensable. However, in order to maintain the previous productivity without changing the process and energy costs, it is necessary to reduce the coating time or exposure time. Therefore, in order to achieve a rapid coating speed, the wettability of the photocurable coloring composition to the glass support is increased, or the high sensitivity corresponding to a shorter exposure time (less exposure amount) becomes necessary. Further, when the display is enlarged, since the micro defects after the color filter is manufactured have a large yield, the heat resistance or light resistance of the hard-fat composition forming the colored pattern is required to be higher than before. Leveled and stabilized. In the past, as a curable composition for producing a color filter, for example, a combination of a carboxyl group-containing binder polymer, a polyfunctional acrylate such as pentaerythritol hexaacrylate, and a photopolymerization initiator is used. Radioactive composition, as a highly sensitive photopolymerization initiator for such a radioactive composition, there are proposals to disclose 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl Diimidazole, 2,2,-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, etc. (refer to Japanese Patent Laid-Open No. Hei 6-75372, and JP-A No. 6 -75373). In addition, a photopolymerization initiator which can be applied to a curable composition can be used as a photopolymerization initiator which can be applied to a radioactive composition used in a printing plate or a photoresist, and such a photopolymerization initiator has a proposal to disclose 2 , 2'-bis(2-chlorophenyl)-4,4',5,5,-tetraphenyldiimidazole, 2,2,-bis(2-chlorophenyl)-4,4',5, 5'-tetrakis(alkoxyphenyl)diimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5,-tetrakis(dialkyloxyphenyl)diimidazole, 2 , 2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)diimidazole, etc. (refer to Japanese Patent Publication No. 4-8-3 8403 and JP-A-62_ 1 74204). (1) However, the sensitivity of the curable composition of any of the above is not satisfactory, and it is necessary to irradiate high-energy radiation when it is cured. The curable composition is used to form a color filter. When the coloring pattern is insufficient, if the amount of radiation is insufficient, problems such as falling off or missing of the pattern, residual film rate, or low pixel strength may occur, and the coloring pattern of the obtained color filter may cause resolution and support. The problem of the lowering of the adhesiveness. As described above, it is required to obtain a sclerosing group I which can be cured with high sensitivity even when a coloring agent is contained at a high concentration, and which has good pattern formability, and is obtained by using the same. The color filter has a coloring pattern excellent in resolution and adhesion to a support. However, the present invention cannot be provided. [Invention] The present invention has been made in view of the prior problems. That is, the present invention can provide a color filter. A photocurable coloring composition which is useful for a light sheet, and the photocurable coloring composition can be high even if it contains a toner at a high concentration a colored pattern which is excellent in adhesion to a glass substrate and which is excellent in adhesion to a glass substrate, and provides a color filter 200815918 piece obtained by using the photocurable coloring composition, the color filter The present invention has been able to solve the above problems by providing a coloring pattern having a high resolution and excellent adhesion to a support. The present inventors have found that the above problems can be solved by a specific photopolymerization initiator and a curable coloring composition of a specific black pigment. In other words, the composition of the present invention is as follows: <1> A photocurable coloring composition containing a photopolymerization initiator, a black pigment, and a compound having an ethylenically unsaturated group capable of addition polymerization, the photopolymerization The initiator is represented by the following formula (1); and the black pigment contains f. (A) carbon black having a specific surface area of 110 m 2 /g or less and a pH of 2 to 9; At least one of the group consisting of cerium oxide-coated carbon black and (C) resin-coated carbon black; general formula (1)

In the formula (I), R1 and R2 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a group represented by the following formula (Ι-A) or (I-B). R3 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. The W system represents a halogen atom. The χ and γ systems each independently represent a chlorine atom or a bromine atom. The m and η systems each independently represent 0, 1, or 2. General formula (I-Α) Formula (Ι-Β) 200815918 In the formulae (I-A) and (Ι·Β), R5, R6 and R7 each independently represent an alkyl group or an aryl group. &lt;2&gt; A color filter comprising a glass support and a colored pattern provided on the glass support, the colored pattern being formed by a method comprising an exposure step and an imaging step, In the exposure step, the layered body formed by providing the photocurable colored layer composed of the photocurable coloring composition of &lt; i &gt; is subjected to pattern exposure to cure the exposed region of the photocurable colored layer; The developing step forms the coloring pattern by developing the exposed layered body to remove the unexposed areas. The photocurable coloring composition of the present invention (hereinafter, simply referred to as a curable composition) contains a specific photopolymerization initiator having a hetero ring in the molecule, a black pigment, and an ethylenically unsaturated group capable of addition polymerization. a compound, the black pigment containing carbon black selected from (A) a specific surface area of 110 m ^ 2 /g or less and having a pH of 2 to 9, (B) coated ceria carbon black, and (C) resin-coated carbon At least one of the group consisting of black. The mechanism of action of the present invention is not clear, but it is estimated as follows. The carbon black which is useful as a black pigment has high self-cohesiveness and is difficult to be uniformly dispersed. Further, the photopolymerization initiator having a three-trap ring structure used in the present invention, although having high sensitivity, is also known to be liable to cause self-aggregation due to its structure. The specific photopolymerization initiator used in the photocurable coloring composition of the present invention has a very high affinity with the specific carbon black described above, and in the state of the coating film, the presence of the initiator and the carbon black does not repel each other. Disperse evenly. As a result, it is considered that since the spatial distance between the photocurable component and the photopolymerization initiator is small in the entire range of the formed film, the hardening efficiency of the light 200815918 can be substantially improved as compared with the case of the film in the unevenly dispersed state. And highly sensitized. The cured film (exposure portion) obtained by exposing and curing the photocurable coloring composition in a uniformly dispersed state is considered to be caused by a high-efficiency hardening reaction, and the film is uniformly adhered to the lower layer while improving the strength of the film itself. It is also possible to achieve high adhesion of the cured film. On the other hand, in the unexposed portion, since the coating liquid permeability is uniformized, the coating film is quickly dissolved, so that excellent developing performance can be exhibited. It is considered that the intensity of the exposed portion and the development of the unexposed portion can be achieved in the same manner, and even a fine pattern can exhibit good pattern formation property, and high visibility can be obtained. [Embodiment] Hereinafter, the photocurable coloring composition of the present invention and a color filter obtained by using the same will be described in detail. [Photocurable coloring composition] The photocurable coloring composition of the present invention is characterized by containing (1) a photopolymerization initiator represented by the following formula (I) (hereinafter, simply referred to as "specific initiator") (2) The black pigment contains carbon black selected from (A) a specific surface area of 110 square Å / metre or less and a pH of 2 to 9; (B) a cerium oxide carbon black; and (C) At least one or more of the group consisting of resin-coated carbon blacks, and (3) a compound having an ethylenically unsaturated group capable of addition polymerization. Hereinafter, each component contained in the photocurable coloring composition of the present invention will be described in order. &lt;(1) Photopolymerization initiator represented by the following formula (1)&gt; The curable colored layer of the present invention contains a photopolymerization initiator containing a three-till ring structure in the molecule, and -10-200815918 I)

CHnY3, PHmX3.m In the formula (1), R1 and R2 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a group represented by the following formula (Ι-A) or (I-B). R3 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. The W system represents a halogen atom. The X and γ systems each have a chlorine atom or a bromine atom on the surface. The m and η systems each independently represent 0, 1, or 2. The above alkyl group, aryl group, or alkoxy group may further have a substituent. Examples of the substituent which can be introduced include an aryl group such as a phenyl group, a halogen atom, an alkoxy group, an alkoxymethyl fluorenyl group, an aryloxymethyl fluorenyl group, a fluorenyl group, a nitro group, a dialkylamino group, and a sulfonium group. Base derivatives, etc.

In the formula (I-A) 〇 r5-c—in the formulae (Ι-A) and (Ι-Β), R5, R6 and R7 each independently represent an alkyl group or an aryl group. The above alkyl group and aryl group may further have a substituent. Examples of the substituent which can be introduced include an aryl group such as a phenyl group, a halogen atom, an alkoxy group, an alkoxymethyl fluorenyl group, an aryloxymethyl fluorenyl group, a fluorenyl group, a nitro group, a dialkylamino group, and a sulfonate. Mercapto derivatives and the like. In the formula (I), R1 and R2 can form a heterocyclic ring composed of a non-metal atom together with a nitrogen atom bonded thereto. In this case, the heterocyclic ring may be as described in the following -11-200815918.

I, Ν - Specific examples of the specific initiator represented by the formula (I) include 4-[m-bromo-p-quinone, fluoren-di(ethoxycarbonylmethyl)aminophenyl]-2. 6-bis(trichloromethyl)-s-three tillage, 4·[m-chloro-p-oxime, Ν-bis(ethoxycarbonylmethyl)aminophenyl]·2,6-di(trichloromethane) -s-triterpene, 4-[m-fluoro-p-indene, indole-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triad , 4-[o-bromo-/p-oxime, Ν·bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-two-well, 4-[o Chloro-p-oxime, Ν--*(Ethyl-based methyl)aminophenyl]-2,6-di(trichloromethyl)-s-trimole, 4-[o-fluoro-p-quinone, Bismuth-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl tritonate, 4-[o-bromo-p-N,N-bis(chloroethyl)aminobenzene -2,6-di(trichloromethyl three-till, 4-[o-chloro-p-N,N-di(chloroethyl)aminophenyl]-2,6-di(trichloromethyl) -s-Triple, 4-[o-fluoro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-three tillage, 4-[ Bromo-p-N,N-bis(chloroethyl)aminobenzene 2,6-dif (trichloromethyl)-s-three tillage, 4-[m-chloro-p-oxime, fluorene-bis(chloroethyl)aminobenzene\^yl]-2,6- Bis(trichloromethyl)-s-tripper, 4-[m-fluoro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyltrimoxide, 4 -[Interbromine-p-N-ethoxycarbonylmethylaminophenyl]-2,6-di(trichloromethyl)-s-trimole, 4-[m-chloro-p-N-ethoxycarbonylmethyl Aminophenyl]-2,6-di(trichloromethyl)-s-tripper, 4-[m-fluoro-p-N-ethoxycarbonylmethylaminophenyl]-2,6-di(three Chloromethyl)-s-tripper, 4-(o-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-trimole, 4-( o-Chloro-p-N-ethoxycarbonylmethylaminophenyl]-2,6-di-12- 200815918 (trichloromethyl)-s-triterpene, 4-(o-fluoro-p-N-ethoxyl Carbonylmethylaminophenyl]-2,6-bis(trichloromethyl)-s-tripper, 4-(m-bromo-p-N-chloroethylaminophenyl)-2,6-di(trichloro) Methyl)-s-three tillage, 4-(m-chloro-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-tripper, 4-(m-fluoro-pair N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triterpene, 4-(o-bromo-p-N-chloroethylamine Phenyl)-2,6-bis(trichloromethyl)-s-tripper, 4-(o-chloro-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)- S-three tillage, 4-(o-fluoro-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-triad, etc., and introducing two or more η halogen atoms in the phenyl moiety Made of three farming and so on. These specific initiators have a radical generating site and a triple well skeleton in the molecule, and it is preferred that the benzene ring at the central position has two halogen atoms or a substance having a bromine atom. The specific initiator may be used alone or in combination of two or more. The content of the specific initiator of the photocurable coloring composition is preferably in the range of 0.1 to 15.0% by mass in terms of the solid content, and more preferably in the range of 0.5 to 1% by mass. In this range, the polymerization reaction can be efficiently carried out (the hardness of the obtained cured film is also excellent. (Other photopolymerization initiators) In addition to the specific initiator described above, the curable composition does not impair the present invention. In the range of the effects of the invention, other photopolymerization initiators may be used. The photopolymerization initiator which can be used herein is capable of causing polymerization of a compound having an ethylenically unsaturated group capable of addition polymerization which will be described later. The compound is preferably an absorption material in a region having a wavelength of from 00 to 500 nm. The photopolymerization initiator may, for example, be an organic halogenated compound, oxadiazole-13-200815918, a carbonyl compound or a ketal. a compound, a benzoin compound, an acridine compound, an organic peroxidation compound, an azo compound, a coumarin compound, an azidation, a metal-missing compound, a diimidazole compound, an organoboric acid compound, a diterpene compound, an oxime ester compound a key salt compound, a mercaptophosphine (oxide) compound, wherein, from the viewpoint of high sensitivity, selected from a trihalomethyl triple trap At least one compound selected from the group consisting of a compound, a diimidazole compound, and an anthraquinone compound is preferred, and a diimidazole compound is preferred. f A photopolymerization initiator can be used in combination with the specific initiator described above. &quot; The amount is preferably 75% by mass or less, more preferably 5% to 50% by mass. Further, the total amount of the specific initiator and the other photopolymerization initiator is 〇.1 with respect to the total solid content of the composition. It is preferably 50% by mass, more preferably 0.1 to 30% by mass, more preferably 0.3 to 20% by mass, and good sensitivity and pattern formation can be obtained in this range. (Sensitizer) These specific initiators Sensitivity can be used. / The sensitizer which can be used in the present invention is preferably one which can sensitize a radical initiator by an electron moving mechanism or an energy moving mechanism. The compounds are listed and have an absorption wavelength in a wavelength region of from 300 nm to 450 nm, preferably in a wavelength region of from 330 nm to 450 nm. Specific examples of the sensitizer include polycyclic aromatics. Family (such as Philippine蒽, 芘, 茈, tri-o-phenylene, 9,10-dialkoxy fluorene), thioxanthens (eg luciferin, eosin, erythromycin, rhodamine B), rose Red), thioxanthone (isopropyl thioxanthone, diethyl thioxanthone, chlorothioxanthone), cyanine-14-200815918 cyanine (such as thiablycine, anthocyanin) Anthocyanins, merocyanines (eg, anthocyanins, carbonaceous anthocyanins), phthalocyanines, thiazide (eg, thionine, methylene blue, toluidine) Blue), acridines (such as acridine orange, chlorsulfurin, acridine yellow), terpenoids (such as sputum), snail key (such as snail key), coumarin (such as 7 - 2 Amino-4-methylcoumarin), oxocoumarin, morphine trap, morph, styrene benzene, azo compound, diphenylmethane, triphenylmethane, diphenylethylbenzene, Carbazoles, porphyrins, spiro compounds, quinophthalones, trichosyl, styryl, /pyranyl compounds, methylene pyrrole compounds, pyrazole triazole compounds, benzoxazole compounds, barbituric acid derivatives , Thiobarbituric acid derivatives, acetyl benzene, diphenyl ketone, thioxanthone, M. Le which one (Michler's ketone) and the like aromatic ketone compounds, N · fathoms aryl and heterocyclic oxazolidinone compounds. In order to improve the characteristics of the curable composition, various sensitizers may be subjected to various chemical modifications. For example, a sensitizer and an addition polymerizable compound structure (for example, an acrylonitrile group or a methacryl fluorenyl group) are bonded by a covalent bond, an ionic bond, a hydrogen bond, or the like, and the exposed film is made to have high strength. The formation or suppression of the specific sensitizer from the exposed film produces unwanted precipitation. Further, a sensitizer and a partial structure having a radical generating property in the photopolymerization initiator (for example, a reductive decomposition site of a halogenated alkyl group, a key, a peroxide, a diimidazole or the like or a borate, an amine, or a third) The bonding of an oxidatively cleavable site such as a methyl decylmethyl group, a carboxymethyl group, a carbonyl group or an imine, in particular, can significantly improve the photosensitivity with an initiator system in a low concentration state. The sensitizer may be used alone or in combination of two or more. The content of the sensitizer is preferably from -15 to 200815918 of 0.1% by mass to 20% by mass, more preferably from 0.2% by mass to 20% by mass, based on the total solid content of the curable composition. When the concentration of the coloring agent of the curable composition is very high, and the light transmittance of the formed coloring pattern (photosensitive layer) is extremely low (specifically, for example, when the sensitizer is not added, the photosensitive layer is 3 When the light transmittance of 6 5 nm is 1% or less, the effect can be remarkably exhibited by adding a sensitizer. &lt;(2) selected from the group consisting of carbon black having a specific surface area of 110 m 2 /g and having a pH of 2 to 9, (B) coated ceria black, and (C) resin-coated carbon black At least one or more kinds of black pigments in the group&gt; f, and the coloring agent used in the present invention is selected from specific black pigments (hereinafter referred to as specific black pigments) described in detail below. [(A) Carbon black having a specific surface area of 110 m 2 /g or less and having a pH of 2 to 9 (specific black pigment (A))] The carbon black which is suitably used in the present invention may have a specific surface area of 110 square. A material having a pH of 2 to 9 and a pH of 2 to 9 or less. When the specific surface area is more than 110 m ^ 2 /g, the amount of the polymer dispersant necessary for dispersion stabilization must be large, but since the polymer dispersant is insoluble in the developing solution, the solution of the curable composition is obtained. Sex and imaging are easy to decline. Further, since the material having a pH 値 of more than 9 is easily adsorbed to the polymer dispersant, it is difficult to disperse and stabilize. The industrial manufacture of carbon black having a pH of less than 2 is very difficult and impractical. Here, the specific surface area and pH of the carbon black can be measured by a usual method. In the present invention, the BET method (N2 gas adsorption amount) is applied to the specific surface area, and the ruthenium measured by the KOH neutralization titration method is applied to the pH system. The carbon black having such a physical property can be purchased from a commercially available product, and specifically, for example, carbon black #2400, #2350, #2300, #2200, -16-200815918 manufactured by Mitsubishi Chemical Corporation.

#1000, #980, #970, #960, #950, #900, #850, MCF88, #650, MA600, MA7, MA8, ΜΑΗ, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B &gt;# 4000, #40 10 &gt;#55,#52,#50,#47,#45,#44,#40,#33,#32&gt;#30,#20,#10,#5,CF9,# 3050, #3150, #3250, #3750, #3950, DIABLACK A, DIABLACK N220M, DIABLACK N23 4, DIABLACK I, DIABLACK LI, DIABLACK II, DIABLACK N 3 3 9 , DIABLACK SH, DIABLACK SHA, DIABLACK LH, DIABLACK H , DIABLACK HA, DIABLACK SF, DIABLACK 5 5 0M, DIABLACK E, DIABLACK G, DIABLACK R, DIABLACK 760M, DIABLACK LR; Carbon Black THERM CAN N9 90, N99 1, N907, N908, N990, N991, N908 ; ASAHI CARBON company carbon black Asahi #80, Asahi #70, Asahi #70L, Asahi F-200, Asahi #66, Asahi #66HN, Asahi #60H, Asahi #60U, Asahi #60, 旭#55, Asahi 50H, Asahi #51, Asahi #50U, Asahi #50, Asahi #35, Asahi #80, Asahi #15, ASAHITHERMAL; DEGUSS A company's carbon black Color Black Fw200, Color Black Fw 2, Color Black Fw2V, Color Black Fwl, Color Black Fwl8, Color Black S170, Color Black S160, Special Black6, Special Black5^ Special Black4^ Special Black4A&gt; Special Black2 5 0 &gt; Special Black3 5 0 ' PrintexU^ PrintexV &gt; Printexl40U, Printexl40V (any one is a trade name), etc., and any of these can satisfy the above physical conditions. [(B) Bismuth dioxide-coated carbon black (specific black pigment (B))] -17- 200815918 Another aspect suitable for use in the specific black pigment of the present invention is a carbon black obtained by coating a surface of cerium oxide. (Specific black pigment (B)). By using (B) ruthenium dioxide-coated carbon black, the photocurable coloring composition of the present invention can exhibit excellent image formability and high light-shielding property. The carbon dioxide-coated carbon black is not particularly limited, and furnace black or ethylene carbon black having a specific surface area of 25 to 500 g/m 2 can be usually used. Specifically, for example, carbon black shown below can be mentioned. Mitsubishi Chemical Corporation: MA7, MA8, ΜΑΗ, MA100, MA220, r, MA230, #52, #50, #47, #45, #2700, #2650, #2200, #1000, l: #990, #900 Etc.; DEGUSSA company: Printex95, Printex90, Printex85, Printex75, Printex55, Printex45, Printex40, Printex30,

Printex3, PrintexA, PrintexG, Special Black550, Special Black350, Special Black250 &quot; Special BlacklOO ^ ; CABOT company: Monarch460, Monarch43 0,

Monarch2 8 0, Monarchl20, Monarch8 00, Monarch4630, REGAL99, REGAL99R, REGAL41 5, REGAL415R, REGAL2 5 0, REGAL2 5 0R, REGAL 3 3 0, BLACK PEARLS 4 8 0, PEARLS 13 0, etc.; COLOMBIAN CARBON Company: RAVEN11 , RAVEN 15, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, etc. (all are trade names). When the carbon black-coated ruthenium dioxide is used, the total amount of ruthenium dioxide relative to the dioxin-18-200815918 ruthenium carbon black is usually 0.5 to 50% by weight of 'i~2' and is about 1 to 40% by weight. It is better. The amount of silica sand coated in the specific black pigment (B) can be measured by the T G - D T A differential thermogravimetric weight change measurement or the E S C A method. The coating of cerium oxide on carbon black can be carried out by gas phase or liquid phase, which can be carried out by any method. As an example of coating a ceria by a vapor phase method, first, carbon black is placed in a closed container, and the sealed container is degassed. A source of ruthenium dioxide such as tetramethyl, oxoxane or tetraethoxy decane is introduced therein to adsorb a decane source on the surface of the 4 carbon black to react the carbon black with the decane source. After the completion of the reaction, the excess cerium oxide source is removed under reduced pressure. Then, a base such as ammonia is introduced into a sealed vessel to convert the methoxy group and the ethoxy group into a trans group. By this series of operations, a ceria coating layer can be formed on the surface of the carbon black. The amount of cerium oxide deposited on the carbon black can be controlled as necessary. In an example in which the ceria is coated with a liquid phase method, an aqueous dispersion of carbon black is prepared, and a base such as potassium hydroxide or ammonia is added to the carbon black aqueous dispersion, and a source of cerium oxide is added thereto. In this case, a citric acid solution obtained by deactivating a water glass aqueous solution by a cation exchange resin or the like can be suitably used as a silica sand source. Further, in other means of the liquid phase method, a sol-gel reaction such as tetramethoxynonane or tetraethoxysilane may be used. In the method of the sol-gel reaction, if the carbon black aqueous dispersion is made acidic by hydrochloric acid or the like, or is made alkaline by ammonia or the like, a secondary oxidation such as tetramethoxy decane or tetraethoxy decane is added. Let the source react to make it react. The carbon black coated with cerium oxide can be used without any pre-treated carbon black, and -19-200815918 can directly use the aforementioned carbon black. Alternatively, it is also possible to use carbon black which is subjected to surface modification by introducing a hydroxyl group into the surface by steam plasma treatment. The steam plasma treatment is, for example, a method in which carbon black is added to a sealed container, and after degassing, water vapor is introduced and plasma is irradiated to introduce a hydroxyl group on the surface of the carbon black. Further, other surface modification methods for increasing the coating efficiency of cerium oxide on the surface of carbon black may also oxidize the surface of carbon black. Examples of the oxidation treatment are high temperature calcination by heating at 100 to 300 ° C in an air environment; contact with an acid such as nitric acid or perchloric acid or hydrogen peroxide at a temperature of 100 to 2 50 t. The acid treatment method; the ozone oxidation method which is heated at a temperature of 100 to 300 ° C in an ozone environment, etc. The method of coating the cerium oxide such as the liquid phase method or the gas phase method, and steaming the carbon black. Various pretreatment methods such as slurry treatment and oxidation treatment can also be carried out in any combination, and (a) the carbon black treated by the pretreatment of the steam plasma, and the state of coating the cerium oxide by the vapor phase method (b) For untreated carbon black, coated with cerium oxide by gas phase method, I f and (c) with untreated carbon black, coated with cerium oxide by liquid phase method Any one of the aspects is preferred, wherein (a) carbon black obtained by introducing a hydroxyl group on the surface by steam plasma treatment is used to coat the cerium oxide by a gas phase method, or It is more preferable that the untreated carbon black is coated with cerium oxide by a liquid phase method. The cerium oxide can be coated on the surface of the carbon black of the specific black pigment (B), and a cerium oxide coating layer may be present on a part of the surface. The effect of the present invention can be obtained in either case. The presence of silica sand on the surface of the pigment (B) can be confirmed by the method of -20-200815918 ESCA. [(C) Resin-coated carbon black] 'An additional aspect of the specific black pigment suitable for use in the present invention can be Carbon black (specific black pigment (C)) coated with a resin. The carbon black used to form a specific black pigment (C) is furnace black, channel black, acetylene black, lamp black, and furnace black. The particle size of the carbon black is usually 20 μm or less, preferably 5 μm or less, more preferably 1 μm or less, and the particle diameter is preferably 0.01 μm or more from the viewpoint of dispersibility and workability. A specific black pigment (C) suitable for the present invention can be obtained by coating a resin on the surface of the carbon black. Examples of the resin covering the surface of the carbon black include an epoxy resin, an anthracene resin, a melamine resin, and a xylene resin. Phthalate Thermosetting resin such as allyl ester resin, glyptal resin, alkyl benzene resin, polystyrene, polycarbonate, polyethylene terephthalate, polybutyl phthalate, modified poly Phenyl ether, polyfluorene, poly(p-phenylene terephthalamide), polyamidoximine, polyimine, polyamine bis-butenylene imide, polyether sulfonate polyphenyl hydrazine, polyallyl A synthetic resin such as a thermoplastic resin such as an ester or a polyether ether ketone, or the like, and an epoxy resin is preferable. The epoxy resin which is suitably used for forming a resin coating layer may, for example, be a glycidylamine-based epoxy resin. Triphenylglycine oxime dimethane epoxy resin, tetraphenylglycine oxime dimethane epoxy resin, amino phenol epoxy resin, diamine diphenylmethane epoxy resin, phenol novolak type A polyfunctional epoxy resin such as an epoxy resin, an o-cresol epoxy resin, or a bisphenol A novolak epoxy resin. -21 - 200815918 The method for producing the resin-coated carbon black is not particularly limited, and examples thereof include a method of forming a coating layer on carbon black by using an emulsion of a resin. That is, when an epoxy resin is used as the resin, a carbon black dispersion is prepared, and a curing agent and an epoxy resin emulsion may be added thereto. In the formation of the coating layer, the curing agent used together with the epoxy resin may, for example, be 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-(meth)imidazole, 2-pyridylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4-diamino-6-[2-methylimidazole-(1) -ethyl-S-three (% tillage, etc. The amount of the curing agent used is usually from about 1% by mass to about 3% by mass, based on the total amount of the epoxy resin and the curing agent, and is 5% to 25°/. In the resin other than the carbon black-coated epoxy resin, for example, in the state in which the carbon black is dispersed in the dispersion medium, the resin emulsion may be added and heated and dispersed. When the epoxy resin is used as the resin and the carbon black is coated together with the curing agent, the carbon black may be dispersed in the dispersion medium, and the resin emulsion and the curing agent may be added. The ratio of the resin and the mass fraction is usually 5% or more and 40% or less, preferably 7% or more and 20% or less. When the content is less than 5%, the electric resistance of the black matrix tends to decrease, and when it is more than 40% or more In the black photosensitive resin composition or the black matrix, there is a possibility that it is difficult to uniformly disperse the resin-coated carbon black. The resin can be coated on the surface of the carbon black of the specific black pigment (C), and may also be on the surface thereof. A resin coating layer is present in part, and the effect of the present invention can be obtained in either case.

The presence of the resin of the surface of the specific black pigment (C) can be confirmed by the method of TG-DTA-22-200815918 or esca. The photocurable coloring composition of the present invention contains one or more kinds of black pigments selected from the above specific black pigments (A) to specific black pigments (C). When these plural kinds are used, different physical properties, coating materials, and/or coating materials may be combined from the same black pigment, for example, (B) coated with ceria carbon black and (C) coated resin black The way to combine different kinds. Further, these specific black pigments may also be used in other black inorganic pigments and organic pigments. It is preferable that the light-shielding property is more than 50% by weight or less based on the total amount of the black pigment which is the main [black carbon black contained in the material] as the specific black pigment. Other black pigments include, for example, titanium black, aniline black, iron oxide black pigment, and black pigments in which three colors of red, green, and blue are mixed. The specific black pigment of the present invention is preferably used as a light-shielding material. From this point of view, for example, when a black matrix having a light-shielding ratio of a film thickness of 1 μm and a high light-shielding ratio of 3.5 or more is formed, the specific black pigment is photocurable with respect to the total solid content in the curable composition. The amount of the coloring composition to be added must be an appropriate amount. In the photocurable coloring composition of the present invention, the content of the black pigment is based on the total solid content of the constituent pigment (including the content of the dispersant) and the total solid content of the curable composition from the viewpoint of the curing sensitivity and the color density. 20% by mass or more and 90% by mass or less is preferable, and it is preferably 20% by mass or more and 75% by mass or less, and more preferably 30% by mass or more and 60% by mass or less. When the content of the specific black pigment is too small, a color filter is produced from the curable composition of the present invention, and particularly when a black matrix is produced, an appropriate light-shielding property tends not to be obtained. On the other hand, when the amount of the -23-200815918 is too large for the specific black pigment, the photohardening cannot be sufficiently performed, and the strength of the film is lowered, and the development range at the time of alkali development tends to be narrow. However, since the specific initiator of the present invention has high light absorption efficiency and can be uniformly dispersed in the curable composition by interaction with a specific black pigment, it can be exhibited remarkably even if it contains a black pigment at a high concentration. The effect of sensitivity is improved, and the adhesion to the support of the cured film is also excellent. (Coloring Pigment) In addition to the specific black # pigment, the photocurable coloring composition of the present invention may be used in accordance with the purpose of selecting one or two kinds of previously known various pigments suitable for color filter applications. In the photocurable coloring composition of the present invention, various inorganic pigments or organic pigments which have been known in the art can be used as the pigment which can be used. It is considered that the photocurable colored layer formed has a high light transmittance. It is preferable that any of the inorganic pigment and the organic pigment is a pigment having a fine particle diameter as much as possible. When the balance is considered, the average particle diameter of the above pigment is preferably from 0.01 μm to 0.1 μm, more preferably from 0 · 0 1 μm to 0 · 〇 5 μm. Further, the inorganic pigment may be a metal compound such as a metal oxide or a metal complex, and specific examples thereof include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. And a composite oxide of the foregoing metal. The organic pigment may, for example, be CI Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 1〇9, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185. 199; C · I. Pigment Orange 3 6 , 3 8 , 4 3 , 7 1 ; CI Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, • 24· 200815918 176, 177, 209, 220, 224, 242, 254, 255, 264, 270; C. I · Pigment Violet 9, 9 3, 3 2, 3 9; CI·Pigment Blue 1, 2, 15, 15: 1, i5: 3, I5: 6, 16, 22, 60, 66; C · I · Pigment Green 7, 3 6 , 3 7 ; C. I. Pigment Brown 2 5, 2 8 ; C. I. Pigment Black 1, 7; Carbon Black Wait. ('In the present invention, it is particularly preferable to use a substance having a basic N atom in the structural formula of the pigment. These pigments having a basic N atom show a good dispersant in the composition of the present invention. The reason is not sufficiently clear, and it is estimated that the affinity of the photosensitive polymerizable component and the pigment is high. The preferred pigment which can be used in the present invention includes the following, but the present invention is not limited thereto. Et. CI·Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, / 151, 154, 167, 180, 185; (. / C · I. Pigment Orange 3 6 , 7 1 ; C 丄Pigment Red 122, 150, 171 '175, 177, 209, 224, 242, 254, 255, 264; C. I. Pigment Violet 19, 2 3, 3 2 ; CI·Pigment Blue 15: 1, 15: 3 15: 6, 16, 22, 60, 66; c. I. Pigment Black 1 These organic pigments may be used alone or in order to improve color purity. Specific examples of the above combinations are as follows. For example, 'red Pigment can be -25 - 200815918 using a group selected from the group consisting of an anthraquinone pigment, an anthraquinone pigment, and a dioxopyrrole pigment a red pigment composed of a plurality of or at least one of the above, or a red pigment selected from the group consisting of a diazo yellow pigment, an isoindane yellow pigment, or a quinoline yellow pigment One of the group consisting of or containing a plurality of yellow pigments of at least one of these is mixed. For example, the fluorene-based pigment may be C. I. Pigment Red 177. The hydrazine pigment may, for example, be c· I · Pigment Red 1 5 5, C. I · Pigment Red 224. The dioxopyrrole-based pigment is CI·Pigment Red 2 5 4 . From the color reproducibility, the aforementioned red pigment is with C · I It is preferable to use a mixture of pigment yellow 139. Further, the content ratio (mass ratio) of the red pigment to the yellow pigment in the mixture of organic pigments is preferably 1 〇 0 : 5 to 1 0 0 : 5 0. Less than 1 0 0: 4, because it is difficult to suppress the light transmittance of 400 nm to 500 nm, there is a case where the color purity cannot be improved. Also, when 100 ° or more, the main wavelength of the absorption wavelength of the pigment is biased. By short wavelength, there will be a large shift from the NTSC target hue. Especially on The mass ratio is optimal in the range of 1 0 0 : 1 0~1 〇〇: 3 。. Also, when the red pigment is combined, the content ratio (mass ratio) can be adjusted simultaneously with the chromaticity. The green pigment may be used alone as the halogenated indigo pigment, or may be used in combination with the diazo yellow pigment, the quinacin yellow pigment, the azomethine yellow pigment or the isoindane yellow pigment. Examples of such mixing are mixed C. I · Pigment Green 7, 3 6 , 3 7 and C. I. Pigment Yellow 8 3, C · I. Pigment Yellow 1 3 8 , C · I · Pigment Yellow 1 3 9 C. I · Pigment Yellow 1 50, C · I · Pigment Yellow 1 800 or C. I · Pigment Astragalus 8 5 is preferred. The content ratio (mass ratio) of the green pigment to the yellow pigment is preferably 100 : 5 to 1 00 : 1 50 . When the above mass ratio is less than 100:5, since the light transmittance of 4 〇 〇 nanometer to 4 5 〇 nanometer is -26-200815918, it is difficult to improve the color purity. Further, when it is larger than 1 〇 ο : 1 5 0, since the dominant wavelength of the absorption wavelength of the pigment is biased by a short wavelength, there is a case where the phase shift from the N T S C target is large. In particular, the above mass ratio is particularly good in the range of 1 〇 〇 : 30 〜 1 00 : 1 20 . The blue pigment may be used alone as the indigo pigment, or the blue pigment and the diterpene violet pigment may be used in combination. For example, it is preferred to mix C.I. Pigment Blue 15:6 with C.I. Pigment 23. The content ratio (mass ratio) of the blue pigment to the purple pigment is preferably 100:0 to 100:30, more preferably 100:0 to 100:1 Torr. Further, the pigment for the black matrix can be used alone or in combination of carbon pigment, titanium, carbon, iron oxide, titanium oxide or the like. It is preferred to combine a specific black pigment with titanium carbon. Further, the content ratio (mass ratio) of the specific black pigment to titanium carbon is preferably in the range of 100:0 to 10,000:60. 1 〇〇 : When 6 1 or more, there is a case where the dispersion stability is lowered. The average particle diameter r (unit: nanometer) of the pigment of the present invention is preferably 20 S I* $300, preferably 125^1*^250, to satisfy 30$ι·$200. By using such a pigment having an average particle diameter r, it is possible to obtain a red and green pixel with high contrast and high light transmittance. The term "average particle diameter" as used herein means the average particle diameter of secondary particles obtained by aggregating primary particle diameters (single microcrystals) of a pigment. Further, the pigment which can be used in the present invention is a secondary particle having a particle diameter of (average particle diameter ± 100) nanometers as a whole 70 mass% or more, preferably a secondary particle diameter of 80% by mass or more. Particle size distribution. &lt;Pigment Dispersant&gt; Since a pigment is used as a colorant in the present invention, a well-known pigment dispersant can be used. The pigment dispersant may be a polymer dispersant [for example, -27-200815918 Polyamide amine and a salt thereof, a polycarboxylic acid and a salt thereof, a high molecular weight unsaturated acid ester, a modified polyurethane) , modified polyester, modified poly(methyl)propionate, (meth)acrylic copolymer, naphthalenesulfonic acid formalin condensate], and polyoxyethylene alkyl phosphate, polyoxyethylene alkyl Amines, alkanolamines, pigment derivatives, and the like. The polymer dispersant can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer according to the structure. The polymer dispersant is adsorbed on the surface of the pigment to prevent re-agglomeration #. Therefore, the high molecular weight dispersant having a preferred structure may be a terminal-modified polymer, a graft-type polymer, or a block-type polymer having an anchor site which can be fixed to the surface of the pigment. On the other hand, the pigment derivative has an effect of promoting adsorption of the polymer dispersant by modifying the surface of the pigment. Specific examples of the pigment dispersant used in the present invention include "Disperbyk-101 (polyammoniumamine phosphate), 1〇7 (carboxylate), 11〇 (copolymer containing acid group) manufactured by BYK Chemie Co., Ltd. ), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), "ΒΥΚ_ι〇4, P105 (high molecular weight unsaturated polycarboxylic acid), manufactured by EFKA) "EFKA 4047, 4050, 4010, 4165 (polyurethane type), EFKA 4330, 4340 (block copolymer), 4 4 0 0, 4 4 0 2 (modified polyacrylate), 5 0 1 0 ( Polyester phthalamide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (anthracene derivative), 67 5 (azo pigment derivative), AJINOMOTO FINE TECHNO "AJIS" UP ER-PB821, PB822", "Flowlen TG-710 (urethane oligomer)", "POLYFIOWNO.50E, Νο·300 (acrylic copolymer)", and Kwanmoto Chemical Co., Ltd. 28- 200815918 Manufactured by company company "DISPARLON KS- 8 6 0, 8 7 3 SN, 8 74, #2150 (月月 aliphatic polycarboxylic acid), #7004 (polyether ester), DA- 7 0 3 - 5 0, DA-70 5, DA-725", "DEM OR RN, N (formalin naphthalenesulfonate polycondensate), MS, C, SN-B (aromatic sulfonate fumarin polycondensate)", "HQMOGENOL L-18 (polymer polycarboxylic acid)", "EMULGEN 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "ACE ΤΑ MIN 86 (stearylamine acetate)" , manufactured by LUBRIZOL Co., Ltd. "SOLSPERSE 5000 (indigo derivative), 22000 (azo pigment derivative), 1 32 24 (polyesteramine), 3 000, 1 7000, 27000 (polymer having a functional moiety at the end) ), 24000, 28000, 3 2000, 3 8 5 0 0 (grafted polymer), NIKKO CHEMICALS company "NIKKOL T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene) Monostearate) and the like. In the polymer dispersant used for dispersing the specific black pigment of the present invention, for example, a polyisocyanate compound and a compound having one or more hydroxyl groups in the molecule (the number average molecular weight is 300 to 10,000), and A compound having an active hydrogen and a tertiary amino group in the same molecule is subjected to a reaction, and the obtained dispersion resin is characterized in that it is preferably a polymer dispersant having a weight average molecular weight of 1,000 to 200 Å. Hereinafter, a useful dispersing agent for dispersing a specific black pigment of the present invention will be described. The polyisocyanate compound may, for example, be p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate or naphthalene-1,5-diisocyanate. Aromatic diisocyanate such as tolidine diisocyanate, hexamethylene diisocyanate, methyl isocyanate diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diiso-29 - 200815918 An alicyclic diisocyanate such as a fatty acid diisocyanate such as cyanate ester, isophorone diisocyanate, 4,4,-methylene bis(cyclohexyl isocyanate) or dimethylcyclohexane ω,ω,-diisocyanate, Aliphatic diisocyanate having an aromatic ring such as phenyldimethyl diisocyanate, α,α,α,, α'tetramethylbenzene diisocyanate, orthoester type diisocyanate, 1, 6 , 1 1 - Eleventh isocyanate, methyl sheep compound 1,8-diisocyanate-4-isocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, ginseng (phenylmethane isocyanate), ginseng (isocyanate) Phenyl) thiophosphate Isocyanate trimer, and these r, the water Jiatian thereof, and such adducts of polyols and the like. A preferred polyisocyanate is a terpolymer of an organic diisocyanate, and the most preferred is a trimer of toluene diisocyanate and a trimer of isophorone diisocyanate. These may be used singly or in combination. The isocyanate terpolymer may be prepared by using an appropriate trimerization catalyst (for example, a third-order amine, a phosphine, an alkoxide, a metal oxide, a carboxylate or the like) to form the polyisocyanate. The isocyanate group is trimerized, and after the trimerization is stopped by adding a catalytic poison, the unreacted polyisocyanate is removed by solvent extraction and thin film distillation to obtain a polytrimide containing the target trimeric isocyanate group. Method of isocyanate. A compound having one or more hydroxyl groups (a number average molecular weight of 300 to 10,000) in the same molecule is preferably a compound having one or two hydroxyl groups, and an example of a particularly preferable one is a polyether diol, a polyester diol, A polycarbonate diol, a polyolefin diol, or the like, and a terminal hydroxyl group of the compound of the above are alkoxylated with an alkyl group having 1 to 25 carbon atoms, and a mixture of two or more kinds thereof. The polyether diol may, for example, be a polyether diol, a polyether ester diol, or a mixture of the above two types of -30-200815918 or more. The polyether diol is obtained by separately or copolymerizing an epoxy compound, and examples thereof include polyethylene glycol, polypropylene glycol, polyethylene glycol propylene glycol, polybutylene oxide diol, and polyethylene oxide hexane. An alcohol, a polyepoxyoctanediol, and a mixture of two or more of these. The polyether ester diol can be obtained by reacting an ether group-containing diol or a mixture with another diol with an anhydride of a dicarboxylic acid or the like, or by reacting a polyester diol with an alkylene oxide or the like. The substance may, for example, be polyadipate (polybutylene oxide) or the like. The best material of the polyether diol is polyethylene glycol, polypropylene glycol, polyglycidyl diol or the like. One of the compounds is a terminal alkoxy group having a carbon number of 1 to 2 5 . Made of things. The polyester diol is a dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, citric acid, etc.) or an anhydride thereof, and a diol. (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol , 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1, 3-propanediol, 2-butylethyl-1,3·propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4·pentanediol, 2,2,4 ·Trimethyl/yl-1,3-pentanediol, 2-ethyl-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-exetylene glycol, 2-methyl Aliphatic diol such as ketone-1,8-exryoctanediol, 1,9-nonanediol, alicyclic diol such as bishydroxymethylcyclodecane, benzene dimethyl glycol, bishydroxyethoxy group Examples of polycondensation are obtained by polycondensation of an aromatic diol such as benzene or an anthracene-alkyl dialkanolamine such as fluorene-methyldiethanolamine, and examples thereof include polyethylene adipate, polypropylene adipate, and poly(adipate). Hexamethylene adipate, polyhexyl A polylactone diol or a polylactone monool obtained by using an ethylene glycol/propylene diester or the like, or a polyglycol diol obtained by using the diol or a monovalent alcohol having 1 to 25 carbon atoms as an initiator, for example, polycaprolide An ester diol, a polymethyl valerolactone diol, and a mixture of two or more of these -31-200815918. The polyester diol is preferably a polycaprolactone obtained by using polycaprolactone diol or an alcohol having 1 to 25 carbon atoms as an initiator. Examples of the polycarbonate diol include poly(1,6-exexhexyl) carbonate, poly(3-methyl-1,5-exopentyl) carbonate, and the like, and the polyolefin diol may be polybutene. Alcohol, hydrogenated polytetramethylene glycol, hydrogenated polyisoprene diol. The number average molecular weight of the compound having 1 or 2 in the same molecule is 300 to 10,000, preferably 500 to 6,000, more preferably 1,000 to 4,000. A compound having active hydrogen and a tertiary amino group in the same molecule, which is used as a dispersing agent constituting a specific black pigment suitable for the present invention, particularly a specific black pigment (A) having no surface coating layer, is used. The active hydrogen, that is, the hydrogen atom directly bonded to the oxygen atom, the nitrogen atom or the sulfur atom, may be a hydrogen atom in a functional group such as a hydroxyl group, an amine group or a thiol group, and a 1-based amine group in the amine group. Hydrogen atoms are particularly good. The tertiary amine group is not particularly limited. Further, the tertiary metal group may be an amine group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically an imidazole ring or a diazole ring. Such a compound having an active hydrogen or a tertiary amino group in the same molecule may, for example, be N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propane. Amine, hydrazine, hydrazine-dipropyl-1,3-propanediamine, hydrazine, hydrazine-dibutyl-1,3-propanediamine, hydrazine, hydrazine-dimethylethylenediamine, hydrazine, hydrazine-bis Ethylethylenediamine, hydrazine, hydrazine-dipropylethylenediamine, hydrazine, hydrazine-dibutylethylenediamine, hydrazine, hydrazine-dimethyl-1,4. butyldiamine, hydrazine, hydrazine-diethyl Base-1,4-butanediamine, hydrazine, hydrazine-dipropyl-1,4-butanediamine, hydrazine, hydrazine-dibutyl-1,4-butanediamine, and the like. Further, examples of the compound of the tertiary amine group containing a fluorene hetero ring include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an anthracene ring, an indazole ring, an indazole ring, and -32-200815918. a N-hetero 5-membered ring such as a benzimidazole ring, a benzotriazole ring, a benzoxazole ring, a benzothiazole ring, a benzothiadiazole ring, a pyridine ring, a ruthenium ring, a pyrimidine ring, a triple well ring, An N-containing heterocyclic 6-membered ring such as a quinoline ring, an acridine ring or an isoquinoline ring. Preferred such N-containing heterocycles are imidazole rings or triazole rings. Specific examples of the above-mentioned compound having an imidazole ring and an NH 2 group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, and 1-(2-aminoethyl). Imidazole and the like. Further, when a compound having a triazole ring and an NH2 group is specifically exemplified, for example, 3-amino-1,2-tetrazole or 5-(2-amino-5-chlorophenyl'yl)-3 -phenyl-1H-1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H- 1,3,4-triazole, 5-amino-1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1Η-2,4-triazole, etc. . Among them, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, 3-amine The base-1,2,4-triazole is preferred. A preferred blending ratio of the raw material of the dispersion resin used for dispersing a specific black pigment is a number average molecular weight of one or two hydroxyl groups in the same molecule relative to 1 part by weight of the polyisocyanate compound (j 3 00~ 1〇, the hydrazine compound is 10 to 200 parts by weight, preferably 20 to 190 parts by weight, more preferably 30 to 180 parts by weight, and has active hydrogen and a tertiary amine group in the same molecule. The compound is preferably 0.2 to 25 parts by weight, preferably 0. 3 to 24 parts by weight. The weight average molecular weight of the dispersion resin is measured by GPC, and the conversion of polyethylene is from 1,00 to 200,000, preferably from 2,000 to 1,00,000. The range of 3,000 to 50,000 is more preferable. When the molecular weight is less than 1,000, the dispersibility and dispersion stability are deteriorated, and when it is more than 200,000, the solubility is lowered, the dispersibility is deteriorated, and gelation is likely to occur. The control of the reaction becomes difficult. -33- 200815918 The production of a polymer dispersant for dispersing a specific black pigment can be carried out in accordance with a well-known method for producing a polyurethane. The solvent used in the production can usually be acetone or methyl ethyl ketone. Methyl Ketones such as ketone, cyclopentanone, cyclohexanone, isophorone, ethyl acetate, butyl acetate, celecoxib acetate, etc., hydrocarbons such as benzene, toluene, xylene, hexane, diacetone Alcohol, isopropanol, second butanol, third butanol and other alcohols, chlorides such as dichloromethane and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-A An aprotic polar solvent such as propylpyrrolidone or dimethyl sulfoxide. The catalyst used in the production may be a usual urethane-based reaction catalyst, and examples thereof include dibutyltin dilaurate and dilauric acid. A tin-based system such as dioctyltin, dibutyltin dioctoate or stannous octoate; an iron-based compound such as iron acetylate pyruvate or iron chloride; a tertiary amine such as triethylamine or triethylenediamine; The introduction amount of the active hydrogen and the compound of the tertiary amino group, and the amine valence of the dispersion resin after the reaction is preferably controlled in the range of 1 to 1 〇〇 mg KOH / gram, and is in the range of 5 to 95 mg KOH / gram. More preferably, when the amine price is below the above range, the dispersibility is likely to decrease, and / / is greater than the above range In the above reaction, when an isocyanate group remains in the dispersion resin, and further reacts with an alcohol or an amine compound to prevent the isocyanate group from remaining, the stability of the dispersion resin can be improved. It is preferred that the dispersing resin and the pigment are subjected to dispersion treatment before being formulated in the photoresist. Specifically, for example, the pigment and the dispersing resin and the solvent are added to the binder resin as a case, and a ball mill or a sanding machine is used. The machine, the bead mill, the three-roller, the paint vibrator, the ultrasonic wave, the bubble homogenizer, etc., are dispersed and processed. These methods may also be combined in two or more types. -34- 200815918 The preferred pigment obtained by dispersion treatment The particle size is in the range of 0·00 5 to 0·7 μm, preferably 0.01 to 0.5 μm. Further, the particle diameter of the carbon black used as the specific black pigment or its raw material in the present invention can be measured by a laser Doppler type particle size analyzer. When the particle diameter is larger than the upper limit of the above range, development, resolution, and stability are deteriorated. Further, in order to be at least the lower limit, it is necessary to refine the pigment particles to primary particles or primary particles of carbon black, and the production of such pigment particles is extremely difficult. The content of the other coloring pigment of the photocurable coloring composition of the present invention of the present invention is preferably in the range of 〇 to 50% by mass based on the content of the specific black pigment. The total content of the specific black pigment and the other coloring pigment is preferably 30% by mass or more and 90% by mass or less, and preferably 40% by mass or more and 85% by mass or less, based on the total solid content of the curable composition. It is more preferably 50% by mass or more and 80% by mass or less. &lt;(3) Compound having an ethylenically unsaturated group capable of addition polymerization&gt; A compound having an ethylenically unsaturated group capable of addition polymerization (hereinafter, simply referred to as a polymerizable compound) used in the present invention has The addition polymerizable compound of at least one ethylenically unsaturated double bond can be selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Such a group of compounds is widely known in the industrial field, and the present invention can be used without particular limitation. These are, for example, monomers, prepolymers, i.e., dimers, trimers, and oligomers, or mixtures thereof, and copolymers thereof. Examples of the monomer and the copolymer thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, guanamines, and the like. It is preferred to use an ester of an unsaturated carboxylic acid and an aliphatic polyol compound, an unsaturated carboxylic acid and a guanamine of the aliphatic-35-200815918 aliphatic polyamine compound. Further, an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amine group or a thiol group, or an addition reaction of a guanamine with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional group A dehydration condensation reaction product of a functional carboxylic acid or the like can also be suitably used. Further, an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanate group or an epoxy group or an addition reaction of a guanamine with a monofunctional or polyfunctional alcohol, an amine or a thiol, and having a halogen Substituted reactants of unsaturated carboxylic acid esters or decylamines such as a base or a p-toluenesulfonyl group and a monofunctional or polyfunctional alcohol, an amine or a thiol are also suitable. Further, as another example, a group of compounds obtained by substituting an unsaturated carboxylic acid, styrene, vinyl ether or the like in place of the above unsaturated carboxylic acid may be used. Among the monomers of the ester of the aliphatic polyol compound and the unsaturated carboxylic acid, specific examples of the acrylate include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and butyl Diol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, tricarboxymethylpropane tris(propylene methoxypropyl) ether, trimethylolethane Triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, neopentyl alcohol diacrylate, neopentyl alcohol triacrylate, neopentyl Alcohol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate , tris(propylene methoxyethyl) trimeric isocyanate, polyester acrylate oligomer, trimeric isocyanate EO modified triacrylate, and the like. Specific examples of the methacrylate are butanediol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and tri-36-200815918 methyl propane trimethacrylate. Ester, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, neopentyl glycol Methacrylic acid, neopentyl alcohol trimethacrylate, neopentyl alcohol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol three Methacrylate, sorbitol tetramethacrylate, bis[p-(3-methylpropenyloxy-2-hydroxypropoxy)phenyl]dimethylmethane, bis[p-(methacryl oxime) Oxyethoxy)phenyl]dimethylmethane and the like. Specific examples of f-iconic acid esters include ethylene glycol dicone ester, propylene glycol diconconate, 1,3-butanediol diconconate, 14-butanediol diconcanate, Butylene glycol diconconate, pentaerythritol diconconate, sorbitol diconcanate, etc. Specific examples of the crotonate include ethylene glycol dicrotonate, butanediol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetracrotonate. Specific examples of the isocrotonate include ethylene glycol diisocrotonate, pentaerythritol diisocrotonic acid, and sorbitol tetraisocrotonic acid. Specific examples of the maleic acid ester are ethylene glycol dimaleate, triethylene glycol I dimaleate, pentaerythritol dimaleate, sorbitol tetras Butylene diester and the like. Examples of the other esters include, for example, the aliphatic alcohol esters described in JP-A-51-47 3 3 4 and JP-A-57-1 962 31, or JP-A-5-9-5240, JP-A-59-524 It is also suitable to use the amine group-containing substance described in the Unexamined-Patent No. 1 - 1 6 5 6 1 3, which is described in the Japanese Patent Publication No. Hei. Further, the aforementioned ester monomers can also be used in the form of a mixture. Further, specific examples of the monomer of the 'aliphatic polyamine compound and the decylamine of the unsaturated carboxylic acid-37-200815918 include methylenebis propylene amide, methylene bis methacrylamide, and 1,6 - hexamethylene bis decylamine, 1,6-hexamethylene bis methacrylamide, di-ethyltriamine propylene amide, phenyl dimethyl propylene amide, benzyl dimethyl dimethyl C is suspected of indoleamine. Examples of other preferred amine-derived monomers include those of the cyclohexylene structure described in Japanese Patent Publication No. 5 4 - 2 1 2 2 6 . Further, an urethane-based addition polymerizable compound prepared by an addition reaction of an isocyanate and a hydroxyl group is also suitable. Specific examples of the polyisocyanate compound having two or more isocyanate groups per molecule as described in JP-A-48-41708, and the inclusion of the following formula (A) are included. A vinyl urethane compound having two or more polymerizable vinyl groups in one molecule, which is a vinyl group of a hydroxyl group. CH2 = C(R4)COOCH2CH(R5)OH (A) (wherein, in the formula (A), R4 and R5 are Η or CH3) Further, JP-A-Open 5:1-3 7 1 9 3 Fair 2-3 2293, special fair 2- 1 676 No. 5, the urethane urethanes, or special public Zhao 5 8-49 8 60, special public Zhao 5 6- 1 7654, special public Zhao 62-3 An oxirane-based urethane compound having an ethylene oxide type as described in JP-A No. Hei. In addition, it is also possible to have an amine group in the molecule as described in the publication of JP-A-63-207 7 5 5 3, JP-A-63-26〇9〇9, and JP-A-1-15-1523. Addition-polymerizable compounds of structure or thioether structure, which can be photo-sensitized @® ® 2 % ® &lt;匕;丨生1 @,组$物1 ° Other examples include, for example, special opening 4 8 - 6 4 1 8 3, special public Zhao 4 9_43 191, special public Zhao 5 2-3 0490 A polyfunctional acrylate or methacrylate such as a polyester acrylate described in each of the publications, or an epoxy acrylate obtained by reacting an epoxy resin with (meth)acrylic acid. In addition, it is also possible to use -38-200815918 to identify the specific unsaturated compound described in JP-A-46-43 946, special fair 1 - 403 3 7 and special fair 1 - 403 3 6 or special opening 2 - 2 A vinyl sulfonic acid compound as described in No. 5, 4, 3, and the like. Further, in some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is also suitable. Further, as the photocurable monomer and oligomer, the Japanese Adhesive Society Publication No. 20, No. 7, and No. 3 0 0 to 308 (196) can also be used. The details of the methods of use, such as the structure, the use alone, or the amount of the addition polymerizable compound, can be arbitrarily set in accordance with the final performance design of the curable composition. For example, it can be selected from the following points of view. In terms of sensitivity, a structure having a large content of unsaturated groups per molecule is preferred, and a majority of the cases are preferably two or more. Further, in order to increase the strength of the cured film, it is preferable to use a trifunctional or higher functional group, and to use a different functional number or a different polymerizable group (for example, an acrylate, a methacrylate, a vinyl compound, or a vinyl ether compound). ), to adjust both sensitivity and strength, is also effective. Moreover, the compatibility and dispersibility of other components contained in the curable composition (for example, photopolymerization initiator, colorant (pigment, dye), etc., binder polymer, etc.), addition polymerization compound The selection and the use method are also important factors. For example, when a low-purity compound is used or two or more types are used, compatibility can be improved. Further, in order to improve adhesion to a substrate or the like, a specific structure can be selected. The photocurable coloring composition of the present invention contains the above-mentioned (1) specific initiator, (2) a specific black pigment, and (3) a compound having an ethylenically unsaturated group capable of addition polymerization, and as needed The sensitizer used may also contain any of the ingredients detailed below as needed in the same period of -39-200815918. Hereinafter, any component that can be used in the present invention will be described. &lt;Adhesive Polymer&gt; In the photocurable color composition of the present invention, a binder polymer may be used as needed for the purpose of film properties formed by the cylinder. The binder is preferably a linear organic polymer. Such a "linear organic polymer" can be arbitrarily used in a well-known manner. In order to enable water imaging or weak alkaline water development, it is preferred to select a linear organic polymer having soluble f or swellability in water or weakly alkaline water. The linear organic polymer is not only used as an i film forming agent, but can be selected for use as a water, weak alkaline water or organic solvent developing agent. For example, when water-soluble organic polymers are used, water can be imaged. Examples of such a linear organic polymer include a radical polymer having a carboxylic acid group in a side chain (for example, JP-A-59-446-15, JP-A-5-4-3, No. 27, No. 1 2 5 7 7 , Special Gong Zhao 5 4-2 5 9 5 7 , Special Opening 54-92723, Special Opening 5 9 - 5 3 8 3 6 , Special Opening 5 9-7 1 048 Further, even if the monomer having a carboxyl group is used alone or in a copolymerized state, an acid anhydride unit having an acid anhydride monomer alone or copolymerized is hydrolyzed, half-esterified or fully esterified. Resin, an epoxy acrylate modified with an unsaturated monocarboxylic acid and an acid to modify the epoxy resin, etc.). Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene; and the monomer having an acid anhydride may be exemplified by Diacid anhydride, etc. Further, there is likewise an acidic cellulose derivative having a carboxylic acid group in a side chain. Further, it is useful to add a cyclic acid anhydride to a polymer having a hydroxyl group. -40- 200815918 When a soluble resin is used as the copolymer, the copolymerized compound may be a monomer other than the monomers exemplified above. Examples of the other monomer include the following compounds (1) to (13). (1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, A Acrylates and methacrylates having an aliphatic hydroxyl group such as 3-hydroxypropyl acrylate or 4-hydroxybutyl methacrylate. ^ (2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid -2-chloroethyl ester, glycidyl acrylate, methyl 3,4-epoxycyclohexyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2 - An alkyl acrylate such as ethyl allyloxyacrylate or propargyl acrylate. (3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, methacrylic acid 2-ethylhexyl ester, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate Ester, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-H enyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, acetyl acrylate An alkyl methacrylate such as propyl ester. (4) Acrylamide, methacrylamide, N-methylol acrylamide, N-ethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, • 41- 200815918 N-hydroxyethyl acrylamide, N-phenyl acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, vinyl acrylamide, vinyl Acrylamide such as acrylamide, N,N-diallyl acrylamide, N,N-diallyl methacrylamide, allyl acrylamide, allyl methacrylamide Or methacrylamide. (5) Ethyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether. f (6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate. (7) Styrene such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene or p-ethoxylated styrene. (8) Vinyl ketone such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone or phenyl vinyl ketone. (9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene. (10) Ν-vinylpyrrolidone, acrylonitrile, methacrylonitrile, and the like. f (11) maleimide, N-propylene decyl acrylamide, N-ethyl decyl propyl amide, N-propyl decyl methyl propyl amide, N- (p-chlorophenyl) Sulfhydryl) unsaturated quinone imine such as methyl propylamine. (12) A methacrylic monomer obtained by bonding a hetero atom at the α-position. For example, the compounds described in the specification of Japanese Patent Application No. 20 01- 1 1 5 5 9 5 and the specification of Japanese Patent Application No. 00 1 -1 1 5 5 9 8 may be mentioned. Among these, the (meth)acrylic resin having an allyl group, a vinyl ester group, and a carboxyl group in the side chain is described in JP-A-2000-187A, and JP-A-2002-6269. Alkali-soluble resin having a double bond in a side chain-42 - 200815918 or a wide-chain alkali-soluble resin having a guanamine group in the side chain, which is described in JP-A-2001 - 2 4 2 6 1 2 The balance between degree and imaging is excellent, but it is better. In addition, special fair 7-12004, special fair 7-120041, special fair 7-120042, special fair 8-12424, special open 63-287944, special open 63-287947, special Kaiping 1 The acid group-containing urethane-based adhesive polymer described in Japanese Patent Application Laid-Open No. Hei 10-116232, or the like, and the acid group and the double bond in the side chain described in JP-A-2002- 1 079 186 The amine-based (formate-based binder polymer is advantageous in terms of abrasion resistance and low-exposure properties because of its excellent strength. Also, in European Patent 9 9 3 916, European Patent 1 2 The acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in the above-mentioned 0 0 0 0 0, 2K 0 1 - 3 1 8 4 6 3 is excellent in the balance between film strength and development. Further, polyvinylpyrrolidone or polyethylene oxide is useful as another water-soluble linear organic polymer. Further, in order to improve the strength of the hardened film, alcohol-soluble nylon or 2,2-bis-(4-hydroxyphenyl)-propane, epichlorohydrin, etc. are also useful. The weight average molecular weight of the binder polymer which can be used in the present invention It is preferably 5,00 or more, more preferably in the range of 10,000 to 300,000, and the number average molecular weight is preferably 1 or more, more preferably 2,000 to 250,000. Polydispersity (weight) The average molecular weight/number average molecular weight is preferably 1 or more, more preferably 1 to 1 to 10. The binder polymers may be random polymers, block polymers, and graft polymers. Any of the binder polymers which can be used in the present invention can be synthesized by a conventionally known method. Examples of the solvent used in the synthesis include tetrahydrofuran, dichloroethane, cyclohexanone, and the like. Methyl ethyl ketone, acetone, methanol, 'ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethyl 2-methoxyacetate, diethylene glycol dimethyl ether, 1-methoxy 2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, toluene, ethyl acetate, lactic acid Methyl ester, ethyl lactate, dimethyl hydrazine, water, etc. These solvents may be used alone or in combination of two or more. f. Synthesis The present invention enables The radical polymerization initiator to be used for the binder polymer may, for example, be a well-known compound such as an azo initiator or a peroxide initiator. When using such a binder polymer, the total amount of the composition with respect to the curable composition The mass of the solid component is preferably from 0 to 50% by mass, more preferably from 〇 to 30% by mass. &lt;Co-sensitizer&gt; The photocurable coloring composition of the present invention preferably contains a co-sensitizer. The co-sensitizer of the present invention has the ability to further enhance the sensitizing colorant or initiator pair

V The sensitivity of the active radiation, or the inhibition of the polymerization of the polymerizable compound by oxygen. Examples of such a co-sensitizer include amines, for example, MR. Sander, and the Journal of Polymer Society, Vol. 10, p. 3173 (1972), and Tegong Sho 44-20189. Bulletin of the Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei 52- 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Japanese Laid-Open Patent Publication No. SHO-62-A No. Hei. No. Hei. No. Hei. No. Hei. Ethyl p-dimethylaminobenzoate, p-methylaniline, p-methylthiodimethylaniline, and the like. Further examples of the co-sensitizers include those described in the publications of the Japanese Patent Publication No. Sho-35-702, and the Japanese Patent Publication No. Hei 5-5-500 The thiol compound, the disulfide compound of JP-A-56, and the like, specifically, 2-hydrothiazol, 2-hydrothiobenzoxazole, 2-hydrothiobenzimidazole, 2-hydrogen sulfide f', quinazoline, /3-hydrothionaphthalene, and the like. Further, as another example of the co-sensitizer, a metal compound (for example, tributyltin acetate, etc.), or a metal compound (for example, tributyltin acetate) of the Japanese Patent Publication No. 4-8-429 6 5, The hydrogen donor described in the publication No. 5-3 0 8 727, for example, a sulfur compound (for example, trimeric methyl mercapaldehyde or the like). From the viewpoint of improving the balance between the growth rate of the polymerization and the chain transfer, the content of the total sensitizer is preferably in the range of 0.1 to 30% by mass, based on the mass of the total solid content of the curable composition, i / %. The range is preferably in the range of 0 · 5 to 2 0% by mass. &lt;Polymerization Inhibitor&gt; The photocurable coloring composition of the present invention has an undesired thermal polymerization in which a polymerizable ethylenic compound is produced during the production or storage of a hard substance, and a small amount of anti-static is added. good. The heat-resistant polymerization agent which can be used in the present invention may, for example, be hydroquinone, phenol, di-tert-butyl-p-cresol, pyrogallol or t-butyl; in particular, mercapto dimethyl, for example, special, special-opening- No. 75643 benzobenzoyl 4(3H)- (for example, the amount of hardening speed described in Organic No. 34414, such a 1 to 25 mass composition saturated double bond thermal polymerization agent p-methoxy catechol Benzene-45- 200815918 醌, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-mercapto-6-third Butylphenol), N-nitrosophenylhydroxylamine, first sulfonium salt, etc. The amount of the heat-resistant polymerization agent added is preferably from about 0.01% by mass to about 5% by mass based on the mass of the total composition. In order to prevent polymerization inhibition by oxygen, it is also possible to add a higher fatty acid derivative such as rosin or rosin as necessary, or to be deposited on the surface of the photosensitive layer by a drying step after coating. Higher fatty acid derivatives The amount of addition is preferably from about 0.5% by mass to about 10% by mass of the total composition. &lt;Adhesion Enhancer&gt; The adhesion of the surface (substrate) is preferably added to the photocurable coloring composition of the present invention. The adhesion improving agent may, for example, be a decane coupling agent or a titanium coupling agent. Examples of the decane coupling agent include r. -(2-Aminoethyl)aminopropyltrimethoxydecane, 7-(2-aminoethyl)aminopropyldimethoxydecane, /3 -(3,4-ethoxyl ring Hexyl)ethyltrimethoxydecane, r-aminopropyltrimethyl/oxydecane, r-aminopropyltriethoxydecane, r-methacryloxypropyltrimethoxydecane, r- Methyl propylene methoxy propyl triethoxy decane, r propylene methoxy propyl trimethoxy decane, r propylene methoxy propyl triethoxy decane, r - isocyanate propyl trimethoxy decane , r-isocyanate propyl triethoxy decane, Ν-β-(Ν-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxydecane-hydrochloride, r-glycidoxy Propyltrimethoxydecane, r-glycidoxypropyltriethoxydecane, amine brothel, T-aminothiopropyldimethoxy sand, T-chlorothiopropyl Ethoxy decane, methyl three Oxydecane, methyltriethoxydecane, vinyl-46- 200815918 triethoxydecane, 7-chloropropyltrimethoxydecane, hexamethyldiazepine, 7-anilinopropyltrimethyl Oxygen sand yard, vinyl trimethoxy sand yard, vinyl triethoxy decane, vinyl ginseng (/3-methoxyethoxy) decane, octadecyl dimethyl chloride [3-( Trimethoxydecyl)propyl]ammonium, r-chloropropylmethyldimethoxydecane, r-hydrothiopropylmethyldimethoxydecane, methyltrichlorodecane, dimethyldichloro Decane, trimethylchlorodecane, 2-(3,4-ethoxycyclohexyl)ethyltrimethoxydecane, bisallyltrimethoxydecane, tetraethoxydecane, bis(trimethoxydecanealkyl) Hexane, phenyltrimethyl, oxoxane, hydrazine-(3·propenyloxy-2-hydroxypropyl)-3-aminopropyltriethyl\:oxydecane, N-(3-methyl Propyloxy-2-hydroxypropyl)-3-aminopropyltriethoxydecane, (methacryloxymethyl)methyldiethoxydecane, (acryloxymethyl) Methyl dimethoxy decane, and the like. Among them, r-methacryloxypropyltrimethoxydecane, r-methylpropenyloxypropyltriethoxydecane, r-propyleneoxypropyltrimethoxydecane, r-acrylonitrile Oxypropyl triethoxy decane, thiopropyl propyl trimethoxy sylvestre, 7-aminopropyl triethoxy sane, phenyl trimethyl oxy decane, preferably r-methyl Acryloxypropyltrimethoxy sands are preferred. The addition amount of the adhesion extracting agent is preferably from 0.5 to 30% by mass based on the total solid content of the curable composition, more preferably from 0.7 to 20% by weight. &lt;Other Additives&gt; In addition, in order to improve the physical properties of the cured film, an inorganic pigment or a plasticizer may be added to the photocurable color composition of the present invention, and the ink on the surface of the photosensitive layer can be improved. A well-known additive such as a lipid stabilizer. Plasticizers are, for example, dioctyl phthalate, decyl dodecyl ester, triethylene glycol dioctyl-47-200815918 acid ester, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate adipate In the case of using a binder, the total mass of the compound having an ethylenically unsaturated double bond and the binder is 10% by mass or less in the case of using a dibutyl acrylate or a triethyl hydrazine glycerin. &lt;Diluent&gt; When a color filter is produced, when the photocurable coloring group of the present invention is applied onto a support, it can be used by being dissolved in various organic solvents. f. The organic solvent used herein is acetone, methyl ethyl ketone, alkane, ethyl acetate, dichloroethane, tetrahydrofuran, toluene, ethylene glycol ether, ethylene glycol monoethyl ether, ethylene Alcohol dimethyl ether, propylene glycol monoether, propylene glycol monoethyl ether, acetonitrile acetone, cyclohexane, diacetone ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Isopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanoloxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether glycol dimethyl Ether, diethylene glycol diethyl ether, propylene glycol monodecyl ether ethyl g, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, hydrazine, hydrazide, dimethylamine, dimethyl Aarene, r-butyrolactone, methyl lactate, lactic acid, and the like. These solvents may be used singly or in combination. The coating liquid obtained by dissolving the photohardenable composition of the present invention in an organic solvent preferably has a solid concentration of 2 to 60% by mass. [Color Filter] Next, the color filter of the present invention will be described. The color filter of the present invention is formed by forming an ester on the surface of a glass support, a cyclohexamethylene alcohol having an additivity, a diol, a methyl ester, and a dimethyl ester. The photocurable colored layer composed of -48-200815918 photocurable coloring composition is subjected to pattern exposure by means of a mask or the like, and the exposed photocurable coloring composition is developed to form a surface of the glass support. Obtained by coloring the pattern. The photocurable coloring layer can be formed by applying a photocurable coloring composition to a glass support and drying it, or by laminating a sheet made of a photocurable coloring composition in advance by lamination. Formed on a glass support. &lt;Glass Support&gt; ^ The support which can be used in the present invention is, for example, soda lime glass, Pyrex (registered trademark) glass, quartz glass, etc. used for liquid crystal display elements, and the like. A transparent conductive film is adhered to a material, or a photoelectric conversion element substrate such as an image sensor or the like, or a germanium substrate or a complementary metal oxide film semiconductor (CMOS). These substrates also have a black matrix to isolate each pixel. Further, on these supports, an undercoat layer may be provided as necessary to improve adhesion to the upper layer, prevent diffusion of substances, and/or flatten the surface of the substrate. Ky: The method of applying the curable composition of the present invention to a support can be carried out by various coating methods such as slit coating, inkjet coating, spin coating, cast coating, roll coating, and screen printing. Usually, the curable composition coated on the support is dried at 70 to 11 ° C for about 2 to 4 minutes to form a layer composed of the photocurable coloring composition. The thickness of the coating film after drying of the curable composition is preferably 1 to 1 〇 micron, preferably 0.2 to 5 μm, and more preferably 2 to 3 μm. -49-200815918 The photocurable coloring composition of the present invention can be cured with high sensitivity by exposure, and is excellent in developability of an unexposed portion after exposure, and is displayed on the surface of a glass support to which a photocurable coloring composition is applied. Has high adhesion. The color filter of the present invention is characterized in that it has a colored pattern formed as described above on a glass support. Specifically, the photocurable colored layer composed of the photocurable coloring composition of the present invention is subjected to pattern exposure by passing through a predetermined mask pattern or by scanning exposure. Next, in the developing step, only the coating film which was irradiated with light in the above/exposure step was partially hardened, and the uncured region was visualized using a developing liquid. Thereby, a pattern-like film composed of black pixels can be formed. This patterned film is useful as a black matrix of a color filter. Further, pixels of other hue can be formed by using a usual method as necessary. By the above steps, the color filter of the present invention can be manufactured. The foregoing development steps and uranium engraving steps will be described below. &lt;Exposure Step&gt; In the exposure step, pattern exposure is performed by exposing the photocurable colored layer or the like through a photomask, and only the coating film which has been irradiated with light is partially cured. \ Exposure is preferably performed by irradiating radiation. It is preferable to use ultraviolet rays such as g-rays and i-rays, and it is preferable to use a high-pressure mercury lamp. The exposure amount is preferably 5 mJ/cm 2 to 1 5 00 mJ/cm 2 , more preferably in square centimeter to lOOOmJ/square centimeter, and preferably 10 mJ/cm 2 to 800 cm·cm 2 . &lt;Exposure Step&gt; The alkali exposure process is carried out in the exposure step, so that the portion not irradiated with the exposure step light is dissolved and precipitated in the aqueous alkali solution. Therefore, only the hardened part of the light -50-200815918 remains on the support. The developing solution is preferably an organic alkali developing solution which does not cause damage to the lower layer circuit or the like. The developing temperature is usually 20 ° C to 30 ° C, and the developing time is 20 to 90 seconds. The base used for the developing solution can be, for example, ammonia, ethylamine, diethylamine, dimethylethanolamine or hydroxide. Organic basic compound such as tetramethylammonium, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-dioxabicyclo-[5·4·0]-7-undecene, diluted with pure water The alkaline aqueous solution has a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. Further, when such a developing solution composed of an alkaline aqueous solution is used, a colored pattern formed by washing (r i n s e ) with pure water is usually used after development. Further, in the method of the present invention, after the step of forming the curable composition layer, the exposing step, and the developing step, the hardening step may be included as necessary to heat the formed coloring pattern or / and exposure to harden it. Subsequently, a process consisting of a desired hue can be produced by repeating a series of processes of forming a photocurable colored layer of another hue, an exposing step, and a developing step (and further in accordance with a necessary hardening step) in accordance with the required number of hue. Color filter. In the present invention, a color filter can be produced by using a laminate having a layer composed of a photocurable coloring composition capable of forming an interaction with glass on a glass support. Therefore, the colored pattern formed by the excellent pattern formation exhibits high adhesion to the support substrate. Moreover, in the unexposed portion, the film structure composed of the curable composition has excellent uniformity, and it is not necessary to worry about the formation of agglomerates by the pigment or the photopolymerization initiator, and the penetration of the liquid is suppressed. Sexually, the penetration of the imaging solution is uniform and rapid, and the stomach is formed. Therefore, the pattern can be suitably used as a black matrix which is a solid-state image sensor such as a liquid crystal display or a C CD, and is particularly suitable for a CCD element or CMOS having a high resolution of, for example, more than 1,000,000 pixels. The color filter of the present invention can be disposed as a color filter by being disposed between a light receiving portion constituting each pixel of the CCD and a microlens for collecting light. [Examples] Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited thereto. Further, [%] and [parts] indicate [% by mass] and [parts by mass], respectively, unless otherwise notified in advance. [Example 1] Here, a photo-curable coloring composition a-1 containing a coloring agent (pigment) is prepared, and a color filter for use in a liquid crystal display element is produced by using the curable coloring composition α-1. example. [1. Preparation of photocurable coloring composition α-1] 1-1. Preparation of pigment dispersion liquid (Q1): Black system \ Carbon black MA-220 containing 27 parts by mass of pigment [Mitsubishi Chemical Co., Ltd., specific black Pigment (A)], 8 parts by mass of benzyl methacrylate/methacrylic acid copolymer (copolymerization ratio 70/30 0 molar ratio, weight average molecular weight 3 0000 b 6 5 parts propylene glycol monomethyl ether acetate The mixed liquid is prepared by mixing and dispersing in a bead mill for 2 hours to prepare a pigment dispersion (Q丨). The obtained pigment dispersion (qi) is measured by dynamic light scattering method. In the case of the average particle diameter, it is 100 nm. 1 2 · Preparation of photocurable coloring composition α - i (coating liquid) - 52 - 200815918 &lt; Composition α -1 &gt; • Pigment dispersion (Q1) 600 parts by mass • 190 parts by mass of alkali-soluble resin (benzyl methacrylate/methacrylic acid copolymer, molar ratio: 70/30, Mw: 10000) • dipentaerythritol hexaacrylate [polymerizable compound] 40 parts by mass • Neopentyl alcohol triacrylate 20 parts by mass • Compound 1 (structure described below) [Specific photopolymerization initiator] 80 Co-sensitizer: 30 parts by mass of N-phenyl-2-hydrothiobenzimidazole • Surfactant: (trade name: Tetonic 15〇m, BASF) 1 part by mass • Solvent: propylene glycol monomethyl Ether acetate 1000 parts by mass • r _methacryloxypropyltriethoxy decane 10 parts by mass of compound 1

CCI3 C2H5〇C〇一\C2H5〇C〇一7

Br [2. Production of color filter] 2-1. Formation of curable composition layer The photocurable coloring composition containing the pigment obtained above was used as a photoresist solution, and the following conditions were used. After being applied to a glass substrate of 550 mm x 650 mm, it was allowed to stand for 1 〇 minute in this state, and then vacuum dried and post-baked (Preake) (100 ° C, 80 sec) to form photohardening. Sexually colored layer. (Slit coating condition) Clearance of the opening of the tip of the coating head: 50 μm Coating speed: 1 mm / sec -53 - 200815918

The gap between the substrate and the coating head: 150 μm coating thickness (dry thickness): 2 μm coating temperature: 2 3 ° C 2- 2 exposure, development, then using a 2.5 k W ultra-high pressure mercury lamp, passing the light through the reticle The surface of the curable colored layer was exposed to a pattern, and after exposure, '1% of the organic-based developing liquid (trade name: CD, FUJIFILMARC®) was used. The aqueous solution covers the entire surface of the coating film and is still for 60 seconds. f, 2-3. After the heat treatment is at rest, the pure water is sprayed in a shower form to wash off the developing liquid, and the coating film which has been subjected to the above photo hardening treatment and development processing is heated in an oven of 22 (TC for 1 hour). (post-baking) A coloring pattern (black matrix) was formed on the glass substrate to obtain a color filter (black matrix). [3. Performance evaluation] The photocurable coloring composition a-1 (coating liquid) prepared using the above-mentioned preparation The exposure pattern formation property of the photo-curable coloring f layer of the color filter laminated body formed on the glass substrate, and the adhesion of the coloring pattern of the color filter to the base v # plate was evaluated as follows. As shown in Table 1. 3-1. Pattern Formability of Coating Film (Colored Layer) The photocurable coloring composition a-1 (coating solution) was applied onto a glass substrate to have a filminess of 1 after drying. 0 μm. The spin coating conditions were at 300 rpm, 5 seconds, at 80 rpm, 20 seconds, and the drying conditions were 10 ° C, 8 〇 seconds. Next, using a test reticle with a line width of 20 μm, Exposure of l〇〇m J/cm ^ 2 exposure. Then use 60% CD-2 000 (FU) JIFILM ELECTRONICS MATERIALS, Inc. - 54-200815918) The developing solution 'is developed at 25 ° C until the residual film in the unexposed portion disappears completely (the disappearance of the residual film is confirmed by the dark field of the optical microscope to confirm the residual state of the pigment component) Then, after rinsing with running water for 20 seconds, pattern formation was carried out by spray drying. The film thickness after development in the region irradiated with light in the exposure step was measured, and the film before exposure was evaluated according to the following criteria. Film reduction of 1% by weight. The lower the film reduction, the higher the exposure sensitivity, and the shorter the development time in the state where no residual film is present (excellent development), both of which have a pattern display property. Good. (\ 〇: 95% or more △: less than 9 5~8 5% or more / X: less than 8 5% 3 _ 2 · Pattern formation of coated film (colored layer) 2 (thin line reproducibility) In the above 3 - For the exposure of 1, a test mask having a line width of 5 μm to 20 μm was used, and exposure was performed at an exposure amount of 80 mJ/cm 2 . Next, a 60% CD-2000 (FUJIFILM ELECTRONICS MATERIALS) developing solution was used, at 25 °C imaging until not When the residual film of the exposed portion completely disappeared (the disappearance of the residual film was confirmed by the dark field of the optical microscope to confirm the residual state of the pigment component), the film was rinsed with running water for 20 seconds, and then spray-dried to complete pattern formation. The film thickness before the exposure was 100%, and it was confirmed that the film thickness after the development of the light in the exposure step can be maintained at a line width of 95% or more as an evaluation index. The film reduction amount in the development is small. In the case of the image of the line width of the line, the fine line reproducibility is excellent. 〇: 1 〇 micron or less △ : 1 0 to 1 5 μm X : 15 to 20 μm - 55 - 200815918 3 - 3 . Substrate adhesion Confirmation of post-baking by the usual confirmation method of optical microscopy and SEM photographic observation The colored pattern of the subsequent color filter. The detailed evaluation method is as follows. &lt;Substrate Adhesiveness&gt; The evaluation of the substrate adhesion type was observed whether the pattern was defective or whether a gap with the substrate occurred. These evaluation items are evaluated based on the following criteria. When 〇 and △, there is no problem in practical use. Fs 〇: No pattern defect or gap with the substrate was observed at all Δ: No pattern was observed to be defective, but a portion having a gap was observed between the substrate and the substrate, but there was no problem in practical use. X: A pattern was observed to be defective and practically problematic. [Examples 2 to 12] In Example 1, except for the specific initiator (compound 1) and the pigment dispersion (q 1) used in the α -1 used for preparing the photocurable coloring composition a -1 At least one of the pigments was prepared in the same manner as in Example 1 except that the materials shown in the following Table 1 were used, and the photocurable coloring composition α - 2 to α -1 2 was prepared. Using these and the like, a color filter having a colored pattern was obtained in the same manner as in Example 1. Further, evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1. Further, the structures of the specific initiators (Compound 2 to Compound 4) used herein are as follows. -56- 200815918 Compound 2

Compound 3 Compound 4 / Table 1 The black pigment (for use in the present invention, comparative use) is as follows. [Specific black pigment (A): non-covered type] Specific surface area (m2 / g) pH CB-1 (trade name: ASAHI THERMAL, manufactured by ASAHI CARBON) 24 8.8 CB-2 (trade name: MA-220, Mitsubishi Chemical Corporation) 31 3.0 CB-3 (trade name: Special Black 350, manufactured by DEGUSSA) 65 3.5 CB-4 (trade name: MA-11, manufactured by Mitsubishi Chemical Corporation) 104 3.5 -57- 200815918 [Comparative black Pigment: Non-coated type] Specific surface area (m^m/g) pH CBX-1 (The above-mentioned CB_1 is immersed in 1N ammonia water for 24 hours, filtered and dried by pressure) 24 10.0 CX-2 ( The above-mentioned CB-20 was immersed in 1N hydrochloric acid water for 24 hours, and then filtered and dried under pressure. 31 1.8 CX-3 (The above CB-4 was used together with pure water and beads having a particle diameter of 1 mm. After 10 hours of treatment with a bead mill, it is dried by pressure filtration and dried.) 300 3.5 [Specific black pigment (B): coated ceria type] CB-5: 10 g of carbon black is added to the flask (Mitsubishi Chemical (Stock), MA1 00), 200 ml of pure water, and 1 gram of concentrated hydrochloric acid, and then stirred to prepare an aqueous dispersion. To the aqueous dispersion, 1.0 g of tetrahydrofuran was added, and the mixture was heated at 60 ° C for 3 hours. After the reaction, the mixture was filtered under pressure and dried to obtain a carbon dioxide-coated carbon black CB-5. [Specific black pigment (C): coated resin type] CB_6 : 100 parts by mass of carbon black (C.; [. Pigment Black 7), an epoxy resin (12 parts by mass) of an emulsion and 2-ethyl-4- Methylimidazole (2 parts by mass) was formed to form a coating layer of an epoxy resin to obtain a resin-coated carbon black CB-6. [Comparative Example 1 to 1 2] In Example 1, except for the specific initiator (the compound hydrazine and the pigment dispersion liquid (() 1)) in the α-1 used for the photocurable coloring composition a-1 At least one of the black pigments was prepared in the same manner as in Example 1 except that the comparative initiators shown in Table 1 below were used instead of the comparative black pigments, and the photocurable coloring composition-1 to /3 was prepared. 1 2, using the same procedure as in Example 1 to obtain a color-58-200815918 filter having a colored pattern, and evaluation was carried out in the same manner as in Example 1, and the results are shown in Table 1 as follows. The structure of the comparative specific initiator (Comparative Compound Comparative Compound 4) used in the comparative example is as follows. Comparative Compound 1

Comparative compound 2

Comparative compound

Comparative compound 4

-59- 200815918 [Table i]

Evaluation of Photopolymerization Initiator Pigment Dispersion - Black Pigment Pattern Forming Substrate Adhesion Type Sensitivity &amp; Development Thin Line Reproducibility Example 1 α-1 Compound 1 CB-1 〇〇〇 Example 2 α-2 Compound 1 CB-2 〇〇〇 Example 3 α-3 Compound 1 CB-3 〇〇〇 Example 4 α-4 Compound 1 CB-4 〇〇〇 Example 5 α-5 Compound 1 CB-5 〇〇〇 Example 6 α-6 Compound 1 CB-6 〇〇〇 Example 7 a -7 Compound 2 CB-2 〇〇〇 Example 8 α-8 Compound 3 CB-2 〇〇〇 Example 9 α-9 Compound 4 CB-2 〇〇〇 Example 1 〇 α-10 Compound 2 CB-5 〇〇〇 Example 11 (2-11 Compound 3 CB-6 〇〇〇 Example 12 αΛ2 Compound 4 CB- 6 〇〇〇Έ®Γι Compound 1 CBXA XXX Comparative Example 2 β-2 Compound 1 CBX-2 Δ Δ X Comparative Example 3 /3-3 Compound 1 CBX-3 Δ Δ X Comparative Example 4 /5-4 Compound 2 CBX -1 XXX Comparative Example 5 β-5 Comparative Compound 1 CB-1 X Δ X Comparative Example 6 β·6 Comparative Compound 2 CB-4 XXX Comparative Example 7 / 3-7 Comparative Compound 3 CB-6 Δ XX Comparative Example 8 0-8 Comparative Compound 4 CB-5 XXX Comparative Example 9 /3-5 Comparative Compound 1 CBX-1 XXX Comparative Example 1〇/3-6 Comparative Compound 2 CBX-2 XXX Comparative Example 11 β-Ί Comparative Compound 3 CBX-3 XXX Comparative Example 12 /3-8 Comparative Compound 4 CBX-1 XXX From the results of Table 1, it was found that the use of a specific initiator and a specific black pigment was observed. The color filters of Examples 1 to 12 produced by the photocurable coloring composition are excellent in pattern formability, particularly fine line reproducibility, and have good adhesion between the obtained color pattern and the substrate, and the present invention is used. The light-curing composition of 60-200815918 can obtain a color filter excellent in exposure sensitivity, high in developability, high-difference pattern formation, and excellent in adhesion between the formed color pattern and the substrate. On the one hand, Comparative Examples 1 to 4 using carbon black outside the scope of the present invention as a black pigment, or Comparative Examples 5 to 8 using a comparative compound outside the scope of the present invention as a photopolymerization initiator, and an initiator and a black pigment Both sides are In any of Comparative Examples 9 to 2, which are outside the range of the invention, when compared with the examples, the pattern formability, the fine line reproducibility, and the adhesion to the substrate were inferior. As described above, it has been found that the excellent effects of the present invention can be obtained by using the photocurable coloring composition of the present invention containing both a specific initiator and a specific black pigment. [Simple diagram] &gt;fnr pick 0

I -61-

Claims (1)

200815918 X. Patent Application Range: 1 · A photocurable coloring composition characterized by containing a photopolymerization initiator, a black pigment, and a compound having an ethylenically unsaturated group capable of addition polymerization, the photopolymerization initiator The black pigment contains carbon black selected from (A) a specific surface area of 110 m ^ 2 /g or less and a pH of 2 to 9; f, (B) coated with dioxide At least one of the group consisting of ruthenium carbon black; and (C) resin-coated carbon black; general formula (I) In the formula (1), R^R2 each independently represents a hydrogen atom, an alkyl group, an aryl group, a group represented by the following formula (Ι-A) or (IB); and R3 represents a hydrogen atom, a halogen atom, or a compound. a group or an alkoxy group; W means a halogen atom; X and Y each independently represent a chlorine atom or a bromine atom; and m and η each independently represent 〇, 1 or 2, and the formula (Ι-Α) (Ι-Β) D6 In the formula, R5, R6 and R7 each independently represent a hospital group or an aryl group. 2. The photocurable coloring composition according to claim 1, wherein the 200815918 photopolymerization initiator contains a group selected from 4-[m-bromo-p-N,N-bis(ethoxycarbonylmethyl)amino group. Phenyl]-2,6-bis(trichloromethyl)-s-three tillage, 4-[m-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6 -Bis(trichloromethyl)-s.Tritrap, 4-[m-fluoro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl) )-s-tripper, 4-[o-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-three tillage, 4-[o-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)_s-trimole, 4-[o-fluoro-p-N , N-bis(ethoxycarbonylmethyl)amino (phenyl)-2,6-di(trichloromethyl)-s-tripper, 4-[o-bromo-p-N,N-di(chloro Ethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-tripper, 4-[o-chloro-p-N,N-bis(chloroethyl)aminophenyl]-2 ,6-bis(trichloromethyl)-s-three tillage, 4-[o-fluoro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl) -s-triple trap 4-(m-bromo-p-N,N-bis(chloroethyl)aminophenyl)-2,6-di(trichloromethyl)-s-trimole, 4-(m-chloro-p-N,N -bis(chloroethyl)aminophenyl)-2,6-bis(trichloromethyl)-s-triterpene, 4-(m-fluoro-p-N,N-bis(chloroethyl)aminobenzene -2,6-bis(trichloromethyl methyl)-s-tripper, 4-(m-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethane) -s-Triad, 4-[m-chloro-p-N-ethoxycarbonylmethylaminophenyl]-2,6-bis(trichloromethyl)-s-three tillage, 4-[m-fluorine -p-N-ethoxycarbylmethylaminophenyl]-2,6-bis(trichloromethyl)-s-trimole, 4-(o-bromo-p-N-ethoxycarbonylmethylaminobenzene -2,6-bis(trichloromethyl)-s-tripper, 4-(o-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl) )-s-tripper, 4-(o-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-trimole, 4-(interbromine- For N-chloroethylamine-63- 200815918 phenyl)-2,6-bis(trichloromethyl)-S-tripper, 4-(m-chloro-p-N-chloroethylaminophenyl)-2 ,6-bis(trichloromethyl)-s-three tillage, 4-(m-fluoro-p-N-chloroethylaminophenyl) -2,6-bis(trichloromethyl)-s-tripper, 4-(o-bromo-p-N-chloroethylaminophenyl)_2,6-bis(trichloromethyl)-s-triad , 4-(o-chloro-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-trin, 4-(o-fluoro-p-N-chloroethylaminophenyl) At least one of a group consisting of 2,6-bis(trichloromethyl)-s-tripper and the like, and a group of three tillages in which two or more halogen atoms are introduced into the phenyl moiety. The photocurable coloring composition of claim 1, wherein the black pigment contains the (A) carbon black having a specific surface area of 24 to 1 〇 4 m 2 /g and a pH of 3.0 to 8.8. 4. The photocurable coloring composition according to claim 2, wherein the black pigment contains the (A) carbon black having a specific surface area of 24 to 平方04 m 2 /g and a pH of 3.0 to 8.8. 5. The photocurable coloring composition of claim 3, wherein the black pigment contains 1 to 40% by weight of Si2 in terms of the amount of cerium oxide relative to the total amount of (B) cerium oxide-coated carbon black. The range of (B) coated with cerium oxide carbon black. 6. The photocurable coloring composition according to claim 2, wherein the black pigment contains 1 to 40% by weight of Si2 in terms of the amount of cerium oxide relative to the total amount of (B) cerium oxide-coated carbon black. The range of (B) coated with cerium oxide carbon black. 7. The photocurable coloring composition according to claim 1, wherein the black pigment is contained by containing a resin selected from the group consisting of epoxy resins, phenol resins, tri-64-200815918 melamine resin, xylene resin, and adjacent Glyptal resin, yard-based benzene resin, poly-polyethylene terephthalate, polybutylene terephthalate, poly(p-phenylene terephthalamide), polyamidoximine, poly A right (C) resin-coated carbon black of at least one of the group consisting of maleimide and polyether sulfonate. 8. Photocuring according to item 2 of the patent application scope f The black pigment is contained by containing an epoxy resin, a xylene resin, a glyposide resin (glyPU1) resin, an alkylbenzene resin. Polybutyric acid ethylene terephthalate, polybutylene terephthalate, 3 polyparaphenylene terephthalamide, polyamidoximine, polysynylene imine, polyether sulfonate At least one of the group consisting of phenyl ether ether ketones (C) coated with resin black. 4 9 . A color filter characterized by comprising a colored pattern on a glass glass support, the coloring pattern step and a method of developing a step, wherein the clear pair has a coloring effect from the first to the sclerosing color The photocuring of the composition is patterned to expose the photocurable color; and the developing step is performed by removing the unexposed regions by exposing the exposure to form the colored diallyl acrylate resin, ethylene. a color composition composed of polycarbonate, polyphenylene ether, polyfluorene, styrene, polyamine bis, polyallyl ester, and poly If, wherein the resin, phenol resin, triacid a support body coated with a diallyl resin, a vinylidene fluoride, a polycarbonate, a polyphenylene ether, a polyfluorene, a quinone imine, a polyamine bis, a polyallyl ester, and a polyresin, and is provided thereon The case is cured by exposing the layered body layer containing the layer of the optically colored layer of any one of the items of the exposed light step of the I light step. -65- 200815918 VII. Designated representative figure (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 ^\\\ 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: