TW201115267A - Colored curable composition, method for forming colored pattern, color filter, and liquid crystal display - Google Patents

Abstract

A coloring curable composition, method for forming coloring pattern, color filter and liquid crystal display with suppressed color ununiformity and wide development latitude are provided. A coloring curable composition contains a compound of general formula 1, non-imidazole compound, polyerizable compound, coloring agent, and alkali soluble binder resin having double bond at the side chain. The coloring curable composition further contains pigment dispersing agent.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coloring hardening (tetra) compound, a method of forming a coloring pattern, a color filter, and a liquid crystal display device. [Prior Art] The s-curable composition is, for example, a composition obtained by adding a photopolymerization initiator to a polymerizable compound having an ethylenically unsaturated bond. Since such a color hardening composition is polymerized and cured by irradiation with light, it is used in photocurable inks, photosensitive printing plates, color light-emitting sheets, various photoresists, and the like. Further, as the coloring curable composition, for example, an acid is generated by irradiation of light, and another aspect in which the generated acid is used as a catalyst is also known. Specifically, a coloring reaction of a dye precursor using a generated acid as a catalyst is used for forming an image, preventing forgery, detecting a quantity of energy lines, and utilizing the generated acid as a catalyst. The decomposition reaction is used for semiconductor manufacturing, such as TFT (thin film transist〇r, thin film transistor manufacturing, color polishing sheet manufacturing, and micro-mechanical parts manufacturing, etc.) In view of various uses, it is desired to develop a color hardening composition which is sensitive especially to a short-wavelength (365 nm or 405 nm) light source, and a compound which exhibits excellent sensitivity to the above-mentioned short-wavelength light source, such as photopolymerization. The requirements for the initiator are getting higher and higher. However, since the photopolymerization initiator which is generally excellent in sensitivity lacks stability, it is desired to develop a photopolymerization which is improved in sensitivity while the stability over time is also satisfied. Doc 201115267 priming agent. Therefore 'as a photopolymerization initiator for coloring a curable composition, in US Pat. No. 4,255,513, U.S. Patent No. 4,590,145 An oxime ester derivative is proposed in the Japanese Patent Publication No. 2000-80068, and Japanese Patent Laid-Open No. 2001-233842. However, these well-known oxime ester derivatives have a wavelength of 365 nm. The absorbance at a wavelength of 405 nm is low', so it is not a satisfactory photopolymerization initiator from the viewpoint of sensitivity. Also, as a coloring curable composition, it is also desired to have excellent stability over time' and for 365 A short-wavelength light such as nm or 405 nm has a composition excellent in sensitivity. Further, for example, Japanese Laid-Open Patent Publication No. 2006-195425 discloses a color filter containing a ruthenium compound having a specific structure. Coloring the radiation-sensitive composition 'but the stability over time and the sensitivity to light of short wavelengths are not sufficient. Moreover, for the color-hardening composition for color filters, the reproducibility of the hue after pattern formation As a new subject, the problem that the coloring property changes with time is strongly expected to be improved. On the other hand, the color filter for a liquid crystal display device is strongly enlarged due to the color reproduction region. A high coloring density of a color filter is required. If a large amount of a coloring agent is added in order to obtain a high coloring concentration, there is a tendency that the sensitivity is insufficient and the pattern is detached as a whole. In addition, in order to eliminate the detachment, a higher energy is required. Light irradiation, so the exposure time becomes longer, and the yield in manufacturing is remarkably lowered. According to the above, the color hardening composition for a color filter desirably contains a coloring agent at a concentration and has a good pattern 147754. Doc 201115267 Formatability. Further, in the manufacturing process of pure photo-transparent film, it is usually used to improve the effect (4) when the coloring pattern is formed, and the post-heating place is the post-stomach baking step, but it is determined that there is heat treatment. A color unevenness will be produced at the end of the pattern. [Embodiment] [Problem to be Solved by the Invention] A first object of the present invention is to provide a coloring pattern which can form a good linearity and has no defects, and has a large development latitude when forming a pattern, and is post-baked. The coloring composition which suppresses the color unevenness of the colored pattern caused by the baking step. 0. A second object of the present invention is to provide a high-resolution image forming property, a high development latitude, and a high productivity, and a method for forming a color pattern with a high resolution and a good pattern shape. The color pattern of the color pattern:: 'Light 2' and the liquid crystal display device including the color filter. [Technical means for solving the problem] The present inventors have repeatedly conducted diligent research, and as a result, the compound and the joint (4) are used by using a specific structure. The above-mentioned problem is solved by a compound and a binder resin having a specific structure. Specific technical means for solving the problem are as follows. One less color-curable composition contains (4) a compound represented by the following formula (1), (A2) a surface compound, (B) a polymerizable compound, (6) 147754.doc 201115267 coloring agent, and (D) an alkali-soluble adhesive resin having a double bond in a side chain: [Chemical Formula 1] °曰

In the above formula (1), R, B〇 &amp; Q each independently represent a monovalent organic group, wherein z represents a hydrogen atom or a monovalent substituent, and n2 represents an integer of 〇~5. &lt;2&gt; The colored hardening composition of &lt;&gt;, wherein the (c) coloring agent is a pigment, and further contains (E) a pigment dispersing agent. &lt;3&gt; - a method for forming a coloring pattern, comprising: forming a color-curable composition layer using a color-curable composition such as <b> or <2>; and layering the colored curable composition layer The step of exposing and hardening in a pattern, and the step of developing the color-curable composition layer after the three-time exposure, and partially removing the uncured color-curable composition to form a colored pattern. <4> A color filter which has a colored pattern formed by using a method such as &lt;3&gt; on a support. &lt;5&gt; A liquid crystal display device comprising a color filter of &lt;4&gt;. [Effects of the Invention] According to the present invention, it is possible to provide a coloring pattern which is excellent in linearity and free from defects, and has a large development latitude when forming a pattern, and color unevenness of the colored pattern caused by the post-baking step is suppressed. The coloring composition of the combination 147754.doc ^ 201115267. Further, according to the present invention, there is provided a method of forming a colored pattern having good pattern formation property, large development latitude, and excellent productivity. Further, according to the present invention, a color light-receiving sheet having a colorless pattern having a colorless unevenness, a high resolution, and a good pattern shape, and a liquid crystal display device including the color filter can be provided. [Embodiment] Hereinafter, a coloring composition of the present invention, a coloring pattern using the coloring composition, a coloring sheet having the coloring pattern, and a color filter using the color filter will be described in detail. Liquid crystal display device and solid-state imaging device. &lt;&lt;Coloring-curable composition>> The color-curable composition of the present invention is characterized by comprising: (Αι) a compound represented by the formula (I) (hereinafter, sometimes referred to as a specific anthracene compound), and (A2) An imidazole compound, (B) a polymerizable compound, and (c) a colorant, and (D) a test-soluble adhesive resin having a double bond in a side chain. First, the color hardening composition of the present invention will be described. &lt;(A1) Compound of the formula (I)> [Chemical 2]

147754.doc 201115267 In the formula (I), R, B0 and Q each independently represent an organic group of _, B represents a hydrogen atom or a monovalent substituent, and n2 represents an integer of 0 to 5. In the present invention, (A1) the compound represented by the above formula (1) (hereinafter, referred to as a specific ruthenium compound as appropriate) has light which is decomposed by light to start and promote polymerization of the (B) polymerizable compound described below. The function of the polymerization initiator. In particular, since a specific ruthenium compound has excellent sensitivity to a light source of 365 nm, 44 Å, 5 nm, it is excellent in the case where it is used as a photopolymerization initiator in combination with a polymerizable compound in a colored curable composition. The color-curable composition of the present invention can form a cured film having high sensitivity to light having a wavelength of 365 nm*4〇5 nm, excellent stability over time, and further suppressing coloration caused by heating time. The fine mechanism of the material is not clear, and it is generally considered that the reason is that since the specific ruthenium compound has a structure in which the radical is re-bonded upon cleavage by suppressing the absorption of light, a large amount of free radicals can be generated to achieve high sensitivity. Further, in terms of suppressing the radical re-bonding, the coloration derived from the reaction is suppressed by suppressing the reaction of the cleavage products of the specific deuterated quinones with each other as the heating time elapses. Further, in the present invention, in order to evaluate the coloring of the cured film due to the passage of the heating time, the color difference Δfab can be used. Here, the color difference can be measured using iMcpD_3 manufactured by Otsuka Electronics Co., Ltd. As a condition for evaluation, the present invention is first used with an ultrahigh pressure mercury lamp proximity type exposure machine or an i-line stepwise exposure apparatus (365 nm) 'money exposure amount in the range of 1 〇 mJ/cm 2 to 25 〇〇 mJ/cm 2 . The coloring curable composition 147754.doc 201115267 was subjected to exposure 'to thereby form a cured film. Further, after development as necessary, the cured film was heated at 200 ° C for 1 hour. The coloring state caused by the heating of the hardened film can be evaluated by measuring the color difference Δfab before and after the heating of the cured film. When the colored curable composition of the present invention is used, the color difference ΔΕ ab before and after heating can be made 3 or less, and the color change due to heating can be greatly reduced, whereby a color filter having high color purity can be obtained. The specific ruthenium compound of the present invention can be synthesized, for example, by the method shown in JP-A No. 2-7778778 [0067] to [0069], but is not limited to this method. In the above formula (I), 'R represents a monovalent organic group. The organic group which is a monovalent value represented by R in the general formula (I) may, for example, be an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkyne which may have a substituent An alkylsulfonyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkyl group which may have a substituent, an arylsulfonyl group which may have a substituent, may have a mercapto group, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, a phosphinium group which may have a substituent, a heterocyclic group which may have a substituent, an alkyl group which may have a substituent a thiocarbonyl group, an arylthiocarbonyl group which may have a substituent, a dialkylaminocarbonyl group which may have a substituent, a dialkylaminethiocarbonyl group which may have a substituent, etc., among which a substituent may be preferably used.醯基. The alkyl group which may have a substituent is preferably an alkyl group of a carbon number, and examples thereof include a methyl group, an ethyl group, a propyl group and the like. The aryl group which may have a substituent is preferably an aryl group having 6 to 3 carbon atoms, and 147754.doc -10·201115267, for example, a phenyl group, a biphenyl group or the like. The 1-naphthyl group, the 2-naphthyl group and the 9-fluorenyl group are preferably a mercapto group having a substituent, and a dilute group having a carbon number of 2 to 1 () is preferable, and examples thereof include a vinyl group, an allyl group and a benzene group. Vinyl and the like. The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 1 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group. The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having a carbon number, and examples thereof include a methylsulfinyl group, an ethylsulfinyl group, and a propyl group. Sulfosinyl and the like. ^ is an aryl group which may have a substituent, preferably a carbon number (a) fluorene, and an aryl group is arbitrarily called, for example, a stupid sub-glycosyl group, a brechyl yttrium group, a 2-naphthyl group. Sulfonyl and the like. The alkylsulfonyl group which may have a substituent is preferably a decyl group having a carbon number of 1 to 1, and examples thereof include a methyl group, an ethyl group, a propyl sulfonyl group, and the like. . The arylsulfonyl group which may have a substituent is preferably an aryl group which has a carbon number of from 6 to 2, and examples thereof include a phenyl group, a naphthyl group, a 2-naphthylsulfonyl group, and the like. . The fluorenyl group which may have a substituent is preferably a fluorenyl group having 2 to 2 carbon atoms, and examples thereof include a group I group, a propyl group, a butyl group, a trifluoromethan group, a amyl group, a methyl group, and a naphthyl group. Sulfhydryl, 2_naphthylmethylidene, 4_mercaptothio-based, benzyl, 4-phenylthiolphenyl, 4-diaminobenzoyl, 4-i-B Aminobenzyl fluorenyl, 2 _ benzoyl thiol, 2-methylphenyl fluorenyl, 2 methoxy benzyl benzyl, 2 • butoxy benzoyl, % chloroben 147,754. Doc 201115267 曱二—the basic fluorenyl group, 3-cyanobenzene f fluorenyl group, 3-mercaptophenyl fluorenyl fluorenyl group, 4-cyanobenzoquinone, 4-methoxybenzene曱浐 window: can be "alkoxy group with a substituent, preferably an oxygen number of 2 to 20 carbon. methoxy group, ethoxy group, propylene: soil, butoxy a group, a hexyloxy group, an octyloxy group, an anthracene 1 group, an octadecyl group, a trifluoromethoxy group, etc. : · ', can be a substituted aryloxycarbonyl group, Examples thereof include a phenoxycarbonyl hydrazine, an i-naphthyloxycarbonyl group, and a 2-naphthyloxycarbonyl group. The phosphinyl group which may have a substituent is preferably a phosphine having a total carbon number 其, and the diol is exemplified by dimethylphosphonium, diethylphosphonium, dipropylene, and the like: a bisphosphonium fluorenyl group such as a phenylphosphonium fluorenyl group, a dimethoxyphosphonium fluorenyl group or a diethoxy phosphine, or a bis(2,4,6-trimethylphenyl)phosphonium fluorenyl group. The heterocyclic group having a substituent is preferably an aromatic or aliphatic heterocyclic group containing a hetero atom selected from a gas atom, an oxygen atom, a sulfur atom and a phosphorus atom. Examples of the heterocyclic group ' include a thienyl group, a benzoxenyl group, a naphthoquinone [2,3-b] stilbene group, a thiol group, a furyl group, a pyranordolofuranyl group, and a benzene group. And a piperidyl "xanthenyi", a quinone thiol group, and the like. The mountain is a thiol group which may have a substituent, and examples thereof include a methylthio group, a propylthio group, and a butyl sulfide. a thiol group, a hexylthio group, an octylthiocarbonyl group, a thiol group, an octadecylthio group, a trifluoromethylthio group, etc. 乍 is an arylthio group which may have a substituent, Example 0 can be exemplified by: 1 · naphthyl sulfide 147754.doc 12 201115267 carbonyl group, 2-naphthylthiocarbonyl group, 4-methylsulfanylphenylthio group. As a dialkylaminocarbonyl group which may have a substituent For example, a methylamino group, a diethylamino group, a dipropylamino group, a dibutylaminocarbonyl group, etc. may be mentioned. As a dialkylaminothio group which may have a substituent Examples of the group include a dimethylaminothiocarbonyl group, a dipropylaminethiocarbonyl group, a dibutylaminethio group, and the like. Among the above, 'in terms of high sensitivity, it is represented by R. One price The organic group 'better is fluorenyl'. In particular, it is preferably ethyl acetyl, ethyloyl, propi〇yi, alum, and benzoyl. As a specific example of the organic group which is one of the valences represented by R in the above formula (I), from the viewpoint of high sensitivity, the group shown below is preferred.

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In the general formula (1), the organic group which is a monovalent value represented by bq may, for example, be a phenyl group which may have a substituent, an alkyl group having a carbon number of 取代~(10) which may have a substituent, and a carbon number which may have a substituent of 1~ An alkenyl group of 20, a fast group having a carbon number of the substituent (9), a cycloalkyl group having 5 to 8 carbon atoms which may have a substituent, and a calcined base having 2 to 20 carbon atoms which may have a substituent, may have a phenylhydrazine group of a substituent, an alkoxycarbonyl group having 2 to 12 carbon atoms which may have a substituent, a phenoxycarbonyl group which may have a substituent, -S(0)m-R12 (wherein Ri2 represents a carbon number of 1) ~6 alkyl, 0~2 integer), -S(0)m-R13 (where 'r&quot; represents an aryl group having a carbon number of 6 to 12, which may be substituted by a carbon number of 1 to 12, m is An integer of 〇~2), an alkoxysulfonyl group having 1 to 6 carbon atoms which may have a substituent, an aryloxysulfonyl group having 6 to 1 ring of carbon having a substituent, or a diphenylphosphinium group . 147754.doc -14- 201115267 In the case of the formula (I), when B 〇 represents a phenyl group, examples of the substituent which can be introduced include an alkyl group having a carbon number of 6 and a dentate atom. _R8, -SR or _N(Rl) (Rn) may have a plurality of such substituents. Further, in the case of an alkyl group having 2 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 2 carbon atoms or an alkoxycarbonyl group having 2 to 11 carbon atoms, it may be constituted. The carbon atom of the main chain has one or more oxygen atoms or S atoms, or may be substituted with one or more hydroxyl groups. In the case where BQ represents a clumpy group or a phenoxycarbonyl group, examples of the substituent which can be introduced include an alkyl group having a carbon number of 丨6, a phenyl group, _〇R8, _sr9 or -N(R1G). (R&quot;) may have two or more such substituents. R8 represents a hydrogen atom, an alkyl group having a carbon number of 1212, and a substituted alkyl group having a carbon number of 2 to 6 (wherein the substituent includes a hydroxyl group, a mercapto group, a cyano group, an alkoxy group having 1 to 4 carbon atoms, Alkenyloxy group having 3 to 6 carbon atoms, 2-cyanoacetinyl group, 2 to 7 carbon atoms of _(alkoxy group) ethoxy group, phenyl group having 2 to 5 carbon atoms, phenyl group a carbonyloxy group, a carboxyl group or more than one alkoxycarbonyl group having 2 to 5 carbon atoms], an alkyl group having 2 or more carbon atoms having one or more oxygen atoms between carbon atoms in the main chain, and a carbon number of 2 to 8 Alkanoyl group, _(CH2CH2〇)nH (wherein n is an integer of 丨~2〇), an alkenyl group having 3 to 12 carbon atoms, an olefin group having a carbon number of 3 to 6, a cyclohexyl group, a phenyl group (wherein , which may also be substituted by a halogen atom, an alkyl group of carbon number 12 or an alkoxy group of carbon number 4, a phenylalkyl group having a carbon number of 7 to 9, and _si(Ri4)r(R丨5)3r (wherein , R represents the base of the slave number 1-8, R15 represents a phenyl group, and ^ is an integer of ^). R9 to R11 represent a hydrogen atom, an alkyl group having a carbon number of 1212, an alkenyl group having a carbon number of 3 to 12, a cyclohexyl group, and a substituted alkyl group having 2 to 6 carbon atoms (wherein the substituent includes a hydroxyl group or a mercapto group). , cyano group, alkoxy group having a carbon number of 丨4, alkene having a carbon number of 3 to 6 147754.doc •15- 201115267 oxy '2-cyanoethoxy group, carbon number 4 to 7 2_(alkoxy group a carbonyl group), an alkylcarbonyloxy group having 2 to 5 carbon atoms, a phenylcarbonyloxy group, a carboxyl group or an alkoxycarbonyl group having 2 to 5 carbon atoms; and having a carbon atom constituting the main chain An alkyl group having 2 to 12 carbon atoms or a phenyl group having more than one oxygen atom or sulfur atom (wherein may also be substituted by a _ atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having a carbon number of 4) In the general formula (I), Z represents a hydrogen atom or a monovalent substituent, and examples of the substituent represented by z include a fluorine atom and the like. a halogen group; an alkoxy group such as a methoxy group, an ethoxy group or a third butoxy group; an aryloxy group such as a phenoxy group; an alkoxycarbonyl group such as a methoxycarbonyl group; a methoxy group such as an ethoxy group; Base, benzhydryl group, etc.; methyl sulfide An alkylsulfanyl group such as an alkyl group; an arylsulfanyl group such as a phenylsulfanyl group; an alkylamino group such as a methylamino group or a cyclohexylamino group; a dialkylamino group such as a dimethylamino group; and a phenyl group; An aryl group such as an amino group or a p-phenylphenyl group; an alkyl group such as a decyl group, an ethyl group, a tributyl group or a dodecyl group; a strepyl group, a p-tolyl group, a tolyl group, a cumyl group, An aryl group such as a naphthyl group, an anthracenyl group or a phenanthryl group; and examples thereof include a hydroxyl group, a carboxyl group, a fluorenyl group, a fluorenyl group, a sulfo group, a sulfonyl group, a p-toluenesulfonyl group, an amine group, a nitro group, and the like. Cyano, trifluoromethyl, dichloromethyl, trimethyldecyl, phosphonic acid group), phosphonic acid group, dimethylammonium ion group, dimethyl sulfonate group, diphenylbenzene曱醯Methyl scale ion base, cyano group and the like. The monovalent substituent represented by Z in the formula (I) is preferably an alkoxy group, an anthracenyl group, an arylamine group, an alkyl group or an aryl group. As Z of the formula (I), a hydrogen atom or a substituted one of the above ones is preferred. 147754.doc -16- 201115267 Better is 0 or 1. The substituent may be an integer of G to 5 which is not n2, and may be the same substituent when the core represents an integer of 2 to 5, and represents a structure in which the oxime ester is removed from the compound represented by the above formula (1). An example of the structure represented by the following general formula (1-1). [化4] 0

(I a 1) pm

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Wait. The compound of the above formula (I) has a molar absorption coefficient of 12,000 to 500,000 at 365 nm. The molar absorption coefficient of any of the specific examples shown below is in the range of 12,000 to 500,000. [Chemical 6]

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[Chemistry 7]

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[Chemistry 16]

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The aliphatic polymerization initiator represented by the above formula (I) is a compound having a maximum absorption wavelength in the region around 3 65 nm and having a high absorption efficiency for light having a wavelength of 365 nm. The specific hydrazine compound represented by the formula (I) may be used alone or in combination of two or more kinds in the coloring curable composition. The content of the (A1) specific cerium compound in the coloring curable composition is preferably 100 parts by mass in terms of the total solid content of the colored curable composition in terms of hardenability and coloring property. It is 0.1 parts to 8.0 parts 'better 0.5 parts to 6.0 parts. 147754.doc -34- 201115267 &lt;(A2) biimidazole compound&gt; It is further necessary to contain (A2) a imiprazole compound in the color hardening composition of the present invention. (A2) The biimidazole compound is a compound having a function of decomposing by exposure in a region of a wavelength of 300 nm to 500 nm to cause polymerization of a polymerizable compound described below, in the same manner as the (A1) specific ruthenium compound. The (A2) biimidazole compound which can be used in the present invention is preferably a hexaarylbiimidazole, and the porphin described in Japanese Patent Publication No. Sho 44-86516 Dimers, '2 double (o-chlorophenyl)-4,4',5,5'-tetraphenylbiphenyl, 2,2,_bis(o-bromophenyl)-4, 4,5,5,-tetraphenylbiimidazole, 2,2,_bis(o-, p-diphenyl)_4,4',5,5,_tetraphenylbiimidazole, 2,2,_ Bis(o-phenyl)_4,4,5,5|_tetrakis(m-methoxyphenyl)biimidazole, 2,2,_bis(indole, dichlorophenyl)-4,4,, 5,5,_ tetraphenylbiimidazole, 2,2,_bis(o-nitrophenyl)-4,4·,5,5,-tetraphenyl-biphenyl 2,2-bis(o-methyl) Phenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2,-bis(o-difluorophenyl).4,4,5,5,_tetraphenylbiimidazole, etc. In the coloring composition of the present invention, the biimidazole compound may be used singly or in combination of two or more kinds. In the colored composition of the present invention, the (肟1) specific hydrazine compound and (Α2) are conjugated to each other. Total amount of saliva in coloring The total solid content of the curable composition is 0.1 to 30% by mass, preferably 5% to 25% by mass, particularly preferably 2 to 20% by mass. Further, '(Α) specific 肟 compound is combined with (Α2) The content ratio of imidazole is preferably in the range of 90:10 to 50:50 in terms of mass, more preferably in the range of 9 〇:1 〇 to 65:35. 147754.doc

-35-201115267 &lt;Other polymerization initiators&gt; The color-curable composition of the present invention may also contain a formula (1) other than the above-mentioned polymerization initiator, within the range not impairing the effects of the present invention. A well-known polymerization initiator of a specific compound and a compound material. (4)) a specific monthly loss compound and (A2) (4) Compound 1 is included in the coloring composition of the present invention, and other polymerization initiators are decomposed by light to start and promote the following polymerizable compound. The polymerized compound is preferably a compound having absorption in a region of a wavelength of 300 to 5 Å. Specific examples thereof include an organic functional compound, an oxadiazole compound, a certain group compound, a ketal compound, a benzoin compound, an organic peroxidic compound, an azo compound, a coumarin compound, an azide compound, and a metallocene. a compound, an organoboric acid compound, a disulfonic acid compound, an oxime ester compound, a sulfonium salt compound, or a mercaptophosphine (oxide) compound having a structure different from the above (A1) specific hydrazine compound. More specifically, for example, the polymerization initiators described in paragraphs [〇〇81] to [0100], [0101] to [0139] of JP-A-2006-78749 can be cited. The content of the other polymerization initiator is preferably 3% by mass or less based on the total mass of the (A) specific hydrazine compound and (A2) biimidazole. &lt;(B) Polymerizable compound&gt; The (B) polymerizable compound is preferably a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 1 〇 or more at normal pressure. As the above-mentioned ethylenically unsaturated group having at least one addition polymerizable group, the boiling point of 147754.doc -36 - 201115267 is 1 Torr under normal pressure. (: The above compound may, for example, be a polyethylene glycol single Monofunctional acrylate or methyl acrylate such as (meth) acrylate, polypropylene glycol mono (meth) acrylate, or phenoxyethyl (meth) acrylate, polyethylene glycol Di(meth)acrylate, trihydroxydecylethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylic acid Ester, dipentaerythritol hexa(meth) acrylate, hexanediol (mercapto) acrylate, trimethylolpropane tris(propylene methoxypropyl) ether, tris(propylene methoxyethyl) isocyanuric acid ® oxime on polyfunctional alcohols such as propylene glycol or dimethylolethane After alkane or propylene oxide, a (meth) acrylated product, a pentaerythritol or a pentaerythritol poly(meth) acrylate is obtained, and the patent is disclosed in Japanese Patent Publication No. Sho 48-41708, Japanese Patent No. Sho. The urethane urethanes described in Japanese Laid-Open Patent Publication No. SHO-51-37193, Japanese Patent Laid-Open No. SHO-48-64183, Japanese Patent No. Sho 49-43191, and Japanese Patent Application No. The polyester acrylate described in the publication No. 52-30490, which is a polyfunctional acrylate or mercapto acrylate such as an epoxy acrylate which is a reaction product of an epoxy resin and (mercapto)acrylic acid. It can be used as a photocurable monomer and oligomer in the Japanese Association of Associations magazine v〇1 2〇, No. 7, pages 300 to 308. ^ ^Using the Patent Publication No. 10-62986 The compound obtained by adding (meth)acrylic acid to the polyfunctional alcohol described above as a specific example of the general formulae (1) and (2), wherein the epoxy group or the propylene oxide is added to the polyfunctional alcohol. , preferably dipentaerythritol penta (methyl Acrylate, dipenta 147754.doc -37- 201115267 tetraol hexa(meth) acrylate, and the structure of the propylene sulfhydryl group via ethylene glycol, propylene glycol residues. The oligomer type can also be used. In addition, the urethane urethane described in Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. An amine-based brewing ester having an ethylene oxide skeleton as described in Japanese Patent Publication No. Sho-58-49860, Japanese Patent Publication No. Sho 56-17654, Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-39418 Compounds are also suitable. Further, the addition of an amine-based structure or a sulfur-synchronized structure in the knife described in Japanese Patent Laid-Open Publication No. SHO-63-277, A polymerizable compound is used, and a photopolymerizable composition having a very excellent photospeed is obtained. As a commercially available mouth, Urethane 〇lig0mer UAS-10, UAB-140 (made by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Manufactured by Sakamoto Chemical Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoei Co., Ltd.). Further, 'an ethylenically unsaturated compound having an acid group is also suitable, and as a commercial product', for example, TO-756 which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a mercapto group are mentioned. The 5-functional acrylic acid is brewed in TO-13 8 2 and the like. The polymerizable compound used in the present invention is more preferably a tetrafunctional or higher acrylate compound. The photopolymerizable compound may be used alone or in combination of two or more kinds of 147754.doc -38 to 201115267 5 as a photopolymerizable compound in the coloring curable composition. The total solid content component is preferably from 3 to 55 parts, more preferably from 1 to 5 parts. When the content of the (B) polymerizable compound is within the above range, the curing reaction is sufficiently carried out. &lt;(C) Colorant&gt; As the coloring agent which can be used in the color hardening composition of the present invention, various inorganic pigments or organic pigments which have been known in the past can be used. Alternatively, a dye may be used as needed. For the pigment, it is preferable to use a pigment having a particle diameter as small as possible and a small particle size, regardless of whether the inorganic pigment or the organic pigment has a high transmittance, and if it is considered to be operability, it is preferably an average. The primary particle size is 001 μπι~0·3 μιη, and more preferably the pigment of 〇〇1 is called 〇15 _. If the particle diameter is within the above range, it is effective for forming a color filter having high transmittance, good color characteristics, and high contrast. It is suitable to measure the particle diameter of the pigment by a transmission electron microscope, for example, by measuring the total number of particles in the observation field under 30,000 to 1 million times and the particles of the pigment which are less than 2 μηι and more than 0.08 μηι. Master the particle size distribution. Regarding the ratio of the primary particles of the secondary particle size of less than 2 μm, and the ratio of the secondary particles exceeding 0·08 tons, the length of each primary particle can be determined by observing the pigment powder using a transmission electron microscope. The diameter was calculated by calculating the ratio (number of %) of the pigment particles which were less than 0.02 μΐη and more than 0.08 μηη. More specifically, the pigment powder was observed under a transmission electron microscope at 30,000 to 10,000 times and a photograph was taken, and the length of one of the primary particles was measured. # ' Calculated as less than 〇·〇2 (four) and exceeded 〇 · The ratio of primary particles of 08 μιη I47754.doc -39- 201115267. The position of the pigment powder was changed in total, and the operation was performed on three places, and the results were averaged and used. Examples of the inorganic pigment include a metal compound represented by a metal oxide or a metal salt, and specific examples thereof include iron, cobalt, aluminum, cadmium, ship, copper, titanium, magnesium, chromium, and rhodium. a metal oxide and a composite oxide of the above metals. Examples of the organic pigment, the inorganic pigment, and the metal oxide particles include the pigments described in paragraphs _ 〇 _ _ 44 of Japanese Patent Laid-Open No. 22, or c "Pig Green". α The α substituent of the pigment blue 79 is changed to a ruthenium or the like; among these, as the pigment which can be preferably used, the following may be mentioned. However, the present invention is not limited to these. C·I. Pigment Yellow 11, 24, log 151, 154, 167, 180, 185 C · I. Pigment Dial 3 6, CI Pigment Red 122, 150, 171 c. I. Pigment Violet 19, 23, 32, CI Pigment Blue 15:1, 15:3, 15:6, i6, uc·I·Pigment Green 7,36,37,58, C·I. Pigment Black 1, 7 109 , 11〇, 138, 139 150 Ϊ75 , 177, 209, 224 60, 66, 242 or titanium black [13M-C, 13R-ND manufactured by the company] may be mentioned. The commercially available σ〇 ’ is the Tilack organic pigment of Mitsubishi Chemical Co., Ltd. 赤 Chian Chemical Co., Ltd. can be used alone or in combination with 147754.doc 201115267 for the purpose of improving color purity. In the present invention, a fine and sieved pigment may be used as the (c) colorant as needed. As the finely pigmented pigment, a so-called solvent salt grinding treatment in which a pigment is mixed with a water-soluble organic solvent or a water-soluble inorganic salt to form a high-viscosity liquid composition and is refined is preferable. Salt milling treatment) pigment. In the present invention, in the case where a dye is used as the (C) coloring agent, a uniformly colored color-curable composition is obtained. The dye which can be used as the (C) coloring agent is not particularly limited, and a well-known dye which has been previously used as a color filter can be used. For example, Japanese Patent Laid-Open Publication No. SHO 64-90403, Japanese Patent Laid-Open No. 64-99N No. 2, and Japanese Patent Laid-Open No. 943. ! Japanese Gazette, Japanese Patent Laid-Open No. Hei 6-11614, Japanese Patent Registration No. 25922-7, U.S. Patent No. 4, Outline, 5Gm Specification, U.S. Patent No. 5,667,92 (), U.S. Patent No. 5, 〇59 , Japanese Patent Application Laid-Open No. Hei No. Hei 6-35183, Japanese Patent Laid-Open No. Hei 6-51115, Japanese Patent Laid-Open No. Hei 6-194828, Japanese Patent Laid-Open No. Hei 8- No. Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Japanese Laid-Open Patent Publication No. Hei 8- No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The chemical substance described can be used as a chemical structure: a ratio of a salivary azo group, an anilino azo system, a triphenylmethane system, an anthraquinone group, an anthrapyrid〇ne system, a benzene=base system, Oxygen (tetra) 幷 three _ nitrogen system, condensed ketone oxime system, cyanine system, 酴 (four) system, material 幷対 methylene azo system, dibenzofuran, phthalocyanine, benzopyran, A dye of indigo or the like. The coloring agent of the coloring curable composition of the present invention is 30 parts by weight to 7 parts by mass based on the total solid content of the colored curable composition. The range is more preferably the range of 36 parts to 5 parts by weight of the car parts of the parts of the car. If the content of the coloring agent is within the above range, it is apparent that the discoloration caused by heat is suppressed. The effect of the ability, even for high pigment concentration, due to (four) the brightness is reduced... The coloring property is sufficient and the color characteristics are excellent. In the present invention, the term "pigment concentration" means the mass % of the total solid content of the coloring agent relative to the color-curable composition. It is particularly preferable to use a pigment as a coloring agent and to prepare a pigment dispersion composition in a pigment solvent by adding a dispersant or the like before the color curing composition. Further, it is preferred to prepare I47754.doc. -42- 201115267 Before the pigment dispersion composition, the pigment is refined by a salt milling step as described later, and it is preferred to use a pigment coated with the local knife compound in the salt milling step or the dispersion step of the pigment. When the pigment is coated with the polymer compound, it is possible to suppress the formation of secondary aggregates in the finely pigmented pigment and to disperse it in the state of the i-order particles. When a pigment coated with a polymer compound is used, the dispersed primary particles can be stably maintained, and a color-curable composition excellent in dispersion stability can be obtained. The coated pigment suitable for the aspect of the coloring agent (c) in the present invention means a pigment coated with a polymer compound, and the so-called coating means that the pigment is subjected to a pigment refining step (salt grinding step). A polymer compound such as a polymer dispersant coexists, and a new interface of a pigment having a high surface activity generated by miniaturization is formed, and a polymer compound is formed by a strong electrostatic interaction with a polymer compound which is useful for pigment dispersion. A strong coating layer is generally considered to form a coating layer to obtain a coated pigment having higher dispersion stability. The coated pigment having the coating layer formed in the miniaturization step is almost free from the ruthenium molecular compound to be coated even if it is washed with an organic solvent in which the polymer compound is dissolved. The salt grinding step for forming the coated pigment will be specifically described. First of all,

In the mixture of i) an organic pigment and ii) a water-soluble inorganic salt, a water-soluble organic solvent is added as a wetting agent, and a kneading machine is used. #强=合合, the mixture is put into water. The machine or the like is stirred to form a slurry. Then, the slurry is filtered, washed with water, and dried as necessary, whereby a finely pigmented pigment is obtained. Further, the pigment is dispersed in the oil L 147754.doc -43·201115267, and the varnish which is directly dispersible in the bismuth cake is removed by using water commonly called a flash material (called a filter cake) to disperse in the varnish of the water system. In the case of use, the method of "flashing" may be used to disperse the surface of the treatment before drying into an oily varnish. Further, in the case of the treatment of the pigment, it is not necessary to dry into the varnish. The iv) at least partially soluble resin can be used in combination with the above-mentioned organic solvent in the case of salt milling to obtain a finer pigment and a surface which is coated with a resin which is at least partially soluble in at least a part of the pigment. Furthermore, for the addition of iv) polymerized human version+.士 — 7 knives. The timing of the material may be added to all of the iv) polymer compound, the knives, and the π σ at the beginning of the salt milling step. Further, it can also be added in the dispersion step. The polymer compound to be coated with the pigment is not particularly limited as long as it has a basis for the absorption of the pigment. It is preferred to use a polymer compound which is well known as a pigment knife to disperse sodium, and it is particularly preferable to use it. The side bond has a heterocyclic polymer compound. &lt;(Ε) Pigment Dispersant&gt; In the color hardening composition of the present invention, when a pigment is used as the coloring ruthenium, it is preferred to use a pigment dispersant in combination. The gossip is a pigment dispersant, and it is preferred that the macromolecular compound having a hetero ring in the side chain as the polymer compound preferably contains a military god from the following formula (1), f遐' or contains a cis. A polymer of a polymerized unit of butene diimine or a maleimide haloper is particularly preferably a polymer comprising a polymer unit derived from a monomer represented by the following formula U). 147754.doc 201115267 [Chem. 22]

In the above formula (1), Ri represents a hydrogen atom or a substituted or unsubstituted alkyl group. R2 represents a single bond or a divalent linking group. γ represents _c〇_, -c(=0)0-, -C0NH..._0C(=0)_ or a phenyl group. z represents a group having a nitrogen-containing heterocyclic structure. The alkyl group of R1 is preferably an alkyl group having 1 to 12 carbon atoms, more preferably a alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having a carbon number of 4. In the case where the alkyl group represented by R1 has a substituent, examples of the substituent include a hydroxyl group and an alkoxy group (preferably, carbon number 5, more preferably carbon number 1 to 3, for example, ruthenium). Oxyl, ethoxy, cyclohexyloxy) and the like. Such a compound is described in detail in paragraphs [0〇2〇] to [0〇47] of Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. 2-266627 (the present FSP-10544), and the compound described therein can be suitably used. It is used as a pigment dispersant in the present invention. As the pigment dispersant, in addition to the above compounds, a well-known pigment dispersant or a surfactant may be appropriately selected, for example. Specifically, a plurality of compounds can be used, and examples thereof include an organic oxime-fired polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and a (meth)acrylic (co)polymer P〇lyfl〇w No&quot; P〇lyfl〇wn〇9〇,

Polyfiow No. 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), 147754.doc -45- 201115267 w〇〇1 (manufactured by Yushang Co., Ltd.) and other cationic surfactants; polyoxyethylene lauryl ether, polyoxygen Vinyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene decyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitol fat Anionic surfactant such as acid ester; anionic surfactant such as W004, W005, W017 (manufactured by Yushang Co., Ltd.); EFKA-46, EFKA-47, EFKA_47EA, EFKA Polymer 1〇〇, EFKA P〇lymer 4〇〇, efka

Polymer 401, EFKA Polymer 450 (either one is manufactured by Ciba Specialty Chemicals), Disperse Aid 6,

Polymer dispersants such as Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco); s〇isperse 3000, Solsperse 5000, Solsperse 9000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000 , Solsperse 24000, Solsperse 26000, Solsperse 28000 and other Solsperse dispersants (made by Lubrizol Co., Ltd., Japan); Adeka Pluronic L31, Adeka Pluronic F38, Adeka Pluronic L42, Adeka Pluronic L44, Adeka Pluronic L61, Adeka Pluronic L64, Adeka Pluronic F68 , Adeka Pluronic L72, Adeka Pluronic P95, Adeka Pluronic F77, Adeka Pluronic P84, Adeka Pluronic F87, Adeka Pluronic P94, Adeka Pluronic L101, Adeka Pluronic P103, Adeka Pluronic F108, Adeka Pluronic L121, Adeka Pluronic 卩-123 Co., Ltd. manufactures) and 13〇1^13-20 (manufactured by Sanyo Chemical Co., Ltd.) 'Disperbyk 101, Disperbyk 103, 147754.doc -46 · 201115267

Disperbyk 106, Disperbyk 108, Disperbyk 109, Disperbyk 111 'Disperbyk 112 ' Disperbyk 116, Disperbyk 130, Disperbyk 140, Disperbyk 142, Disperbyk 162,

Disperbyk Disperbyk Disperbyk Disperbyk 163 167 174 182

Disperbyk 166 Disperbyk 171 Disperbyk 180 Disperbyk 2001 , Disperbyk 164 , ' Disperbyk 1.70 , , Disperbyk 176 ' ' Disperbyk 2000

Disperbyk 2050 'Disperbyk 2150 (manufactured by BYK-Chemie Co., Ltd.). In addition to this, a propionic acid-based copolymer may be mentioned as an oligomer or a polymer having a polar group at a molecular terminal or a side chain. In the case where a pigment is used as the (C) coloring agent, from the viewpoint of improving the uniform dispersibility of the pigment, it is preferred to first prepare a pigment dispersion composition and then add it to the coloring curable composition. In the case of preparing the pigment dispersion composition, it is preferred to add 1 to 100 parts of the (E) pigment dispersant, more preferably 3 to 7 parts by weight, based on the amount of the pigment (10 parts). A pigment derivative is added as needed in the above pigment dispersion composition. The pigment which has an affinity of 9.1 knife or a polar group to be introduced into the dispersing agent will be adsorbed on the surface of the pigment and used as a adsorption point of the dispersing agent, and 1: dispersed in the form of fine particles in the pigment. In the dispersion composition, the light-proof sheet is more effective.遽, color 优异 excellent in transparency: It is better to use a pigment derivative in the pigment dispersion composition with respect to 100 parts of the pigment. If the content is within the above range, := will be =. The viscosity is suppressed to be lower than M7754.doc •47-201115267, the side is well dispersed, and the dispersion stability after dispersion is improved, the transmittance is high, and excellent color characteristics are obtained, and the pigment dispersion composition is used for preparation. When the color hardening composition of the present invention is used to produce a color filter, a color sheet having high contrast and good color characteristics can be obtained. As a method of dispersing, for example, a method may be employed in which a pigment and an optional dispersing agent are previously mixed in a solvent, and a mass machine or the like is preliminarily mixed, and the rider uses a bead mill dispersing machine using an oxidizing agent or the like. Wait for microdispersion. &lt;(D) Alkali-soluble binder resin having a double bond in a side chain&gt; The alkali-soluble resin functions as a binder component, and in the present invention, a specific base having a double bond in a side chain can be used. The soluble resin is used as an alkali-soluble resin, and in particular, both the curability of the exposed portion and the alkali developability of the unexposed portion are improved. (D) an alkali-soluble adhesive resin having a double bond in the side chain used in the present invention, in order to improve various properties such as non-image portion removability, the structure has a structure for making the resin soluble in the test. An acid group, and at least (10) an unsaturated double bond. As a structure including a saturated double bond, it is preferable that the side chain has at least one selected from the group consisting of the following fraction structure (4) to partial structure (4). The resin which is soluble in an alkaline aqueous solution and used as an adhesive resin of a negative type image recording material has at least one selected from the group consisting of a part of the structure (a) to a part of the structure (c) can. Tian Ran can have a plurality of the above-mentioned bases, and # can have the entry of the bases at the same time. Wang H7754.doc -48 - 201115267 1 'The side chain shown in part structure (a) to part structure (c) is explained. [Chem. 23]

1 2 R1lc—it: 1110 CIR Partial structure (b) R5 ~X—C~C=C 〇 R4R6 Partial structure (a) R16 R19

II—Z—C—C—C R17 R^R20 Partial structure (c) In the knife structure (a) to partial structure (c), r4~r6, Rl0~r12, r16~r2 are not uniquely priced. Substituent. x and z each independently represent an oxygen atom or -N(R)-, and R22 represents a gas atom or an organic group of _. Gamma table = oxygen atom, sulfur atom, phenyl group which may have a substituent or although 23)_, R represents a hydrogen atom or a monovalent organic group. The adhesive resin having the above partial structure is described in detail in Japanese Laid-Open Patent Publication No. 262958, and the compound described therein can also be used in the present invention. The alkali-soluble adhesive resin having a double bond in the side chain (D) used in the color hardening composition of the present invention has an acid group in its structure in order to improve various properties such as non-image portion removability. The above (1)) alkali-soluble adhesive resin having a double bond in a side chain preferably contains a radical polymerizable compound having an acid group as a copolymer component. The acid group may, for example, be a carboxylic acid group, a sulfonic acid group, a phosphoric acid group or a phenolic hydroxyl group, and particularly preferably a carboxylic acid group. These may be used in the form of lanthanum or more, and the content of the copolymerized component is suitably 5 to 5 〇 mol%, which is particularly preferable from the viewpoint of suppressing image strength damage caused by alkali water development. 47754.doc -49· 201115267 is 1 0~40% by mole. Further, the (D) alkali-soluble adhesive resin having a double bond in the side chain of the present invention has various properties such as improvement in image strength, and is free from the above-described specific functional groups as long as the effects of the present invention are not impaired. In addition to the base polymerizable compound, it is preferable to include other radical polymerizable compound as a copolymer component. The radically polymerizable compound which can be copolymerized with the alkali-soluble adhesive resin which has a double bond in the side chain of (D) of this invention is mentioned, for example, is selected from acrylates, methacrylates, ethylene, and propylene. A radically polymerizable compound in a nitrile, a mercapto acrylonitrile or the like. Among these radically polymerizable compounds, those which are suitable are methyl acrylates, acrylamides, methacrylamides, and styrenes. These may be used in one or two or more kinds, and (D) in the alkali-soluble adhesive resin having a double bond in the side bond, the copolymerization component is suitably used: the amount is 0 to 90 mol%, especially preferably Moer%. When the content is within the above range, the pattern is sufficiently formed. Examples of the solvent used in the synthesis of the above polymer compound include diacetylated acetamidine, cyclohexanone, methyl ethyl epoxide, and propylene steel 'methanol, ethanol, propanol, butanol, and ethylene glycol. Ethylene glycol monoethyl sulphate, : ethyl acetate, methoxy-2-propanol, κ methoxyacetic acid propyl vinegar, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine dimethyl hydrazine One ^ T sulfoxide, A, ethyl acetate, methyl lactate, lactic acid, etc. These solvents may be used singly or in combination of two or more. Specific examples of the above-mentioned (9) specific solvent-soluble resin having a double bond in the side bond are 147754.doc • 50·201115267, and the following exemplified compounds 1 to exemplified compounds 3 1 are exemplified.

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丨HN8 ςΓ , oox/VJ-8 201115267 [Chemical composition 27] exemplified compound composition (mol%) Mw acid value (mgKOH/^) 10 卜 C )20 〇r^°X== ^0 :〇2 /=\ K3 ^2D co2h 97000 70 11 (Di, ^r :〇Ρ^°γ^·, Diέο2 - —ch )02H 128000 59 12 &lt; 七 5 ^ :02 , _ , ko C〇2- —c hs o2h 135000 59 13 έ〇Γ^ c( 80 )2/=% CK$ o2h 132000 56 14 Bu C ^20 1 :〇Ρ^°γ^ 'h〇c〇2-0 c Ήο ;o2h 103000 74 15 C 匕L 〇Γ^0γ^ ck〇onhhQ co2h 97000 73 16 , seven. Co2h ck 〇C^°Y^ }?〇'〇L^&gt; 107000 51 147754.doc -54- 201115267 [Chemical 28] Exemplary compound composition (mol%) Mw Acid value (msKOH/^) 17 C h 〇 Γ^°γ^ c 卜· cof^-^ ck 〇fS^O o2h c r. )e5 i〇2CH3 114000 77 18 'seven. C〇2 y=\ ( t' co^〇*ho I ϊ〇^°γν , -h〇co2h 136000 69 19 C ^2〇〇i〇-%6 ( :〇2h 100000 S3 Z0 会卜0&lt; ' ^60 *W*20 ^OMe O^HO^OX 9000 103 21 Winter 0^, Me 〇人〇H. 人? 14000 30 55- 147754.doc 201115267 [Chemical composition 29] exemplified compound composition (mol%) Mw acid Value (mgKOH/κ) 22 cr^oo^oh ο^γ 50000 72 23 . People 〇 0 入. °ν 50000 70 24 *HK〇*-t&gt;K〇°^° \ \ °^〇H 〇| S0H ^ 0人0 SH 〇30000 70 147754.doc 56- 201115267 [Chemical Formula 30] Illustrative compound composition (mol%) Mw Acid value (mgKOH/g) 25 C k5 ^ c L· -H^o 〇2 /=\ Conh2 co2h &quot;-〇145000 64 26 C 〇Ρ^°γ^·( ϊ〇2 /=^% ( Ο zom2 c! ϊο2η 120000 57 27 , seven 5 L b ο〇ΓΝχχ, 0 γ^ ( 0 ^) 50 )〇2y=x CONH-^ { :o2h 133000 54 28 h· C 〇f^°Y^ c&lt; 0 50 〇2—(^y COMH〆,匕COzH 111000 55 29 ( ^τγ2〇conh2 c ,*) $0 co2h )s〇103000 77 30 &lt; VII. &quot;(^七0 :〇Γ^°γ^= C〇2_^=^ CO?H 5&amp;OOQ 70 31 '^5 I ο〇Γ^°γ ^ ( )so VII, Ή〇-f^·/ :ONH2 C( *15 32H 52000 57 147754.doc -57- 201115267 (D) The acid value of the alkali-soluble binder resin having a double bond in the side chain can be calculated, for example, from the average content of the acid groups in the resin molecule. The content of the monomer unit constituting the acid group of the alkali-soluble adhesive resin having a double bond in the side chain is obtained to obtain a resin having a desired acid value. (D) has a double bond in the side chain in the invention. The mass average molecular weight of the alkali-soluble binder resin is preferably from 30,000 to 300,000, more preferably from 35,000 to 250,000, and still more preferably from 40,000 to 200,000, from the viewpoint of suppressing pattern peeling and developability at the time of development. Good is 45,000~100,000. Further, (D) the mass of the alkali-soluble binder resin having a double bond in the side chain, and the molecular weight of the salt can be determined by GPC (gel permeation chromatography &gt; gel permeation chromatography). In the total solid content of the color hardening composition of the present invention, (D) the content of the alkali-soluble adhesive resin having a double bond in the side chain, and in terms of polymerizability and alkali developability, it is preferably 0.1 to 7.0 mass. % is more preferably from 0.3 to 6.0% by mass, still more preferably from 1.0 to 5.0% by mass, from the viewpoint of suppressing both the pattern peeling and the development residue. Hereinafter, any component which can be contained in the coloring curable composition will be described. &lt;(E) Sensitizer&gt; The coloring curable composition may contain a sensitizer for the purpose of increasing the free radical generating efficiency of the radical initiator and increasing the wavelength of the photosensitive wavelength. As the sensitizer which can be used in the present invention, it is preferred to sensitize the above (A1) specific hydrazine compound by an electron transfer mechanism or an energy transfer mechanism 147754.doc - 58 - 201115267. The sensitizer used in the present invention may be a compound exemplified below, and has an absorption wavelength in a wavelength region of 300 nm to 450 nm. That is, for example, polynuclear aromatics (for example, phenanthrene, anthracene, ketone, flower, tert-triphenyl, 9,1 fluorene-dialkyloxyanthracene), dibenzopyrans (for example, luciferin) (fluorescein), blush 'erythro red, rhodamine b, bengal rose red), 9-oxo-sulfur p-indene (isopropyl _9_ oxysulfonate p, diethyl _9_ oxysulfuron) Anthraquinone, chloro-9-oxopurine, cyanine (eg, thiocarbaphthalene, oxacarbocyanine), procyanidins (eg, merocyanin, carbo merocyanine) )), phthalocyanines, stilettos (eg, thioindigo, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavon, acridine flavin), brewing (eg brewing) i), squalene rust (such as squalene oxime), acridine orange, coumarin (such as 7-diethylamino 4-methyl coumarin), ketocoumarin, phenol sulphate Class, cultivating, styrylbenzene, azo compound, diphenylmethane, triphenylmethane'. distyrylbenzene, carbazole, porphyrin, spiro compound, quinacridone, Indigo, stupid ethylene, pyran rust Thereof, the ratio B ° each methylene compounds, n-Bing laugh than three saliva compound, benzo ° plugs. An aromatic ketone compound such as a compound, a barbituric acid derivative, a thiobarbituric acid derivative, an acetophenone, a benzophenone, a 9-oxopurine, or a ketone. a heterocyclic compound such as a ketone or the like. As a more preferable example of the sensitizer, the compound described in Paragraph No. [〇085] to [0〇98] of JP-A-2002-214395 is exemplified. 147754.doc •59- 201115267 In terms of sensitivity and storage stability, the content of the sensitizer is preferably 0·1 to 3 〇 by mass relative to the total solid content of the colored curable composition. The range of % is more preferably in the range of 1 to 2% by mass, and more preferably in the range of 2 to 15% by mass. &lt;(F) Co-sensitizer&gt; The color hardening composition of the present invention preferably further contains a co-sensitizer. In the present invention, the auxiliary sensitizer further enhances the sensitivity of the sensitizing dye and the initiator to the actinic radiation or suppresses the inhibition of aggregation of the photopolymerizable compound by oxygen. As an example of such a secondary sensitizer, an amine may be mentioned, for example, J. urnal 〇f Polymer Society by R Sander, Vol. 10, p. 3173 (1972), Japanese Patent Publication No. 44-2〇189 Japanese Patent Laid-Open No. 51-82102, Japanese Patent Laid-Open No. SHO-52-134692, Japanese Patent Laid-Open No. 59-138205, Japanese Patent Laid-Open No. Hei. JP-A-62-18537, the compound described in Japanese Patent Application Laid-Open No. Hei 64-33104, and Research Disclosure No. 33825, and the like, specifically, triethanolamine, p-didecylaminobenzoic acid ethyl ester, and palladium Mercaptodidecylphenylamine, p-sulfonyldimethylaniline, and the like. Further examples of the auxiliary sensitizer include thiols and thioethers. For example, Japanese Patent Publication No. Sho 53-702, Japanese Patent Publication No. SHO 55-500806, and Japanese Patent Application Laid-Open No. Hei No. Hei-5-142772 The melamine compound, the thiolated product of the Japanese Patent Publication No. 56-75643, and the like, specifically, 2-mercaptobenzothiazole, 2-mercaptobenzopyrene H7754.doc 201115267 azole, 2-oxime Benzimidazole, 2·indenyl.·4(3Η)_quinazoline, β-mercaptophthalene, and the like. In addition, examples of the other examples include an amino acid compound (for example, fluorene-phenylglycine), an organometallic compound (for example, tributyltin acetate) described in JP-A-48-42965, and a Japanese patent. The hydrogen donor described in Japanese Patent Publication No. 55-34414, and the sulfur compound (for example, three-dimensional plugging or the like) of the Japanese Patent Publication No. 55-34414. From the viewpoint of increasing the rate of curing by increasing the polymerization growth rate and the chain transfer equilibrium, the content of the auxiliary sensitizer is preferably 质量, the mass% of the total solid content of the combination of the hardenability. More preferably, the range of 1 to 25 masses is further preferably a range of G5 to 2% by mass. &lt;(G) a binder polymer which can be used together&gt; for the purpose of improving film properties and the like

In the coloring curable composition, a binder polymer organic polymer may be further used as needed. As such a "Lin No., 曰本专利特公昭58

147754.doc 201115267 54-92723, Japanese Patent Laid-Open No., Japanese Patent Laid-Open No. SHO 59-71-48, which is also known as 'polymerizing or copolymerizing a monomer having a carboxyl group. Resin, you and the female sputum have an anhydride monomer polymerization or this polymerization and then acid hydrolysis of the semi- or semi-amidated tree sap, using unsaturated mono-acid and acid liver to change the epoxy resin Made of epoxy acrylate and so on. Examples of the monomer having a rebel group include: acrylic acid, methyl diacid, itaconic acid, butyric acid, cis-butyl diacid, counter-butadiic acid, styrene-based styrene, etc.; The monomer may, for example, be an acid cellulose derivative having a (4) group similar to maleic anhydride. In addition to this, it is also useful to add a cyclic acid needle to a polymer having a fine base. In the case where an alkali-soluble resin is used in the form of a copolymer, as the compound to be copolymerized, a monomer other than the above-exemplified monomers may be used. Also, Japanese Patent Special Fair 7_12〇〇4 Japanese Patent Special Fair 7-120041, Japanese Patent Special Fair 7_12〇〇42 Japanese Patent Special Fair 8-12424, Japanese Patent Special Open 63_28&gt;7944, Japan The acid group-containing urethane-based adhesive polymer described in Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Adaptability is more favorable. Also, the acetal-modified polyethylene having an acid group described in the European Patent No. 993966, the European Patent No. 12〇4, and the Japanese Patent Laid-Open No. 2001-318463, etc. 147754.doc • 62- 201115267 Alcohol-based adhesive polymer The balance between film strength and developability is excellent, and is appropriate. Further, as a water-soluble linear organic polymer, it is a polyethylene material. Ketone, polyepoxy, etc. are more useful. Further, in order to increase the strength of the hardened film, it is also useful to use alcohol-soluble nylon or 2,2·bis-(4-pyridylphenyl)propane and gas alcohol. Among the hydrazines, etc., especially [(meth)acrylic acid methacrylate/(meth)acrylic acid/other addition polymerizable ethylene monomer] copolymer, and [(meth)acrylic acid allyl ester/ (Sub-base) acrylic acid / other addition-polymerizable vinyl monomer as needed] The copolymer is excellent in the balance of film strength, sensitivity, and developability. The weight average molecular weight of the binder polymer which can be used in the coloring curable composition is preferably 5,000 or more, more preferably in the range of 10,000 to 30,000, and the number average molecular weight is preferably the above. Better is 2, 〇〇〇 ~ 250,000 range. The polydispersity index (weight average molecular weight/number = average molecular weight) is preferably yttrium or more, more preferably yttrium. The binder polymer may be any of a random polymer, a block polymer, a graft polymer and the like. The binder polymer which can be used in the present invention can be synthesized by a previously known method. Examples of the solvent used in the synthesis include tetrahydrofuran 'vinyl chloride, cyclohexanone, and the like. These solvents may be used singly or in combination of two or more. The radical polymerization initiator used in the synthesis of the binder polymer which can be used in the color-curable composition may, for example, be a well-known compound such as an olefin initiator or a peroxide initiator. ° 147754.doc •63- 201115267 &lt;(Η) Polymerization Inhibitor&gt; In the coloring curable composition, heat which is not required to prevent the production of a polymerizable compound during or during the production of the composition Polymerization, a rational addition of a small amount of polymerization inhibitor. As the polymerization inhibitor, a well-known thermal polymerization inhibitor can be used, and specific examples thereof include: hydroquinone, p-nonyloxyphenol, di-tert-butyl-p-nonylphenol, o-stupholol, and t-butyl tea. , benzoquinone, 4,4,-thiobis(3-methyl-6.t-butylphenylhydrazine), 2,2,_methylenebis(4_methyl·6·t-butyl Silk), hydrazine nitrosophenylene sulfhydryl (III) salt, and the like. The addition amount of the ‘,, and the clogging preventing agent is preferably from about 0.1% to about 5% by mass based on the total solid content of the colored curable composition. &amp; It is also possible to add a higher fatty acid derivative such as behenic acid or behenylamine in order to prevent the polymerization inhibition by oxygen, and to make it uneven in the process of drying after coating. Distributed on the surface of the coated film. Preferably, the amount of the higher fatty acid derivative added is from about 5% to about 丨〇% of the total composition. &lt;(Adhesion improving agent&gt; Two-color hardening 1±composition composition] In order to improve the adhesion to a hard surface such as a support, a adhesion improving agent may be added. Examples of the adhesion improving agent include: Shi Xizhuo A coupling agent, a titanium coupling agent, etc. As a residual coupling agent, mercapto propylene methoxy propyl trimethoxy decane, γ methacryl methoxy propyl triethoxy oxime is preferably exemplified. , γ-acryloxypropyltrimethoxy (tetra), γ • propyloxypropyl triethoxy I, γ_(tetra)propyltrimethoxy, γ-aminopropyl III 147754.doc • 64 - 201115267 Ethoxy decane or phenyltrimethoxy decane, more preferably decyl propylene methoxy propyl trimethoxy decane. The adhesion improving agent is preferably added to the coloring curable composition. The total solid content is 〇5 to 3〇% by mass, more preferably 0.7 to 20% by mass. &lt;(J) Thinner&gt; In the coloring curable composition, various organic solvents can be used as a diluent. 0 As the organic solvent used herein, there are C-, methyl ethyl ketone, cyclohexane, ethyl acetate, and dichloride B. , tetrahydrofuran, toluene, ethyl alcohol monomethyl ether: diol diol single sulphate, ethylene glycol dimethyl singer, propylene glycol single; succinct, propylene glycol single y, shredded acetone, cyclohexane, diacetone alcohol, B Alcohol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, Diethylene glycol monomethyl sulphate, diethylene glycol monoethyl hydrazine, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxy Propyl acetate, hydrazine, hydrazine dimethyl carbamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, ethyl lactate, etc. These solvents may be used singly or in combination. The concentration in the organic solvent is preferably from 2 to 60% by mass. <Other additives> Further, in order to improve the physical properties of the cured film, an inorganic filler or a plasticizer may be added to the colored curable composition. , lipid-sensitive agents, etc. are well known: additives. As plasticizers, for example: dioctyl phthalate, phthalic acid 147754.do C -65- 201115267 one (d-12 alkyl) ester, triethylene glycol dicaprylate, dimercapto ethylene glycol phthalate, tricresyl phosphate, dioctyl adipate, bismuth In the case of using a binder, when the binder is used, it may be added in an amount of 1% by mass or less based on the total mass of the polymerizable compound and the binder polymer. The color hardening composition of the present invention The (A1) specific hydrazine compound, (A2) biimidazole compound, (B) polymerizable compound, (C) colorant (preferably prepared to contain a pigment dispersant) may be contained together with a solvent as needed. The pigment dispersion composition) and (D) an alkali-soluble binder resin having a double bond in a side chain, and if necessary, an additive such as a surfactant is mixed. As described above, the color hardening composition of the present invention contains (A1) two kinds of photopolymerization initiators of a specific hydrazine compound '(A2) biimidazole compound and (d) an alkali-soluble resin bond having a double bond in a side chain. The resin, therefore, high-sensitivity hardening' forms a high-definition color map t, and suppresses uneven coloration of the colored pattern after post-baking. Such a color hardening composition can be suitably used for various uses in which various high-definition and color: excellent coloring patterns must be formed, in particular, by using a color filter for forming high definition and suppressing color unevenness. The coloring pattern has a remarkable effect. 〃 &lt;&lt;Color forming method of color pattern and color filter having the same. Hereinafter, a method of forming a coloring pattern of the present invention and a color filter having a colored pattern obtained therefrom will be described. The coloring pattern forming method of the present invention includes the step of forming a colored curable composition layer using the above-described colored curable composition of the present invention / 147754.doc • 66 - 201115267 Exposing the colored curable composition layer in a pattern And a step of curing (hereinafter, simply referred to as "coloring photopolymerizable composition layer forming step"); and developing the colored curable composition layer after exposure to partially remove the uncured color-curable composition a step of forming a colored pattern; and 'the step of forming the colored pattern includes a step of patterning the colored curable composition layer (hereinafter, simply referred to as "exposure step") and a combination of the above-described color hardening after exposure The step of developing the layer to form a colored pattern (hereinafter, simply referred to as "developing step" as appropriate). Further, the color filter of the present invention is characterized in that it is attached to a support and has a colored pattern formed by the above-described colored pattern forming method of the present invention. Hereinafter, the color filter of the present invention will be described in detail by the production method thereof (the color pattern forming method of the present invention). Specifically, the colored curable composition of the present invention is applied onto a support (substrate) directly or via another layer to form a colored curable composition layer (coloring curable composition layer forming step), followed by patterning. Exposure, preferably 疋, exposure by a special mask pattern, only partially cures the coating film irradiated with light (exposure step), and then develops using a developing solution (development step) to thereby form a colored pattern . In the case where the color filter is produced by this method, a colored pattern of each color (three colors or four colors) can be sequentially formed on the support to form a pixel of a desired hue. Further, as described later, the color hardening composition of the present invention can also be used to form a black matrix. Hereinafter, each step will be described. 147754.doc •67-201115267 [Coloring-curable composition layer forming step] In the coloring-curable composition layer forming step, the colored curable composition for color filters of the present invention is applied onto a support to form The layer of the curable composition is colored. As a support which can be used in this step, for example, soda glass used in a liquid crystal display element, Pyrex (registered trademark) glass quartz glass, and a transparent conductive film attached thereto, or an image pickup device, etc. The photoelectric conversion element substrate used in the present invention is, for example, a germanium substrate or the like, or a complementary metal oxide semiconductor (CMOS, complementary metal_〇xide sem). Also, black stripes on each of the substrates are formed on the substrates. Further, in order to improve the adhesion between the support and the upper layer and prevent the substance from spreading or flattening the surface of the substrate, it is also possible to provide an undercoat layer on the support as needed. As a coating method for applying the coloring curable composition for a color filter of the present invention to a support, slit coating, inkjet method, spin coating, cast coating, roll coating, or the like can be applied. Various coating methods such as screen printing. The coating film thickness of the coloring curable composition is preferably μηι 10 μπι, more preferably 〇2 μιη to 5 (four), and more preferably 〇2 μπι 3 μηι 〇, in the manufacture of liquid crystal display elements. When the color filter is used, the coating film thickness of the photopolymerizable composition for a color filter is preferably from η to 3.5 μm, and more preferably 0.5 μm from the viewpoint of resolution and developability. ~2·0·πι 〇147754.doc •68· 201115267 The photopolymerizable composition for color filters coated on a support is usually dried at 70 C to 110 C for 2 minutes to 4 minutes. A color photopolymerizable composition layer is formed. [Exposure step] In the exposure step, the colored photopolymerizable composition layer formed in the colored photopolymerizable composition layer forming step is exposed through a mask, and only the coating film subjected to light irradiation is partially cured. The erbium which is preferably exposed is irradiated with radiation, and it is particularly preferable to use ultraviolet rays such as g-rays, h-rays, x-rays, etc., more preferably high-pressure mercury lamps. The irradiation intensity is preferably 5 mJ/cm 2 to 1500 mJ/cm 2 , more preferably 1 〇 mJ/cm 2 to 1 〇〇〇 mJ/cm 2 , and most preferably 10 mJ/cm 2 to 800 mJ/cm 2 . [Developing Step] After the exposure step, an alkali developing treatment (developing step) is carried out to dissolve the unexposed portion of the light in the exposure step into the aqueous alkali solution. Thereby, only the portion where the light is hardened remains. The developer is desirably an organic developer which does not cause damage to the circuit or the like of the substrate. The development temperature is usually 2 (rc ～ 3 〇〇 c, and the development time is 20 sec to 9 sec. As the base used in the developer, for example, ammonia water, ethylamine, diethylamine-mercaptoethanolamine, Tetramethylammonium hydroxide, tetraethylammonium hydroxide, biliary test, spectroscopy, piperidine, hydrazine, 8-diazabicyclo-[5,4,〇]·7-undecene The compound has a concentration of 〇〇〇1 to 1 〇 mass, preferably 0.01 to 1% by mass, and is diluted with pure water to form an alkaline water solution 147754.doc-69-201115267 liquid, When a developing solution containing such an alkaline aqueous solution is used, it is usually washed (rinsed) with pure water after development. Further, in the method of forming a colored pattern of the present invention, the above-described color hardening may be performed. Composition layer forming step, exposure step: After the step, if necessary, a hardening step of hardening the formed coloring pattern by at least one of heating (post-baking) and exposure is performed. The post-baking is to achieve complete hardening. Heat treatment after development, through the heat curing treatment of wc~24n: In the case of the substrate being glassy 2=in the case of the above temperature range, it is better to use the thief~: under the previous material, using a heating plate or a convection supply box (hot air circulation type dry), a south frequency heating machine and the like The post-baking treatment is performed on the developed coating film in a continuous or batch manner. Fortunately, the coloring pattern formed by the color-curable composition of the present invention is suppressed even if the post-bake is performed. The color unevenness due to heating is due to the formation of a high-intensity coloring pattern with high definition and no hue of unevenness. Light: The number of hue of fr is repeated in the above-mentioned coloring first. The forming step, the exposing step, and the developing step, if necessary, the hardening step), thereby producing a color filter comprising the desired hue. Here, the color forming the bright coloring film is formed by the invention (4). The aspect is described in the center, but the present invention is not limited to the aspect. For example, the present invention and the w 73 formation method of the stone-bearing composition layer forming step, the exposure step, and the development step ( Further, depending on H7754.doc 20111526 7 The required hardening step) is also suitable for forming a black matrix on a substrate. Specifically, I'll perform the above steps by using the color hardening composition of the present invention containing a black colorant such as carbon black titanium black. A black matrix (black pattern) is formed on the substrate. The color filter of the present invention includes a colored pattern formed by using the color-curable composition of the present invention, and the coloring-curable composition is excellent in exposure sensitivity, and the substrate of the exposed portion The adhesion is good, and a high resolution pattern can be formed which provides the desired cross-sectional shape. Even if post-baking is performed to improve the hardenability of the colored pattern, the color due to heat treatment can be suppressed. The color filter of the present invention can be suitably applied to a solid-state imaging element such as a liquid crystal display element or a CCD (charge coupling device), and is suitable for use in a liquid crystal display element requiring an excellent hue. That is, the color filter of the present invention is preferably applied to a liquid crystal display element β "liquid crystal display element". The article is composed of the color filter of the present invention. More specifically, an alignment film is formed on the inner surface side of the color filter, and the electrode substrate is disposed to face each other, and the liquid crystal is filled in the gap portion and sealed, whereby a panel which is a liquid crystal display element of the present invention can be obtained. . According to the aspect of the present invention, it is possible to provide a coloring-curable composition which is excellent in image formability and which suppresses color unevenness even after post-baking, and a coloring pattern forming method using the coloring curable composition, and The color filter 147754.doc-71-201115267 piece of the colored pattern formed by the above-described coloring pattern forming method. In particular, it is possible to provide a right color with good patterning property, uneven color and film defects, and a souther contrast; a light-sensitive sheet 'and a high-quality coloring pixel can be provided by using the color light-emitting sheet' Liquid crystal display element. [Examples] Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited to the following examples unless the subject matter is exceeded. Furthermore, "parts" are quality benchmarks unless otherwise stated. [Synthesis Example 1: (A1) Specific anthracene compound: Synthesis of Compound 1] (A1) A specific anthracene compound [Compound 1] was synthesized by the method shown below. First, Compound A was synthesized by the procedure shown below. Ethylcarbazole (100.0 g, 0.512 mol) was dissolved in 260 ml of gaseous benzene, and after cooling to 0 °C, vaporized aluminum (70.3 g, 0.527 mol) was added. Then, o-benzonitrile (815 g, 0.527 mol) was added dropwise over 40 minutes, warmed to room temperature and stirred for 3 hours. Thereafter, after cooling to 〇 &lt;&gt;c, vaporized aluminum (75 1 g, 0.563 mol) was added. 4-gas butyl hydrazine (79.4 g, 0.563 mol) was added dropwise over 40 minutes, warmed to room temperature and stirred for 3 hours. Will be 35 masses of 156 mi. A mixed solution of hydrazine hydrochloride aqueous solution and 392 ml of distilled water was cooled to 〇 ° C, and the reaction solution was added dropwise. The precipitated solid was subjected to suction filtration, and then washed with distilled water and methanol. After recrystallization from acetonitrile, Compound A (yield: 164.4 g, yield: 77%) of the following structure was obtained. [Chem. 31] 147754.doc -72- 201115267

Next, using Compound A to synthesize compound ja, Compound A (20.0 g, 47.9 mm 〇1) 忿) was cold-dissolved in 64 ml of THF (tetrahydrofuran, tetrahydrofuran), and the force was &lt; g ' 50.2 mmol) Sodium hydride (0.7 g, 4 7Q ... m〇1) ° Then, add sodium hydroxide (2.0 g ' 50.2 mm () n, *, J, and reflux for 2 hours. Then 'cool down to Ot The sodium methoxide (10) methanol solution (1). i g' 57.4 surface 〇 1) was added dropwise over 20 minutes while stirring to room temperature and stirring for 2 hours. Next, after cooling to hydrazine, nitrite nitrite 7 was added dropwise over 20 minutes; g, 57.4 mmol), and the mixture was warmed to room temperature and stirred for 3 hours. . The reaction solution was diluted in 12 G ml of propylene, and the diluted liquid was added to a ΜN hydrochloric acid solution (cooled to ΜN hydrochloric acid solution. The precipitated solid was subjected to a pumping transition, and then washed with distilled water. Then, using B The wax was recrystallized to obtain a solid (yield: 17. g, yield: 64 〇 / 〇). The above solid (46.4 g, 85 mmol) was dissolved in ethyl acetate of 23 〇 147 754.doc • 73- 201115267 Medium ~,, force - ethylamine (10.3 g, 1 〇 1 mmol). Secondly, after cooling to 0 ° C, acetonitrile gas (8 〇g, 1 〇 2) was added dropwise over 20 minutes, then the temperature was raised to It was given for 1 hour. It was cooled to 1 〇 (8) d of distilled water, washed with π, extracted with ethyl acetate. After concentration under reduced pressure, it was added dropwise to 100 ml of water, and the precipitated solid was evacuated and then cooled. &quot; 卩1 to 150 ml of isopropanol was washed and dried to obtain the compound 1 of the following structure (yield 49 7 g, yield 99%).

Further, the structure of the obtained specific compound oxime was identified by NMR. (4-NMR 400 MHz CDC13): 8 86 (s, 1H), 8 6 〇 (s, called, 8.31 (d, 1H, J = 8.0 Hz), 8.81 (d, lHj J=8.0 Hz), 7.51- 7.2^ (m, 10H), 7.36 (q, 2H, 7.4 Hz), 3.24-3.13 (m, 4H), 2.36, 3H), 2.21 (s, 3H), 1.50 (t, 3H, 7.4 Hz). %, Comparative Example 1 used in the following comparative example instead of (4)) specific two compounds (Ciba Specialty Chemical Co., Ltd., Irgacure OXE 01), Comparative Compound 2 (Ciba Specialty Chemicals Co., Ltd. = 147754) .doc •74· 201115267

The structure of Irgacure OXE 02) and Comparative Compound 3 (manufactured by Ciba Specialty Chemicals Co., Ltd., Irgacure 3 69) is as follows. [化33]

IRGACURE OXE 01

IRGACURE 369 [1. Preparation of coloring curable composition A-1] A coloring curable composition A-1 containing a negative coloring agent (pigment) was prepared as a coloring curable composition, and a color filter was produced using the coloring curable composition. 147754.doc -75- 201115267 [Synthesis Example 2: Synthesis of Resin (i_i)] Mix 6.4 g of n-octanoic acid, 200 g of ε-Hexene, and 5 g of titanium (IV) tetrabutoxide. After heating at ° C for 8 hours, 'cooling up to room temperature, a polyester resin (i-Ι) β flow is shown below. [34]

.〇--iLc7H15_n J40 [Synthesis Example 3: Synthesis of Resin (j_i)] 1 〇g of polyethyleneimine (SP-018, number average molecular weight of 1,8 〇〇, manufactured by 曰本catalyst) and 1〇 The 〇g polyester resin (i-Ι) was mixed and heated at 12 ° C for 3 hours to obtain an intermediate (J-1B). Then, it was left to cool until 65 ° C. ' Slowly add 2 g of propylene glycol monoacetate acetate (hereinafter referred to as PGMEA (Propylene glyc〇 1 m〇n〇 methyl ether acetate)) containing 3.8 g of ruthenium anhydride. Stir for 2 hours. Then, PgmEA was added to obtain a solution of 10% by mass of PGMEA of the resin (J-1). The resin (j-丨) has a side chain derived from the polyacetic acid (1-1) and a carboxyl group derived from succinic anhydride. The synthesis scheme is shown below. 147754.doc -76- 201115267 [Chem. 35] H〇-ILcAs*11 + polyethyleneimine J-40 -(-CHsCHz-N^ 〇 |〇Η2〇Η2Ί|ΐ}ι2

ofCs^O^CyHis-n 〇f—^Oj^H -[CH2CH2-NH2]- 1 +^2(^2-1^2}^ -{-〇Η2ΟΗ2-ΝΗ-|-η+(&lt;

e〇fJ^^s^〇-j-2-C7Hi5-n e〇f**v^ eight~. Seven H °ϋ-〇 intermediate (J-1B) --4-CH2CH2-N4-k fcHaCHrN^ 〇 +CH2CH2-N-}i2

O^S 〇|LsJ^,^0^JLc7H15-n 〇(kx-N^,〇|-H xo2h y •fcH2CH2-NH2|-mi -j-CH2CH2-NH2j-m2 -fcH2CH2-NH4n

-Ι-ΟγΗΐδ-Π ]^~H Resin Ui) 1-1. Preparation of Pigment Dispersion - Preparation of Dispersion of Yellow Pigment PY150 _ Using a bead mill (zirconia beads, 0.3 mm), 40 parts (average Mixture of a solution of CI pigment yellow 150 (PY150) having a particle diameter of 60 nm as a pigment, and a solution of 223 parts by mass of PGME 上述 of the above resin (j1) in terms of 223 parts (2.23 parts in terms of solid content) Disperse for 3 hours to prepare a pigment dispersion. -Preparation of a dispersion of green pigment PG36 · Using a bead mill (yttria beads, 0.3 mm), 40 parts (PG36) containing 40 parts (average particle diameter of 60 nm) as a pigment, and 2〇〇 A mixture of the resin (i_i) was mixed (dispersed in a solid content of 20 parts) and dispersed for 3 hours to prepare a pigment dispersion liquid. Using dynamic light scattering (Microtrac 147754.doc -77· 201115267

Nan〇trac UPA_EXi 50 (manufactured by Nikkiso Co., Ltd.), the average primary particle size of the pigment was determined, and the result was 25 nm. '1 -2 - Preparation of coloring curable composition A-1 (coating liquid) The component of the following composition A-1 was mixed and dissolved to prepare a colored hardening composition A-1. &lt;Composition A-l&gt; (Composition 1) 26.1 parts 14.3 parts 2.0 parts 〇·9 parts 3.54 parts 1.24 parts 〇·57 parts•Dispersion of green pigment PG36 [(〇 colorant] • Dispersion of yellow pigment PY150 [ (c) Colorant] • Benzyl methacrylate-methyl acrylate copolymer (copolymer molar ratio of 7:3, weight average molecular weight of 5 〇 0 〇, acid value: 113) [Alkaline solubility Resin] • Exemplary Compound 21 [(D) Specific Alkali-Soluble Resin]

• A polymerizable monomer having 5 to 6 polymerizable groups in one molecule (manufactured by Sakamoto Chemical Co., Ltd., trade name: KAYARAD DPHA, 7:3 (mass ratio) mixture of pentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) [(b) Polymerizable compound] • Compound 1 [(Α1) specific hydrazine compound] • 2,2'-bis(o-phenyl)-4,4',5,5'-tetraphenyl hydrazine [ (Α2) biimidazole compound] • 1,2-epoxy-4-(2-oxopentyl) having an epoxy ring compound (2,2-bis(radiomethyl)_ι-butanol) Cyclohexane adduct, manufactured by Daicel Chemical Co., Ltd. EHPE_3i5〇) 147754.doc •78- 201115267 • Polymerization inhibitor (p-methoxyphenol) 0.0018 parts • Surfactant (fluorine-based surfactant, 0.0334 parts by DIC) Manufactured under the trade name Megaface F781-F) • decane coupling agent (3-mercaptopropenyloxy-trimethoxyl 0.320 parts of sulphur-based propyl alcohol) • Solvent (PGMEA) 5 1.42 parts The conditions determined by gel permeation chromatography (GPC, Gel Permeation Chromatography) of molecular weight and number average molecular weight are as follows.

Use the column: TSKgel MultiporeHXL-M

(Microporous polydisperse linear column) Tosoh manufacturing solution: THF Flow rate: 1.0 ml/min Temperature: 40 °C Detection conditions: RI system: complete high-speed GPC device (TosohHLC-8220) [2. Color filter Manufactured 2-1. Formation of coloring curable composition layer The coloring-curable composition A-1 containing the pigment obtained above was used as a resist solution, and slit coating was carried out under the following conditions. After drying on a 550 mm X 650 mm black matrix glass substrate, vacuum drying (66 Pa) and prebake (160 seconds at 80 ° C) were carried out to form a color-curable composition coating film (color-curable composition layer). . (Slit coating conditions) 147754.doc -79- 201115267 Clearance of the opening of the front end of the coating head: 100 μm Coating speed: 150 mm/sec Clearance between the substrate and the coating head: 1 50 μm Coating thickness ( Drying thickness): 2 μηη Coating temperature: 23 ° C 2 - 2. Exposure, development and then 'using a proximity exposure machine (manufactured by Hitachi High-Technologies, Inc., LE5565A)' to color the curable composition layer at 60 mJ/cm2 The pattern is exposed. The inorganic developing solution (trade name: CDK-1, manufactured by FUJIFILM Electronic Materials Co., Ltd.) was set to a 0% aqueous solution (25. The spray pressure of 〇 was set to 0.2 MPa, and the spray pressure was used. The entire surface of the exposed color-curable composition layer was developed for 6 sec seconds, and then washed with pure water. 2-3. Heat treatment, then, pure water was sprayed onto the colored curable composition layer and rinsed. The developer 'heated in an oven at 220 ° C for 1 hour (post-baking). A green coloring pattern was formed on the substrate in this way. 2-4. Formation of red, blue colored patterns and then 'using blue coloring The curable composition (CB_95〇〇L; manufactured by Fujifilm Electronic Materials Co., Ltd.) forms a colored pattern, and further forms a colored pattern using a red colored hardening composition (cr_95〇〇l; manufactured by Fujifilm Electronic Materials Co., Ltd.) , vapor deposition of IT〇 (indium Ηη oxide 'indium tin oxide)' was formed using a photopolymerizable composition (csp_321〇L; manufactured by Fujifilm Electronic Materials Co., Ltd.) The spacer is obtained from 147754.doc -80. 201115267 The substrate has green, red and blue light sheets. The color filter of the pattern (pixel) [3. Performance evaluation] - the coloring layer development step, the colored layer in order to evaluate the color ❹m bake) Step · "The same as above: the case, the process is carried out until the above steps are used" (曰: i formed a color hardening composition layer, and then made by ΐΓηί company), using potassium hydroxide-based liquid cdk]u (10) developer 0 parts by mass of cdp, 99 parts by mass of pure water, 25, developer. ^, the spray pressure was set to 0.2 MPa, and development was carried out in units of 10 seconds during a development time of 10 seconds to 11 seconds, and washed with pure water to form a color pattern, thereby obtaining the color pattern of Example 1. Further, in the same manner as in Example 1, except that the type or content of the specific polymerization initiator, the sensitizer, and the auxiliary sensitizer of (Al) and A2) was changed as shown in Table ', Example 2 was carried out in the same manner as in Example 1. The color patterns of Example 9 and Comparative Example 1 to Comparative Example 3. -81 - 147754.doc

S 201115267

w content by mass) 1 1 1 1 1 d 9 Ο m inch c&gt; 5 ο 1 I 1 1 1 1 system I 'w^ type 1 1 1 1 1 5: CN [Xi m (X. 1 coffee 1 1 1 1 sensitizer content (parts by mass) 1 1 inch 〇Ο inch 〇 1 m ο ΓΛ 〇mo 1 1 1 1 1 1 type 1 Cao r—( CN C m &lt; 1 (Ν &lt; CN &lt; CN &lt; ' I 1 f 1 1 Ψ 5 _ 〇〇uo Ο ^Τ) Ο t 4 Ο inch r«-H o inch τTMΗ 寸 inch t—H o inch τ—H o 卜ν ο ο ο 〇 〇 1 Bu 〇Ο On as ο ΟΝ ON O) o &lt;0 # 起¥ &lt;rt ζ S—✓ Ο Ο —·Η Ο o »—Η (Ν m ϊ ι-Η 荽# # τ—Η /—\ 荽荽荽荽龚龚荽&lt;D &lt;0 荽荟&lt;〇々&gt;&lt;0&lt;〇&lt;〇λ3 〇3 δ3 4〇1 &lt;η &lt; Λ3 JJ Jj δ3 -Ο δ3 δ3 jD ZHAO Ling JJ α3 jJ £ jJ The content of the test resin content is 质量 CN 1 ο (N Ο &lt;N Ο &lt;Ν ο &lt;Ν Ο &lt;Ν Ο CN o (N Ο (Ν 〇(Ν Ο CN 〇CN 〇(Ν CN S_✓ i o * * * 寒·〇I CN 荽(N CN(N CN τ-Η CN(N (N (Ν r-Η &lt;Ν 荽 荽 荽 荽 荽 鼓 鼓 & & & 〇 〇 〇 n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n 〇&lt;〇&lt;〇.〇δ3 &gt;γ- Jj Δ3 .〇aJ λ3 aD 〇2 λ3 5 5 5 5 i ϊ ξ ί Ϊ ϊ 5 苳苳军军ΓΝ m Ό Ό 00 00 CN m inch w \ 〇Magnetic anchor {Κ %K ΐΚ Λ〇_〇aJ a3 jJ · 82· 147754.doc 201115267 The sensitizers A1 to A3 in Table 1 'the auxiliary sensitizers F1 to F3 are the compounds shown below. A1 : 4,4·bis(diethylamino)benzophenone A2 ·-ethyl-9-oxothiotene p star

F1 : 2-mercaptobenzimidazole F2 : 2-mercaptobenzopyrene β sitting F3 : Ν-phenyl-2-pyridylbenzopyrene-development time evaluation _ &amp; using optical microscopy to observe each pass 1 The substrate after the development time of leap seconds was evaluated for the state of development' and is collectively shown in Table 2. In Table 2, the lower limit of development time is the lower limit second of the development time that can be used, and if it is shorter than the time, the non-pixel portion cannot be removed. The upper limit of the development time refers to the upper limit of the number of seconds of development time that can be used. If it is longer than this time, the pixel of the beauties will be defective or fall off. Also, considering the constraints of the process (working time 3), the development time is preferably 8 Gsec or less. In addition, the development latitude table indicates the difference between the upper limit of the development time and the lower limit of the development time. «47754.doc -83 - 201115267 - Evaluation of pattern linearity _ Using optical microscopy锖

Ball μ \ Mirror reflection mode, 200 times) Take a photo of the coloring map blank * A and evaluate it. At 5 cm χ 5 cm: The edge is like the edge portion and is evaluated on the basis of the following criteria. +, .W observes ""good": the edge of the pixel looks straighter and slightly better"] the part of the edge of the pixel (1/3 of the overall length is not: straight" but not formed as a sawtooth The "slightly sloppy" pixel edge portion exceeds the overall length, or a part of ήI is non-linear (1/4 or less of the overall length) is formed into a zigzag shape. · The pixel edge portion exceeds 1/4 of the overall length. It is preferably formed into a shape in which the edge portion of the pixel pattern is a linear shape. If the edge portion of the pixel pattern is formed into a mineral tooth shape due to a residual film or undercut, or other reasons, it is necessary. It overlaps with the black matrix to a large extent. In this case, the width of the black matrix is enlarged to reduce the aperture ratio. Moreover, when it overlaps with the black matrix to a large extent, it may be at the edge of the black matrix. In the vicinity of the portion where the coloring layer is not colored and leaks out. Further, when the edge portion of the pixel pattern is in the form of a mineral tooth, there is a problem that the transparent electrode formed thereon is broken and the resistance value is increased. Evaluation - The edge portion of the pixel pattern was photographed and evaluated using an optical microscope (reflection mode, 2 times magnification). The edge portion of the pixel was observed at a photograph of 5 cm x 5 cm to determine whether or not there was a defect. As a criterion for judgment 'When the following was observed In either case, it is considered that 147754.doc -84- 201115267 has a defect 'evaluated as "X": (edge „ main ox-like shape, (2) although missing shape is also observed (1) TC &lt; Inconspicuous, the disc circumference is thinner than the line width, and it is identified as a defect. One/we will not evaluate the defect as "Γ〇". Therefore, it is not good. When the field is defective, 'this part is White light leakage - evaluation of color unevenness after post-baking - Evaluation of the pattern with the pixel pattern: the pattern of the rotation using an optical microscope (reflection mode, 200 times). Evaluation was performed on the basis of the following criteria. A microscope photograph of uneven color is obtained by using an Olympus optical microscope MX51' at a magnification of twice the brightness of a bright field. A microscope photograph that serves as a reference for color unevenness determination. In the case of Fig. 1 (A), it is judged as "colorless unevenness", and the evaluation is "〇". As shown in Fig. 1 (B), the color of the color is confirmed in the pattern. When the time is judged as "color uneven" and is evaluated as "X". 147754.doc • 85- 201115267

[Table 2] Development time (sec) Pattern straightness defect Post-baking color unevenness lower limit upper limit latitude Example 1 20 80 60 Jiayi Example 2 30 80 50 slightly better Example 3 20 80 60 Good 〇〇 Example 4 10 70 60 〇〇 〇〇 Example 5 10 70 60 〇〇 〇〇 Example 6 10 80 70 〇〇 〇〇 Example 7 10 70 60 〇〇 〇〇 8 8 10 70 60 〇〇 〇〇 〇〇 9 10 70 60 Jiahao Comparative Example 1 50 80 30 slightly worse X 〇 Comparative Example 2 40 80 40 slightly different 〇〇 Comparative Example 3 10 40 30 〇〇 Comparative Example 4 10 70 60 〇 X Comparative Example 5 10 70 60佳〇X Comparative Example 6 10 70 60 〇X According to Table 2, in Examples 1 to 9 in which the color hardening composition of the present invention was used, when the pattern was formed, the development latitude was large, and the pattern was linear. It is also good and has good developability without defects. Also, color unevenness did not occur after post-baking. (Example 10, Example 11) Instead of the compound 1 in Example 1, the following compounds 2 and 3 were respectively used (the benzenethiol was changed to the corresponding compound, respectively, and the synthesis example 1 147754.doc -86- 201115267 Synthesize in the same way) Prepare ^ as the same way as humans. In the same manner as in Example 1, the color hardening composition was used, and the ball 庐, 丄 I -, and the yoke example 1 were similarly mussels, '. The same results as in Example 1 were obtained. [化37]

(Example 12) In Example 1, the heat treatment conditions in the post-baking step were changed from tempering at 220 C for 1 hour to 丨(6)^下丨, and the substrate was subjected to n-methyl group. The substrate was immersed for 5 minutes in the ketamine solution (25. 〇, the substrate obtained by the jin was observed under the optical microscope in the same manner as the defect evaluation, and as a result, the surface was slightly cracked. (Example 13) Example 6 The heat treatment conditions in the post-baking step were changed from 1 hour at 220 ° C to 1 hour at 160 ° C, and the substrate was immersed in the N-methylpyrrolidone solution for 5 minutes (25. The obtained substrate was observed under an optical microscope in the same manner as the defect evaluation, and as a result, no surface crack was observed. 147754.doc -87- 201115267 Comparative Examples 12 and 13 show that (4)) specific two compounds and (A2) diazepam When the content ratio of the compound is within a preferable range, the curing property of the coloring pattern is further improved to improve the development resistance. (Example 14) 11.5 parts of the dispersion of the green pigment PG36 used in Example 1 was used instead of the yellow pigment. A dispersion prepared by using a purple pigment pm in the same manner as the pigment type, and using NK Ester Α_τΜΜΤ (manufactured by Shin-Nakamura Chemical Co., Ltd.) instead of the dispersion of PY15G KAYARAD DPHA is a polymerizable monomer having 5 to 6 polymerizable groups in one molecule to prepare a colored curable composition, and the colored curable composition is used, except that the exposure step is changed as described below. EXAMPLES A color filter was produced in the same manner, and the same a flat j was obtained, and as a result, the same good results as in Example 1 were obtained. (Exposure step) Using EGIS (V Technology Co., Ltd., YAG laser (yttrium) The third harmonic of the aluminum garnet laser, 钇-aluminum-garnet laser, with a wavelength of 355 nm and a pulse width of 6 nsec: Ht is a laser exposure device, and the surface of the photosensitive resin composition layer is passed through a photomask. The pulse wave of about 1 mJ/cm2 was irradiated 20 times. According to the results, it was found that the pattern was exposed by a laser exposure machine, and the same effect as the exposure by the high pressure mercury lamp was obtained. (Comparative Example 4) Comparison using The colored hardening composition of Example 1 was obtained by the same exposure step as in the above Example 147754.doc • 88-201115267, result 14 to obtain a surface crack to be colored calender And evaluated, the surface crack, # are the same results as the comparison example i. In addition, the exposure is even worse. x, the heart is better than the comparative example] using the mercury lamp [schematic description] Figure 1 shows The color unevenness determination using the colored pattern of the present invention was made by the polymerizable composition, and the color was not darkened in the pattern, and it was judged as "colorless;: Microscopic: Photo # ' (A) The color of the pattern was confirmed in the pattern. In the case of the judgment of the judgment, (9) is a judgment example of ', color unevenness'. 147754.doc 89-

Claims (1)

201115267 VII. Patent application scope: 1 . A coloring-curable composition which comprises: (A1) a compound represented by the following formula (1), (A2) a biimidazole compound, (B) a polymerizable compound, a coloring agent, and D) Alkali-soluble adhesive resin having a double bond in the side chain: '[Chemical 1] In the above formula (I), R, BG and Q each independently represent a monovalent organic group, Z represents a hydrogen atom or a monovalent substituent, and n2 represents an integer of 〇~5. 2. The colored curable composition according to claim 1, wherein the (c) coloring agent is a pigment, and further contains (E) a pigment dispersing agent. A method of forming a colored pattern, comprising: forming a colored curable composition layer using a color hardening composition as claimed in claim 1 or 2; exposing the colored curable composition layer in a pattern And a step of hardening; and a step of removing the color-hardening composition layer after the exposure, and removing the uncured color-curable composition to form a colored pattern. 4. A color calender having a colored pattern formed using the method of claim 3 I47754.doc 201115267 on a support. A liquid crystal display device comprising the color filter of claim 4. 147754.doc