TW201221520A - Color composition for a color filter, color filter and production method thereof, anthraquinone compound, and liquid crystal display device - Google Patents

Abstract

A coloring composition for a color filter, the color filter, a method for manufacturing the same, an anthraquinone compound, and a liquid crystal display device are provided to improve contrast by increasing colority and brightness. A coloring composition for a color filter includes a dipyrromethene metal complex, a compound, and an anthraquinone compound. In the dipyrromethene metal complex, a compound represented by chemical formula I is coordinated by metal atoms or metal compounds. The compound is selected from a group including dye compounds represented by one of chemical formulas II to VIII. In the chemical formula I, the R1 to R6 are respectively hydrogen or substituent. The R7 is hydrogen, halogen, an alkyl group, an aryl group, or a heterocyclic group.

Description

201221520 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a coloring composition for a color filter containing a dye as a coloring agent, a color filter, a method for producing the same, and an anthraquinone compound And a liquid crystal display device. [Prior Art] A pigment dispersion method is widely used as a method of producing a shirt color filter used in a liquid crystal display device or a solid-state image sensor. As a pigment 77 method, there is a method of producing a color filter by a lithography method using a color-sensing radioactive composition in which a pigment is dispersed in various photosensitive compositions. In this method, the composition containing the pigment is stable to light or heat, and at the same time, due to the pauerning by the lithography method, * sufficiently ensuring the positional accuracy 'is considered to be suitable for making a β, making color The color display uses a method such as a blue light-emitting sheet. 4 used in the production of color filters, ',, v -Ή V—> Fi 4 I to the material, and also widely used for pigment compounds other than pigments such as dyes; (4) Materials: dense bite; wood, pyrazole azo-based sputum A ^ eucalyptus, xanthene dyes and other compounds with various pigment precursors (for example, see special opening. (4) Tekailu. No. 8 bulletin, No. 4 (4), using dye as a coloring agent, by the sharpness of the dye itself (a) or hue, in the ancient phase or the brightness of the stomach..., the image when displayed: The point of the degree is considered to be useful. -4- 201221520 Further, it has been revealed that a specific color filter such as contrast is used for a specific ruthenium compound (Example No. 2001-108815). DISCLOSURE OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The present invention has been made in view of the above prior art. It is an object of the present invention to provide a coloring group for obtaining a high contrast color filter while using a dye. Like the color light method shown as possible' In addition, the liquid crystal display device and the hue are excellent. The object of the present invention is to achieve the object. [Means for Solving the Problem] The present invention has been intensively reviewed, and as a result, it has been found that a compound and a specific dye compound form an image, and the image is greatly improved. The present invention has been completed in a comparative manner. In order to achieve the above-mentioned problem, the specific means is as follows: < 1 > A colored composition for a color filter, which is coordinated by a compound represented by the following formula (I) to A metal compound is a pyrrolemethylene metal complex compound (II) to a dye compound represented by any one of the formula (VIII), and a ruthenium compound (preferably having 蒽_9, 10_) The diketone); as a dye, the high hue or brightener of the present invention, the color photograph and the bismuth compound thereof can be used as compared with the prior art if it is used as a dye. Compound of group la skeleton formed by the following formula 201221520

R 3 , R 4 , R 5 and R 6 each independently represent an argon atom or a substituent; and R 7 represents a hydrogen atom, a li atom, an alkyl group, an aryl group or a heterocyclic group;

R35 Formula (Π) In the above formula (π), Α1 represents a radical selected from the group consisting of 5-pyrazolone, isoxazolone, barbituric acid, thiobarbituric acid, lodanine, and betaine. Urea, thioacetamidine, oxazolidinone, pyrazolidinedione, indandione, warp group. ratio. Ketone,. ratio. Sit and. ratio. S, 1,2,3,4-tetrahydroindole-2,4-dione, 3-oxo-2,3-dihydrobenzo[d]thiophene-1,1-dioxide And an acidic core derived from a compound of the group consisting of 3-dicyanodecyl-2,3-dihydrobenzo[d]thiophene-1,1-dioxide; L1, L2 and L3 represent a fluorenyl group; R33 and R34 each independently represent an alkyl group, an aryl group, an alkoxycarbonyl group or a hydrogen atom; R35 represents a hydrogen atom, a methoxy group, a gas atom, a methyl group or a nitro group; η represents 0 or 1; The substituent 'bonded to at least one of A1 and R33 to R35 has at least one selected from the group consisting of a ruthenium, a sulphate, and an amine sulphate; 201221520 im' CN RIsf

β|ίΛ# N^=N*

R

44N Lu 45 fil' β4β: General formula (III) In the above formula (III), 'R41 represents a heterocyclic ring 42- or a substituent; R43, R44, R45, R46, and R, and R represents a hydrogen atom; An alkyl group, an alkenyl group, an alkynyl group, 4 and R48 each independently, an alkoxycarbonyl group, an aryloxycarbonyl group, an amine carbaryl group, a heterocyclic group, a decylsulfonyl group or an amine sulfonyl group; R43 and R44 may be used. =, fluorenylsulfonyl, aryl, 6-member or 7-membered ring; R45 and R46 can be bonded to each other to form a ring of 5 or 7 members; R47 and ^6 are knotted to form 5 members, 6 or Ring of 7 members; And form 5 members, 6 members

In the above formula (IV), Ra?, Ra2, and Ra3 each independently represent a hydrogen atom or a monovalent substituent, and Rbl, Rb2, and Rb3 are bonded to form a heterocyclic ring of 5 to 7 members; t, Μ2 and Μ3 may mutually indicate a substituted or unsubstituted aliphatic group, a substituted or a., a substituted aryl group, or a substituted or unsubstituted heterocyclic group; η represents 〇'!, 2 or 3' „ When it is 2 or more, the plural Rb2 and Rb3 may be the same or different; 201221520

In the above formula (V), R6I, R62, R63 and r64 each independently represent a hydrogen atom, an alkyl group which may be substituted, an aryl group or _S〇2NH_R; and R65 represents a nitrogen atom and may be substituted. Alkyl, aryl, _s〇3h or ·s〇2NH_r, where R represents alkyl, alkoxyalkyl, cyclohexyl, cyclohexylalkyl, alkoxy, aryl or alkylcarbonyloxy n represents an integer of 0 or more, but when η is 0, at least one of RH to R65 represents an aryl group having -so2nh-r as a substituent;

In the above formula (VI), 'R71 represents an alkyl group having 2 to 2 carbon atoms, a cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain, and the carbon number of the alkyl chain is i~ 4, a group of cyclohexyl groups, an alkyl group having a carbon number of 2 to U substituted by a halogen number of 2 to 12, an alkylcarboxyalkyl group represented by L71-CO-〇-L72-, L 3- a gas-burning group represented by 0-C0-L74-, a phenyl group substituted with a decyl group having 1 to 2 carbon atoms, or an alkyl group having a carbon number of 1 to 20 substituted with a phenyl group; L71 represents a carbon number 2 to 12 alkyl; L72 represents an alkylene group having 2 to 12 carbon atoms; L represents an alkyl group having 2 to 12 carbon atoms; L74 represents an alkylene group having a carbon number of 2 to 12, 201221520; R72, R73, R74 and R75; Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group or a _ atom;

In the above formula (VII), Ζ1 and Ζ2 each independently represent an oxygen atom or a sulfur atom; and R81, R82, R83 and R84 each independently represent a hydrogen atom and a saturated aliphatic hydrocarbon group having a carbon number of 1 to 10; a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted by a hydroxy group, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted with an alkoxy group having 1 to 8 carbon atoms, and a sulfanyloxy group having 1 to 8 carbon atoms a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an indenyl group having 2 to 10 carbon atoms; R85, R86, R87, R88 and R89; R11Ga, Rllla and R112a each independently represent a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a halogenated saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 8 carbon atoms. a group, a carboxyl group, a sulfo group, an amine sulfonyl group or an N-substituted amine sulfonyl group; at least one of R85 to R89 and R11Qa to R11 2 a represents an N-substituted amine stone hydrazine;

201221520 In the above formula (VIII), R91, R92 and R93 each independently represent a hydrogen atom, a halogen atom or a repeating acid group; A3 represents any one of the following (a) to (d); and 1 represents 1 or 2; An integer; when 1 is 2, the plural R91, the plural R92, and the plural R93 may each be the same or different; in the following (a), R94, R95 and R96 each independently represent a hydrogen atom, a methyl group, a halogen atom. And a sulfonic acid group or -S02N(R97)(R98), R97 and R98 each independently represent a hydrogen atom, a lower alkyl group having 1 to 8 carbon atoms or a phenyl group; and at least one of R91 to R96 represents a rhein group.

The colored composition for a color filter according to the above-mentioned <1>, wherein the oxime compound is a compound represented by the following formula (IX):

-10- 8 201221520 each independently indicates that when hydrogen is different from R12a, when hydrogen 1 is an integer of 2 to 4, Rlla and R12a, an alkyl group, an aryl group or a heterocyclic group in the formula (IX) are described. Rlla atom; η11 represents an integer of 1 to 4, and NRllaR]2a of ηι plural may be the same or different. The coloring composition for a color filter according to the above-mentioned <2>, wherein the compound represented by the above formula (IX) is a diamine-based hydrazine represented by the following formula (X). Compound:

In the above formula (X), R21a and n22a each independently represent an alkyl group or an aryl group. The coloring composition for a color filter according to the above-mentioned item (3), wherein the compound represented by the above formula (X) is a diamine hydrazine represented by the following formula (XI). Compound: '11- 201221520

N31 General formula (XI) Ο ΗΝ In the above formula (XI), R31a, R32a, R33a and R34a each independently represent an alkyl group or a halogen atom; and R35a and R36a each independently represent an alkyl group, an alkoxy group or an aryloxy group. a sulfo group or a salt thereof, an aminosulfonyl group, an alkoxysulfonyl group, or a phenoxysulfonyl group; η31 and η32 each independently represent an integer of 0 to 2, and when η31 and η32 are 2, a plural number R35a, R36a may be the same or different. The coloring composition for a color filter according to the above-mentioned <4>, wherein the compound represented by the above formula (XI) is represented by the following formula (XII) or the following formula (XIII) The compound selected from the diamino sulfonium compounds shown: 8 -12- 201221520

In the above formula (XII), R41a, R42a, R43a and R44a are each independently

Ground represents an alkyl or halogen atom; R 45a

R 46a, R47a and R48a each independently represent an alkyl group, a sulfo group or a salt thereof, or an aminosulfonyl group; and any of R45a and R47a and any of R46a and R48a represent a sulfo group or a salt thereof or an amine Base continuation

Formula (0) - 13 - 201221520 In the above formula (XIII), R51a, R52a, R53a and R54a each independently represent an alkyl group or a halogen atom; and R55a and R56a each independently represent an argon atom or an alkyl group; R57a and R58a each independently represent a hydrogen atom or an alkyl group; L51a and L52a each independently represent a divalent linking group, and each of L53a and L54a independently represents an oxygen atom or a -NH- group. The coloring composition for a color filter according to any one of the above-mentioned <1>, which further comprises a polymerizable compound and a photopolymerization initiator. The coloring composition for a color filter according to any one of the above-mentioned, wherein the total content of the brewing compound is 50% by mass based on the total amount of the dye compound. the following. &lt;8&gt; A color filter comprising: a substrate, and a coloring composition for a color filter according to any one of the above-mentioned <7> to <7>, which is formed on the substrate. Shaded area. (9) A method of producing a color filter, comprising the step of applying the colored composition according to any one of the above <1> to <7> to a support to form a colored layer. And a liquid crystal display device comprising the color filter described in the above <8>, which is formed by exposing the formed colored layer to a pattern-like image to form a colored region. _, / iff &lt; 9 &gt; Description &lt; 1 1 &gt; A liquid crystal display device comprising the color extinguishing film produced by the method for producing a color filter of (1): &lt;12&gt; - a variety of products of the following general formula (XIV) 201221520

RX2 IWX4,, Ο HN. ?X1 s〇NH^CHi Y'丫so2mh General formula (XIV) RX1 '3 , ?H·· RX2 In the above formula (XIV), RX1 is independently represented; Rx 2 is independent The ground indicates a carbon number of 1 to 1 烧. The base of the surface is not a carbon number of 1 to 1 ,, and X4 is independently shown. [Effects of the Invention] According to the present invention, it is possible to provide a color by using a dye hue or brightness. A high contrast color light film is obtained. Further, according to the present invention, a color filter which is excellent in hue and possible for display and a method of manufacturing the same can be provided as a display device. Further, according to the present invention, it is possible to provide a method of obtaining a hue. [Embodiment] ~ [Mode for Carrying Out the Invention] Hereinafter, a color filter of the present invention will be described in detail. Furthermore, the method for producing a private color of the present invention using the same, and a liquid crystal display device, and a novel coloring composition for color filters are also described in detail. The coloring composition for a color light-emitting sheet of the present invention The compounds which are not shown in the formula (I) are coordinated to the metal orthomethyl group or the ethyl group X3 independently. On the other hand, an image with a coloring composition ratio and a liquid crystal ruthenium compound are improved. Coloring composition Filters and their brewing compounds. Included in the following: a dipyrromethene metal complex compound obtained by selecting or metallizing -15-201221520 and a dye compound represented by any one of the following formulas (II) to (VIII) The compound in the group and the ruthenium compound; preferably, a polymerizable compound and/or a photopolymerization initiator are used to constitute photosensitivity. In addition, the coloring composition for a color filter of the present invention may further contain a binder such as a soluble resin, an organic solvent, or the like, and various additives. The present invention surprisingly produces a colored image with good hue and contrast by presenting the dye compound together with the ruthenium compound, without sacrificing the desired hue. In this way, for example, when the image is displayed by the liquid crystal display device, the image color and the brightness of the color or the color can be displayed while maintaining the high image hue and brightness while preventing the hue from decreasing. The components of the coloring composition for a color filter of the invention will be described in detail. Further, in the following, the coloring composition for a color light-emitting sheet of the present invention is also referred to simply as the coloring composition or coloring composition of the present invention. In the present specification, "~" means a range equal to or greater than the lower limit value and equal to or less than the upper limit value. ( Brewing Compound) The coloring composition of the present invention contains at least one of cerium compounds. By containing this ruthenium compound, although the reason is not determined, the contrast can be effectively improved. The ruthenium compound in the present invention is a compound having a maximum absorption at 400 to 700 nm, and in the present invention, it is preferably a ruthenium compound having a large absorption of from -16 to 201221520 at 500 to 700 nm, particularly preferably at 550 to 7 Torr. Nm has a great absorption. In the case of the ruthenium compound having such a maximum absorption, the structure is not particularly limited. The contrast improvement effect is excellent. Among the awake compounds of the present invention, an oxime-based quinone compound represented by the following formula (lx) is preferred. Among the diamino-based stilbene compounds, from the viewpoint of absorption characteristics, the compound represented by the following formula (X) is more preferable, and from the viewpoint of thermal stability, the formula is more preferably shown below. Further, the compound represented by the formula (XI) is more preferably a compound represented by the formula (XII) or the formula (XIII) from the viewpoint of coexisting absorption characteristics and thermal stability. First, an amine ruthenium compound represented by the following formula (IX) will be described

In the above formula (IX), R1 la and each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and the rule 113 is a hydrogen atom different from RlZa. The alkyl group represented by R a and R 12a is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having a carbon number of i to 20, and particularly preferably an alkyl group having a carbon number of i to i0. As an example, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an n-octyl group, a n-decyl group, a n-hexadecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group and the like can be given. -17- 201221520 The aryl group represented by Rlla or R12a is preferably an aryl group having a carbon number of 6 to 3 Å, more preferably an aryl group having a carbon number of 6 to 20, particularly preferably an aryl group having 6 to 12 carbon atoms. . As an example, a phenyl group, an o-nonylphenyl group, a p-nonylphenyl group, a 2,6-dimethyl stylyl group, a 2,6-diethylphenyl biphenyl group, a 2 phenyl group, and a naphthyl group are mentioned. , onion base, phenanthryl and so on. The heterocyclic group represented by Rlla or R12a is preferably a heterocyclic group having a carbon number, more preferably a heterocyclic group having a carbon number of from 丨 to 12, and examples of the hetero atom include a nitrogen atom and oxygen. Atom, sulfur atom. Examples of the heterocyclic group include an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a thienyl group, a 2 oxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a naphthylthiazole group, and a benzoxazole. Base, carbazolyl, azepine group, and the like. Further, the alkyl group, the aryl group and the heterocyclic group represented by Rlu and R12a may further have a substituent. Further, as a further substituent in the case of a further substituent, for example, an alkyl group is preferable: a carbon number H0' is more preferably a carbon number (9), and particularly preferably an alkyl group having a carbon number i 0 , and examples thereof include a methyl group. Ethyl, isopropyl tributyloctyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cycloalkyl (preferably having a carbon number of 2 to 3 Å, more preferably a carbon number of 2 to 2) 2〇, 2;, 2: 1 烯基 of the alkenyl group ', for example, a vinyl group, an allyl group, a group, a 3-pentenyl group, etc.), an alkynyl group (preferably a carbon number of 2~) 3〇, more d 2〇, particularly preferably an alkynyl group having a carbon number of 2 to 1 Å, for example, a carbon number I or a triacetylene group, or an aryl group (preferably, a carbon number of 6 to 3 Å, More preferably sigh 6 to 20, especially good for carbon number 6~| Stupid base, pair of square base, for example, base (preferred base 1, base, phenanthryl, etc.), amine is a slave More preferably, it is a carbon number 〇~2〇, particularly preferably an amino group, an alkylamino group, an arylamino group or a heterocyclic amino group having a carbon number of 〇-18- 201221520. As a specific example, An amine group, a decylamino group, a dimethylamino group, a diethylamino group, a dibenzylamino group, a diphenylamino group, a tolyl group. The base isocetyloxy^ (preferably having a carbon number of 30' is preferably a carbon number!~", particularly preferably an alkoxy group having a carbon number of from 10 to 10, and examples thereof include a methoxy group, an ethoxy group, and a butoxy group. a certain 2-ethylhexyloxy group or the like, an aryloxy group (preferably having a carbon number of 6 to 3 Å, more preferably a carbon number of 6 to 20, particularly preferably an aryloxy group having a carbon number of 6 to 12, for example, Examples thereof include a phenoxy group, a naphthyloxy group, a 2 —naphthyloxy group, and the like, and an aromatic heterocyclic oxy group (preferably having a carbon number of 1 to 30, more preferably a carbon number of 1 to 2 Å, particularly preferably a carbon number). The aromatic heterocyclic oxy group of the hydrazine is, for example, an anthraceneoxy group (tetra)oxy group, an oxy group, a quinolyloxy group or the like, and a mercapto group (preferably having a carbon number of 1 to 30, more preferably The fluorenyl group having a carbon number of 1 to 20, particularly preferably a carbon number of 12, may, for example, be an ethyl hydrazide group, a benzamidine group, a decyl group or a dimethyl fluorenyl group, or an alkoxycarbonyl group (preferably Carbon number 2~3〇' is better for carbon number 2~20' especially good for carbon number 2 is called methoxy group, ethoxy group, etc.), aryl oxygen_good is &quot; better for slaves 7~20 Particularly preferred is a oxycarbonyl group having a carbon number of 7 to 12, for example, a sulphide based on a spurt, and a decyloxy group (preferably a carbon number of 2 to 3 0). More preferably a carbon number? .., particularly preferably 2~1 carbon number of acyl group of square

For example, it may be exemplified by the scorpion animal I Jia A stone mountain M soil, the present F methoxy group, etc., and the thiol amine group (more than 2 to 30, more preferably 2 to 20 carbon atoms, particularly preferably carbon number) 2~1〇 of a mercaptoamine group, for example, with Hawthorn H 10 , alkoxylated face A i + ethionylamino group, benzhydrylamine group, etc.) soil (preferably carbon number) 2~30, more preferably carbon number 2~2〇, especially good for carbon number 2~〗 9 &amp; good for slave number 2~20 arylamino group, etc., aryloxy alkoxylated amino group For example, an oxyoxycarbonylamino group (preferably having a carbon number of 7 to 3 Å, more preferably -19 to 201221520, a carbon number of 7 to 20, particularly preferably an aryloxycarbonylamino group having a carbon number of 7 to 12) may be mentioned. For example, a phenoxycarbonylamino group, a sulfonylamino group (preferably a carbon number of 1 to fluorene, more preferably a carbon number of 1 to 20 Å), particularly preferably a sulfonylamine having a carbon number of 1 to fluorene For example, it may be exemplified by a repeating amine group, a benzoylamino group, etc.] an amine continuation (preferably, a carbon number 〇~3 〇, more preferably a carbon number 〇~2 〇, particularly preferably The amine group of the carbon number 〇~U can be exemplified by an amine group, a methylamine group, a dimethyl group, and a phenylamine stone. Etc.), Yue'an f-based (more than two carbon number 32, more preferably carbon number... especially good for carbon number (10) female nail base, for example, amine methyl sulfhydryl, methylamine formazan Base, diethylene: amine methyl, phenylamine, thiol, etc.), alkylthio (preferably di char: i 3 〇 'more preferably carbon number (9), especially good carbon number! ~ i2 alkane The thio group may, for example, be a methylthio group or an ethylthio group, or an arylthio group (preferably having a carbon number of 6', more preferably a carbon number of 6 to 20, particularly preferably a carbon number of 12 arylthio group, for example A phenylthio group or the like, an aromatic heterocyclic thio group (preferably a carbon number (10), more preferably a carbon number, particularly preferably a carbon number-based heterocyclic thio group, for example, an pyridinethio group , 2-benzimidazolylthio group, 2-benzoxazolethio group, I benzoxylthio group, etc.), continuous sulfhydryl group (preferably carbon number 3 (), more preferably carbon number i 'excellent For the carbon number of the carbon number 12, for example, a base can be used to make a base, etc. (preferably, the carbon number is better: two?., particularly preferably a carbon number of 1 to 12) Sulfhydryl group, for example, may be ~3η δ ^ 丰亚s 醯 荨 、), urea group (preferably carbon number 1 is more preferably carbon number 1 to 2 〇, particularly preferably carbon number 1) The urea group of 12, for example, a urea group, a methylurea group, or a soil (preferably a carbon number H, more preferably a carbon number amide group, an inverse number of 1 to 20, particularly preferably a carbon number) 1 8 -20- 201221520 ~1 2 decyl citrate 'for example I + _, Gan * a

+ one ethyl acrylate amide group, phenylphosphonium amide group, etc.), hydroxyl group, 岬A ^ A group, spectrin atom (for example, fluorine atom, chlorine atom, bromine atom 'iodine atom), 訇} cyano group a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, a sulfinyl group, a fluorenyl group, a arylene group, a mercapto group, or a heterocyclic group (preferably a carbon number of 1 to 3 0 'more preferably a carbon number! Examples of the hetero atom include a nitrogen atom, an oxygen atom, a κ ^ , and a force L atom. Specific examples thereof include an imidazolyl group, a ratio of a certain group, a quinine group, a t group, and a fluorinyl group. Furanyl, thienyl, piperidinyl, linyl, benzoxanthyl, benzo, mastyl, benzoyl, etc., decyl group (preferably carbon number 3) ～40, more preferably a carbon number of 3 to 30, a particularly good carbon number of 3~1, a 夂 0 0 24 矽 alkyl group, for example, dimethyl sulphur base 'triphenyl stone 炫 Hyun, its cage, 镗, ^ Replace + soil / condition 丞 4) special. These substituents may be further represented by the above formula (IX), and nH represents an integer of i to 4, and when it is broadly an integer of 24, the plural NR1UR12a may be the same or different.

In the general formula (X), in the formula (X), R2 "and R22a each independently represent a burnt group or a burn group represented by R_2la or R22a" preferably has a carbon number of 1 to It is a thiol group having a carbon number of 1 to 2 0, particularly preferably a carbon number of 1 to 1 -21-21 - 201221520 alkyl group. As an example, I ώ Α τ 甘 出 methyl, ethyl, isopropyl, third Butyl, n-octyl, n-decyl, n-decyl, etc. Tert-octyl, propyl, cyclopentyl, and ring as R21 a, R22a _ ^, aryl &amp; Preferably, the carbon number is 6 to 30, more preferably the carbon number is 6 to 2: it is a square base of $^~屯U, particularly preferably a square having a carbon number of 6 to 12. As an example,山纪# + out of the base, o-mercapto, stetyl, p-methylbenzene, 6-monomethylphenyl, 2,6-diethylpyrazine, its f44-glycine-ethyl group, such as the base, 2,6-dibromobenyl, naphthyl, anthracenyl, phenanthryl, etc. 6: a substituent of an alkyl group, an aryl group or a heterocyclic group represented by R, R, or the like: an example of the description. As an example of the substituent, an alkyl group, a = amino group, an alkoxy group, an aryloxy group, a decyl group, Oxycarbonyl, aryloxycarbonyl, decyloxy, decylamino, sulfonylamino, sulfonyl, sulfonyl, ureido, hydroxy, dentate, sulfo, carboxy, etc. Details of these And a preferred embodiment is as described above. Further, the above-mentioned R~, R~ may be represented by an alkyl group or an aryl group, and as an example of the substituent, it may be mentioned as the former AA 13 1 1 a. _ 1 T ^ v J y

R Formula (XI) 8 -22-201221520 In the above formula (XI), R31a and R32a represent an alkyl group or a halogen atom. R33a and

R 34; each independently as R 3 la, R 32 a, R 33 a, 〇 3 4 a ^ - , , ^ « an alkyl group which is not RR is preferably an alkyl group having 1 to 10 carbon atoms, more preferably a carbon number of 1 to 5. An alkyl group, an alkyl group of 1 to 2 specific. As an example, a mercapto group, an ethyl group, an isobutylene tert-butyl group, an n-octyl group, a n-decyl group, a n-hexadecyl group, a cyclopropyl group, a cyclyl group, a cyclohexyl group and the like can be given. As a R3u, R32a, R33a, a fluorine atom, a chlorine atom, a bromine atom, or a bromine atom. The halogen atom represented by R34a may, for example, be an iodine atom or the like, preferably a chlorine atom. In the above formula (XI), R35a and R36a each independently represent an alkyl group, an alkoxy group, an aryloxy group, a sulfo group or a salt thereof. Aminosulfonyl, alkoxysulfate, or alkoxysulfonyl. The alkyl group represented by the soil p 3 5 a t &gt; 36a R is synonymous with the alkyl group of the above R31a, R32a, R33a, and R, and the preferred embodiment is also the same. The alkoxy group of p35a or p 3 6 a is preferably a carbon number of 1 to 3 Å, more preferably a carbon number of 12 Å, particularly preferably an alkoxy group having a carbon number of i to 丨〇, and for example, Methoxy, ethoxy, butoxy, 2-ethylhexyloxy and the like. • p 3 5 ap 3 6 a , the aryloxy group shown is preferably a carbon number of 6 to 30, more preferably an aryloxy group having a carbon number of from 6 to 12, and examples thereof include oxy Base, 1-naphthyloxy, 2-naphthyloxy and the like. The contiguous group represented by r 3 5 a, r 3 6 a ^ and the salt thereof are preferably a group derived from a sulfonic acid group and a sulfonic acid salt. The sulfonate is preferably a quaternary ammonium salt or an amine salt, particularly preferably a carmine salt having a carbon number of Η〇 (preferably 〇1〇~3〇, more preferably 15~3〇). -23-201221520 The aminosulfonyl group represented by R35a and R36a is preferably a carbon number of 1 to 30, more preferably 2 to 20 carbon atoms, particularly preferably an aminosulfonyl group having 2 to 15 carbon atoms. Specific examples thereof include an ethylaminosulfonyl group, a propylaminosulfonyl group, an isopropylaminosulfonyl group, a butylaminosulfonyl group, an isobutylaminosulfonyl group, and a Dibutylaminosulfonyl, pentylaminosulfonyl, isopentylaminosulfonyl, hexylaminosulfonyl, cyclohexylaminosulfonyl, 2-ethylhexylaminosulfonyl a thiolsulfonyl group, a decylaminosulfonyl group, a phenylaminosulfonyl group, and the like, and a dialkylaminosulfonyl group, which may be dimethylaminosulfonyl sulfonate. Base, diethylaminosulfonyl, dipropylaminosulfonyl, diisopropylaminosulfonyl, dibutylaminosulfonyl, di-butylaminosulfonyl, Second propylaminosulfonyl, dihexylaminosulfonyl, methylethylaminosulfonyl, nonylbutylaminosulfonyl, ethylbutylaminosulfonyl, benzene Methylaminosulfonyl and the like. Among them, the "excellent" alkyl moiety has a carbon number of 4 to 15% of a dialkylaminosulfonyl group. The alkoxysulfonyl group represented by R35a ' R36a is preferably a carbon number of 1 to 30, particularly preferably 2 to 20', more preferably 2 to 15, and particularly preferably 4 to 15 of an alkoxysulfonyl group. Specific examples thereof include a butylsulfonyl group, a hexanesulfonyl group, a decylsulfonyl group, and a dodecylsulfonyl group. The phenoxysulfonyl group represented by R35a and R36a is preferably a carbon number of 6 to 30, more preferably 6 to 20, particularly preferably 6 to 15 substituted or unsubstituted phenoxysulfonyl group'. Examples thereof include a phenoxysulfonyl group and an anthracene phenylsulfonyl group. R35a or R36a may have a more substituent, and examples of the substituent include a substituent of an alkyl group, an aryl group or a heterocyclic group represented by R1 la and R! 2a of the above formula (IX). An example has been stated. 8 -24 - 201221520 In the above formula (χι), an integer, when η31 or n32 a is different. When 11 and 11 each independently represent 〇 〜 2, the plural R... or han 3^ may be the same or the following. In the above, it is preferably two (XI1) represented by the formula (10)), and the following formula (selected from the side core brewing compound).

In the above formula (XII), 'R~, R42a, R and R44a are each independently an exo group or a dentate atom, and are the same as the ruler 313, R..., R-, R in the above formula (XI). - The alkyl group or the atomic element is the same as #, preferably: the same is true. R45a, R46a, R"a and R48a in the above formula (XII) each independently represent a substituent, a base or a salt thereof, or an amino acid group. Any of Han 453 and R47a and R46a and R48a Any one of a sulfo group or a salt thereof or an aminosulfonyl group. R45a, R46a, R47a and R48a are an alkyl group represented by R35a or R36a in the above formula (XI), a sulfo group or a salt thereof, and an amine. The sulfosyl group is synonymous, and the preferred embodiment is also the same. -25- 201221520 [Diamino sulfonium compound represented by the formula (XIII)] R55a 〇57a

In the above formula (XIII), R51a, R52a, 513 and R54a each independently represent an alkyl group or a halogen atom, and are a group or a group of R3 1 a, R32a, R and R in the formula (XJ). The atom is synonymous, and the preferred aspect is also the same as in the above formula (XIII), R55a and R5 "each independently represent a hydrogen atom or an alkyl group, and the alkyl group is R"a, R32a in the above formula (XI). The same applies to the preferred meaning of the alkyl synonymous of R33a and R34a. Further, R57a and R58a each independently represent a hydrogen atom or a leukoyl group, and the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, particularly preferably a methyl group. In the above formula (XIII), L5^ and L52a each independently represent a divalent linking group, preferably an alkylene group having a carbon number of 1 to 1 fluorene, an extended aryl group having a carbon number of 6 to 20, and -0-, - S-, -NR-, -S〇2-, -CO-, or a complex array of such -26-8 201221520. More preferably, L51 a or L5 2 a is a stretching group having a carbon number of 1 to 10, a stretching phenyl group having a carbon number of 6 to 12, a continuating amine group, or a combination of the plurality of divalent linking groups. Particularly preferred is a divalent linking group having a carbon number of 1 to 1 fluorene, a sulfonylamino group, or a plurality of these. The divalent linking group having a carbon number of 1 to 10 or a divalent linking group which is combined with -0- or the like may be an unsubstituted or substituted group, and examples thereof include an ethyl group and a propyl group. , butyl, ethoxy, propyl, ethyl cyano, propyl propyl, butyl hydrazide, butyl sulfhydryl , 1-methyl-ethyl sulfonyl group and the like. Wherein 'preferably an alkylamino sulfonyl group having a carbon number of 2 to 1 Å (for example, an ethylaminosulfonyl group, a propylaminosulfonyl group, a butylaminosulfonyl group, Streptylaminosulfonyl). The diaryl group having 6 to 20 carbon atoms or the divalent linking group which is combined with -0- or the like may be unsubstituted or substituted, and examples thereof include a stretching phenyl group and a stretching phenyl group. Further, a phenylaminosulfonyl group or the like is preferable, and among them, a arylarylsulfonyl group having a carbon number of 6 to 12 (for example, a phenylaminosulfonyl group or the like) is preferable. Further, R of the above -NR- represents a hydrogen atom or an alkyl group having 1 to 1 carbon atom. Specific examples of the alkyl group include a mercapto group, an ethyl group, a propyl group, an isobutyl group, a butyl group, an isobutyl group, a second butyl group, and a 2-ethylhexyl group. In the above formula (XIII), L53a and L54a each independently represent an oxygen atom or a -NH- group. -27- 201221520 [Green onion compound i represented by formula (XIV)

rX2 RX2 Formula (XIV) K, RX3 ?X1 X /RX3

^S〇2NH X4', (pH RX2 In the above formula (XIV), RX1 each independently represents a mercapto group or an ethyl group, preferably an ethyl group. RX2 each independently represents an alkyl group having a carbon number of 1 to 1 fluorene, For example, a mercapto group, an ethyl group, a propyl group, a tert-butyl group, an octyl group, etc. may be mentioned. An alkyl group having 1 to 4 carbon atoms is preferred, and an alkyl group having 1 to 2 is more preferred. Further, 'RX3 is independently Examples of the alkyl group having a carbon number of 1 to 1 Å include a mercapto group, an ethyl 'propyl group, a third butyl group, an octyl group, etc., and preferably a carbon group having 1 to 8 carbon atoms, more preferably 1 to 2 carbon atoms. Further, X4 each independently represents 〇 or 1, preferably 1. In the oxime compound represented by the above formula (XIV), the two S02NH groups substituted in the benzene ring each have - ( CH2) The branched structure shown by X4CH(RX2)RX3 can achieve higher Y value and contrast when forming an image. Next, the synthesis method of the ruthenium compound will be described. The brewing compound can be, for example, the following scheme (scheme) The synthesis is shown. First, the synthesis of the hydrazine nitrogen (B) by the sulfonium compound (A) which is not substituted with the S-sodium amine is followed by the use of an amine compound (for example, R, _NH2 (R' is an alkyl group or the like base ))) is carried out to obtain a sulfonamide (C). -28- 8 201221520

Here, the method for producing the sulfonium gas (B) described above can be obtained by gas-sulfonylating a sulfonamide unsubstituted gull compound by using chlorosulfonic acid. Further, as another method, sulfonation may be carried out using sulfuric acid or fuming sulfuric acid, and chlorination may be carried out by using a chlorinating agent, ruthenium chloride, chlorine, phosphorus, chlorine, etc., to obtain an amine of the desired product. The method of producing the sulfonamide compound (c) is described in the case where the guanidinium is used as a diethyl ether solvent such as meridyl ketone or the amine is used as a base. The chlorinated amine (c) is synthesized by reacting a compound structure (e.g., R _NH 2 ) corresponding to the target with the sulfonium gas (B). For the synthesis, the solvent can be used in the first month. The guanamine solvent (dimercapto, monomethylacetamide, indole, t, methylpyrrolidone, N-ethylpyrrole), S is a solvent (ethyl acetate, butyl acetate, etc.), an ether solvent (岵, tetrahydrofuran, methyl bis(methylethyl _, acetone), :;: =, etc.), B guess, ketone Gengyuan, etc.), water, etc. These two: agents (toluene, dimethyl stupid, compounds can also serve as a solvent for the aforementioned amine compounds, can also be better to coexist. propylamine and other ratios. Ding, two: dimorphic amines (three Ethylamine, ethyl A 5 , f &amp;, H-azabicycloundecene (DBU), etc. Examples of the bases include carbon-opening-sodium, potassium citrate, sodium hydrogencarbonate, and -29. - 201221520 Potassium bicarbonate, potassium acetate, sodium acetate, sodium hydroxide, potassium hydroxide, etc. Purification can be carried out as needed. As a purification method, column chromatography, recrystallization, and crystal can be mentioned. In the above, the preferred oxime compound of the present invention is selected from the above formula (XII) 'diamine ruthenium compound represented by the above formula (XIII) or formula (XIV). The compound is more preferably in the following case. That is, in the above formula (ΧΙΙ), R42a, R43a and R44a are each independently a fluorenyl 'ethyl group or a bromine atom, and R45a and R46a are each independently. The ground is an amino group having a carbon number of 2 to 15, and R47a and R48a are a methyl group. Further, preferably, the above formula is In the above formula, R5 1 a, R5 2 a , R 33 and R54a are each independently a methyl group, an ethyl group or a bromine atom, and R55a and R are each independently a hydrogen atom or a fluorenyl group, and R57a and R58a are each independently hydrogen. The atom or methyl group, L5la and L52a are each independently an alkylaminosulfonyl group having a carbon number of 1 to 10, an alkylenesulfonyl group having a carbon number of 7 to 2, or a carbon number of 2~ Further, in the above formula (XIV), RX1 is each independently methyl or ethyl 'RX2 is independently a carbon number. 1 to 4 of the alkyl group 'rX3 are each independently 1 to 4 alkyl groups, and χ4 is 1. In each of the above cases, the general formula (1) of the ruthenium compound of the present invention and the following dye compounds are used. When the dipyrromethene-based metal-based compound compound in which the compound is coordinated to a metal atom or a metal compound is used in combination, it is preferred from the viewpoint of more effectively achieving the effects of the present invention. 8 -30- 201221520 Hereinafter, specific examples of the ruthenium compound in the present invention are shown. However, the present invention is not limited thereto.

-31 - 201221520

^v^S〇2NH;^^

8 -32- 201221520 Η

-33 201221520

34- 201221520

-35- 201221520

,CH»CH2CH3 Ί〇Η-ΟΗ2€Η3 CHj. CH5 ,0η-CH2*CH3 芩 h-ch2oh3 .../Bay Money

'S02N

C2H5 \CH2)3CH3 SO,N \CH2)3GHj

8 -36- 201221520

Ra

Ff rb Rc rd Re ch3 〇2 ',s,y 八h3 H ch3 H ch3 ch3 〇2 n CH3 H ch3 ch3 H ch3 H ch3 ch3 〇2 ch3 H ch3 ch3 〇2 I vs, nA H ch3 H ch3 ch3 〇 2. 1 H ch3 H CHg CH3 〇z ch3 H ch3 ch3 〇2 .々&quot;CD ch3 H ch3 ch3 J'nM H ch3 H ch3 ch3 〇2 vs-N/\CF H 3 ch3 H ch3 ch3 H CH? H ch3 CHg 〇 2 vS, N, . CH3 H ch3 * represents a moiety bonded to the benzene ring. -37- 201221520

Rb Rq RD Re ch3 02 ·〆$,以八s^O, ch3 H ch3 ch3 〇2 H ch3 H ch3 ch3 ch3 H ch3 ch3 〇2 ch3 H ch3 ch3 ch3 H ch3 ch3 〇2 s ch3 H ch3 ch3 〇2 S °ί ch3 H ch3 ch3 〇2 s 0, ch3 H ch3 CH3 〇2 n ch3 H ch3 ch3 .WcHa H qh3 ch3 H ch3 ch3 〇2 7S, n, (CH2)7CH3· ch3 H ch3 ch3 〇2 •, S ;*n '(CH2)90H^ ch3 H ch3 ch3 vS,n]CH2)i〇CH3 H ch3 H CH3 • ch3 〇2 ^Sn(CH2)17GH3 H QH3 H. ch3 * indicates bonding with a benzene ring section. -38- 8 201221520

Ra. rb Rc Rd Re ch3 VX gh3. H ch3 CHa 6 gh3 H ch3 ch3 gh3 H ch3 ch3 •&gt;S'N CHg H CH3 ch3 CH3 H ch3 ch3 〇2 Vs, ch3 H ch3 ch3 •/S'n' n^Ov^ h 5 GHj H ch3 ch3 •ivk ch3 H ch3 ch3 ch3 H ch3 ch3 〇2 '&gt;S'(two) eight ch3 H gh3 ch3 〇2 CHb H ch3 ch3 vS;n.(CH2)?CH3 (CH2 ) 7CH3 GHj H ch3 * represents a moiety bonded to a benzene ring. -39- 201221520

Rb

Rb R° Ff Re ch3 ch3 H ch3 ch2ch3 〇2 *-S'N^CH3 H ch3 H ch2ch3 CH2CH3 o2 ch3 H CH2CH3 CH2CH3: Oj ch3 H CH2CH3 CH2CH3 Η CH3 H CH2CH3 ch2ch3 〇2 1 Ή CH3 H CH2CH3 CH2CH3 ch3 H Ch2ch3 ch2ch3 〇2 vSfi〇ch3 H ch2ch3 CH2CH3 vftNJ&lt; H ch3 H CH2CH3 CH2CH3: 〇2 *, S'N^CF H ch3 H CH2CH3 ch2ch3 *Λ2νΌ H ch3 H ch2ch3 ch2ch3: 〇2 vs&gt;N^\ ch3 H ch2ch3 * indicates the portion bonded to the benzene ring. 201221520

Re

Rb Rc rd Rh CH2CH3 H ch3 H CH2CH3 ch2ch3 ch3 H CH2CH3 CH2CH3 〇2 *〆纟, N 〇H ch3 H CH2CH3 ch2ch3 *-sb7^^ ch3 H CH2CH3 CH2CH3 〇2 CHg H CH2CH3 ch2ch3 vs, N s °Ί ch3 H CH2CH3 ch2ch3: 〇2 vSH ch3 H CH2CH3 CH2CH3 CH3 H ch3 ch3 H ch2ch3 ch2ch3 ν3, Ν, (ςΗ2χΗ3 H ch3 H CH2CH3 CH2CH3 〇2 ch3 H CHzCH3 CH2CH3 〇2 vS.N.{CH2)n〇H3 ch3 H CH2CH3 CH2CHa ^n,{CH2),〇CH3 H ch3 H CH2CH3 CH2CH3 〇2 ^sN-(CH2)i7CH3 H gh3 H CH2CH3 * indicates a moiety bonded to the benzene ring. -41 - 201221520

Rh Rc R° Re CH2CH3 ch3 H CH2CH3 CH2CH3 *-s!nJ〇ό ch3 H CH2CH3 CH2CH3 〇2. 1 H CHsi H CHzCH3 gh?ch3 〇2 H 5 ch3 H CH2CH3 CH2CH3 〇2 1 ch3 H CH2CH3 ch2ch3 〇2 1 Human V human ch3 H CH2CH3 CH2CH3 〇2 k ch3 H ch2.ch3 CH2CH3 〇2 CH3. H CH2CH3 CH2CH3 〇2 ch3: H CH2CH3 CH2CH3 ^S^^CHzJyCHa (CH2)7CH3 ch3 H ch2.ch3 * indicates a bond with a benzene ring The part of the knot. -42- 8 201221520 rb

Ra rb RC rd re ch2ch3 j'vO H ch3 Η CH2CH3 CH2C.Hb .^^^(CHzhCHa (CH?)2CH3 ch3 Η CH2CH3 ch2ch3 〇2 vS^.fCH^CHa (CH2)3CH3 ch3 Η CHjCHa ch3 H 〇2 •, s), ch3 Η ch3 CHgCHa H &quot;t〇&lt; Η CHaCHj GH2CH3 H 〇2 '〆S, NH Η CHaChb ch3 H 〇2 Η ch3 GH2GH3 H f2丄Η Η CH2CH3 GH2GH3 H Η Η CHjCHa ch2ch3 H 92 9 rr GH GH2CH3 CH2CH3 H Η CH2CH3 ch3 H ^S'O Η ch3 GH2GHa H -ΑΛ Η Η CH2CH3 CH2CH3 H 〇2 Η CH2CH3 GH2Ghb H Η CHaCHa CH2CH3 H *&quot;* 'Ό Η CHaClij * indicates bonding with benzene ring part. -43- 201221520

Y^t'ra 〇hn^L rb ra R8 Rc Rp Re CHjCHa H 〇2 H CH2CH3 ch3 H ·〆S, NHH CHgCHa H 〇2 H CHjCHa CHjC^ H Oj */S, (2) H CI^CHj C^CHg H •-sCQ H CH2GHa CHaCH, HSH CH2CH3 CHj. H 〇2 \ H CHg; CH2GH3 H 〇2 SH GH2CH3 CHg H 〇2 n H ch3 CH2CH3 H CHj ΛΧ^Η3 H ch3 H CH2CH3 CH2PH3 H 〇2 7®·, - (c HjjJyC Hi HH ch2ch3 c eat H (two) this H2) jCH3 H CHa CHaGHa :H 〇2 ^^-(CHzJnCHa HH ch2ch3 03⁄4. H ^siN.(CH2)l0CHa H ch3 CH^CHg H ^S'N- (CH2), 7CH3 H CH2CH3 * indicates a moiety bonded to a benzene ring. -44- 201221520 rb

Ra rb Rc R° Re ch2ch3 HV vs' XH ch2ch3 ch3 H 6 H CH3 ch2ch3 H 〇2 3 KH CH2CH3 CH2CH3 H 〇2 9 H CH2CH3 ch3 H 〇2 9 Η 1 H GH3 CH2CH3 H 〇2 H ch2ch3: CH2GH3 HH CH2CH3 Ch2ch3 H human H GHgCHa GH2CH3 H 〇i 9S'N 八k H CH2QH3 ch2ch3 H •, S, (b) ^sv/ H CH2GH3, gh3 HH gh3 CH2CH3 H 〇2 *〆&amp;, N (CHzJyCHa H CH2CH3 * indicates benzene Part of the ring bond. -45 - 201221520 R〇

Re R. R° Re ch3 HH ch3 ch3 H (CH2|2CH3 H ch3 ch3 H ^s!N.(CH2)3CHa (CH2)3CH3 H ch3 ch3 HH ch3 CH2CH3 〇2 HH GH2CH3 CH2GH3 〇2 •, S'N HHH CH2CH3. Ch3 HH ch3 ch2ch3 HH ch2ch3 ch2gh3 HH CH2CH3 CH2CH3 22 ^ hX^ HH CH2CH3 CH2CH3 〇2 HH CH2CH3 ch3 〇2 ,''〇HH ch3 gh^ch3 HH CH2CH3 ch2ch3 〇2 '^S&quot;N^CF3 HH ch2ch3 ch2;ch3 HH ch2ch3 ch2ch3 〇2 &quot;Ό HH ch2ch3 * indicates the part bonded to the benzene ring. 8 -46- 201221520

Rb Rc R. Re ch2gh3 〇2 HHH CHgCHg CH3 HH CHg ch2ch3 〇2 HH CHjCI^ ch2ch3 〇2 ·〆$,八' HH CHjGKj ch2ch3 HH CHjCHa ch2ch3 Pz HH ΟΗ2〇Η3 ch3 〇2 s Ί HH GHa. ch2ch3 s HH ch2ch3 〇2 n HH ch3 ch2gh3 CHa. .Horse HH CHgCHa ch2ch3 */s, n^(ch士(5)3 HHH CHaCHg gh3 〇2 ^S.nXCH2)3CH3 HHH GHg ch2ch3 〇2 Buy "ch3 ri HH GHaCHa ch3 〇2 .vSSf^(CH2 )ipCH3 HH ch3 CH2CH3 v^ViCH2}17CH3 HHC^CHg * indicates the moiety bonded to the benzene ring. -47- 201221520

R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R Λ HH CH2CH3 CH2CH3 〇2 k HH CH^CHa CHaCHa 〇2 HH CHaCHa CHg 〇2 HH CHa CHaCHs ^siN,(CH2i7CH3 (CH2)tCH3 HH CHgCHa * indicates the moiety bonded to the benzene ring. -4B- 201221520 R8

It is 5 〇 mass ° /. Therefore, the hue of the colored image can be made good while maintaining the fastness, and the contrast can be more effectively improved. (Dye) The coloring composition for a color filter of the present invention contains a dipyrromethene metal complex compound in which a compound represented by the following formula (I) is coordinated to a metal atom or a metal compound, and At least one selected from the group consisting of dye compounds represented by any one of the formula (Π) to the formula (VIII). If these dyes and hydrazine compounds are combined, the contrast improvement effect is particularly large. -49- 201221520 In the above dye, the dipyridyl 2 to the compound may be obtained by using a metal atom or a metal compound represented by the formula (1). This compound is in the hue month + robbery complex u mouth cut p匕邳 and heat resistance Λ 夏 3 Xia Xing &lt; point system is better.

In the above formula (I), Ri, ^, r3, r4, r represent a hydrogen atom or a substituent, and each of them independently represents a halogen atom, a halogen group, a /57 group, a group or a heterocyclic ring. a monovalent group of a quinone atom and a substituent represented by 'R to r6 in the formula (1) (the following is also a list of the following R). The group of the S group is collectively referred to as "substitution". A dentate atom (for example, an alkyl group (preferably a carbon number i to 48 δ y rolling atom, a bromine atom), a branched or cyclic alkyl group, for example, a straight chain of a carbon number of 1 to 24, Base, tert-butyl, pentyl, hexamethylene, ethyl, propyl, isopropyl, benzyl, dodecyl, hexadecanyl, heptyl, octyl, 2-ethylhexyl borneyl, 1- Adamantyl) soil, cyclopentyl, cyclohexyl, and carbon-lowering 2~", for example, B is preferably a carbon number of 2 to 48', more preferably an aryl group (preferably a carbon number of 6 to 48 Å). a group, a propyl group, a hexyl group, a hexyl group, a hexyl group having a carbon number of from 6 to 24, a heterocyclic group having a number of from 1 to 18, For example, the carbon number is 1 to 32, more preferably carbon 2 -. thiophene, 4-pyridyl, 2-furan-5〇 - 201221520, 2-pyrimidinyl, u pyridyl, 2-benzothiazolyl, i-imidazolyl, 1-° ratio, pendant, benzotriazole-oxime-based, decylalkyl (preferably carbon) More preferably, the number is from 3 to 3, more preferably a decyl group having a carbon number of from 3 to 18, such as a trimethyl sulfonyl group, a triethyl sulfonium group, a tributyl decyl group, a tert-butyl decyl fluorenyl group, Trihexyl dimethyl decyl), hydroxy, cyano, nitro, alkoxy (preferably a carbon number of 1 to 48' more preferably an alkoxy group having a carbon number of 1 to 24, such as methoxy, ethoxy , 1, 1-butoxy, 2-butoxy, isopropoxy, tert-butoxy, dodecyloxy and cycloalkyloxy, such as cyclopentyloxy, hexyloxy, aryl An oxy group (preferably a carbon number of 6 to 4, more preferably an aryloxy group having a carbon number of 6 to 24, such as a phenoxy group, a fluorenyl-naphthyloxy group) or a heterocyclic oxy group (preferably a stone inverse number of 1) More preferably, it is a heterocyclic oxy group having a carbon number of 1 to 18, such as a 1-n-tetrazol-5-oxy group, a 2-tetrahydropyranyloxy group, a decyloxy group (preferably a number of 1 3 2, more preferably a carbon number of 1 to 18, such as a trimethyl decyloxy group, a second butyl group a methyl decyloxy group, a diphenylmethyl decyloxy group, a decyloxy group (preferably a carbon number of 2 to 48, more preferably a decyloxy group having a carbon number of 2 to 24, such as an ethoxy group, 2 A Alkoxycarbonyl, benzhydryloxy, decyloxy), alkoxycarbonyloxy (preferably a C 2 to 48, more preferably a C 2 to 24 alkoxyoxy group) For example, ethoxylated oxy, decyloxy &amp;oxy' and ring oxo-alkoxy, such as cyclohexyloxycarbonyloxy)? An oxycarbonyloxy group (preferably having a carbon number of 7 to 32, more preferably a carbon number of L to 24, a methoxyoxyl group such as a phenoxyoxy group), and an amine cerium oxide having a carbon number of 1 to 48. More preferably, the amine has a carbon number of i~24, N,N_-methylamine oxime, N-butylamine oxime, N_ &quot; _ethyl_N-phenylamine oxime Alkoxy), sulfonium sulfonate (preferably a carbon number of 1~, more preferably a carbon number of 1 to 24, an amine, a hydrazine-51-201221520 base, such as N,N-diethylamine a group, an N-propylamine, a fluorenyloxy group, a decyloxy group (preferably a carbon number of 38, more preferably a carbon number of a sulfonyl sulfonyloxy group, such as a methyl group such as a An oxy group, a hexadecanosulfonyloxy group, a cyclohexylsulfonyloxy group, a sulfonyloxy group (preferably a carbon number of 6 to 32, more preferably a carbon number of 6 to aryloxy) , for example, phenylsulfonyloxy), fluorenyl (preferably an anthraquinone 1 to 48, more preferably a fluorenyl group having a carbon number of 1 to 24, such as a methyl group, a 4-yl group, a fluorenyl group, a Anthracenyl, tetradecyl, cyclohexyl) _, alkoxycarbonyl (preferably having a carbon number of 2 to 48, more preferably a carbon number of 2 to 24)

An oxygen-burning group, for example, A, 7 @ I oxyerythroethoxy group, octacarbonyloxycarbonyl, hexyloxy group ' 2,6 · di-t-butyl _4_methylcyclohexane An oxyalkylene group, an aryloxycarbonyl group (preferably, an aryloxycarbonyl group having a carbon number of 7 to 32, more preferably a carbon number of 7 to 24, such as a phenoxycarbonyl group) or an amine formazan group (preferably, a carbon number i to 48) 'More preferably an amine fluorenyl group of 1 to 24, such as an amine fluorenyl group, n, n_diethyl: carbaryl, N-ethyl-N-octylamine fluorenyl, n, n _Dibutylamine A from: soil, propylamine, mercapto, N-phenylamine, mercapto, n-methyl, stupid, "N-N-dicyclohexylamine, mercapto" , an amine group (preferably: two or less, more preferably an amine group having a carbon number of 24 or less, such as an amine group, a formamide, an N,N-dibutylamino group, a tetradecylamino group, a 2·B Anthranylamine, cyclohexylamino) 'anilinyl (preferably having a carbon number of 6 to 32, more preferably 6 aniline, such as anilino, decylamino), heterocyclic amine = is a carbon number of 1 to 32, more preferably a heterocyclic amine group of i to 18, such as a tert-butyl group, and a carboamine group (preferably a carbon number of 2 to 48, more preferably Preferably, it is a 2 - 24 carbon amide group, such as an acetamino group, a benzoguanamine group, Βώ «四院酿*暴, trimethylethyl decyl amide, cyclohexane guanamine), urea Base (more than -52 to 201221520 preferably a carbon number of 1 to 32, more preferably a carbon number} to 24 of a ureido group, such as a urea group, an N,N-dimethylureido group, an N-phenylureido group), an anthracene An imido group (preferably having a carbon number of 36 or less, more preferably a quinone imine group having a carbon number of 24 or less, such as n-succinimide group, N-phthalimido group) or an alkoxycarbonylamino group ( Preferably, the alkoxycarbonylamino group having a carbon number of 2 to 48, more preferably 2 to 24 carbon atoms, for example, an anthraceneoxycarbonylamino group, an ethoxycarbonylamino group or a third butoxycyclohexyloxyamine group is preferably The carbon number is 7 to 32, more preferably an aryloxycarbonylamino group having a carbon number of 7 to 24, such as a phenoxycarbonylamino group, or a sulfonylamino group (preferably having a carbon number of 1 to 48, more preferably a carbon number of 1). a sulfonamide group of 24, such as sulfonylamino, butylsulfonylamine, benzenesulfonylamino, hexadecanesulfonylamino, cyclohexanesulfonylamino), amidoximeylamine ( It is preferably a carbon number i to 48, more preferably an amine sulfonylamino group having a carbon number of i to 24, such as N, N_: Amine sulfonylamino group, ethyl-N-dodecylamidosulfonylamino group, azo group (preferably a carbon number of 〜32, more preferably an azo group of 1 to 24 carbon atoms) , for example, phenyl azo, 3 -pyrazolylazo), sulfur-burning group (preferably, carbon number i to 48, more preferably an alkylthio group having a carbon number of i to 24, such as methylthio group, B Sulfur, octylthio, cyclohexylthio), arylthio (preferably having a carbon number of 6 to 48, more preferably an arylthio group having a carbon number of 6 to 24, such as a phenylthio group) or a heterocyclic thio group ( It is preferably a carbon number of 1 to 32, more preferably a heterocyclic thio group having a carbon number of 1 to 18, such as a 2-benzothiazolylthio group, a 2-pyridinethio group or a 1-phenyltetradecylthio group, Alkylsulfinyl group (preferably having a carbon number of 1 to 3 2 'more preferably an alkylsulfinyl group having a carbon number of from 2 to 4, such as a dodecane arylene group)' arylsulfinyl group (preferably, a carbon number of 6 to 32, more preferably an arylsulfinyl group having a carbon number of 6 to 24, such as a phenylsulfinyl group) or an alkylsulfonyl-53-201221520 group (preferably a carbon number) 1 to 48, more preferably an alkylsulfonyl group having a carbon number of 1 to 24, such as a mercaptosulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, Further thiol, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecanosulfonyl, octylsulfonyl, cyclohexylsulfonyl), arylsulfonyl (preferably More preferably, the carbon number is from 6 to 48', more preferably an arylsulfonyl group having a carbon number of from 6 to 24, such as a phenyl group, a S-group, a 1-naphthylsulfonyl group, or an aminesulfonyl group (preferably having a carbon number of 32 or less). More preferably, it is an aminesulfonyl group having a carbon number of 24 or less, such as an aminesulfonyl 'n, n-dipropylaminesulfonyl group, N-ethyl-N-dodecylsulfonyl group, N-ethyl group Phenylamine sulfonyl, N-cyclohexylamine sulfonyl), sulfo, phosphinyl (preferably having a carbon number of from 1 to 32, more preferably a carbon number! A phosphinyl group of ～24, such as a phenoxyphosphonium fluorenyl group, an octyloxyphosphonium fluorenyl group, a phenylphosphonium fluorenyl group, or a phosphinylamino group (preferably having a carbon number of from 1 to 32, more preferably a carbon number! A phosphinylamino group of ~24, such as diethoxyphosphinylamino, dioctyloxyphosphinylamino). When the above monovalent group is a more substitutable group, it may be further substituted by any of the above groups (substituent R). Further, when there are two or more substituents, the substituents may be the same or different. In the general formula (I), R and R2 may be bonded to each other to form a ring of 5, 6 or 7 members, and R2 and R3 may be bonded to each other to form a ring of 5, 6 or 7 members, R4 and R5. They can be interlocked to form a 5-member, 6-member "7-member ring, and R5 and R6 can be bonded to each other to form a ring of 5, 6 or 7 members. Further, as the formed ring, there is a saturated ring or an unsaturated ring. Examples of the saturated or unsaturated ring of the 5th member, the 6th member, and the 7th member include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, and a carbazole. : each set &amp;, σ bottom bite ring, cyclopentane ring, cyclohexene ring, benzene ring. Than a pyridine ring. It is better than 璜 璜, σ 乂 呀 合 合 合 合 合 合 合 合 合 合 合 合 合 合 合 合-54- 201221520 Further, when the formed ring of 5 members, employees, and 7 members is a more substitutable group, it may be replaced by any of the above substituents R, and when it is 2 or more When substituted by a substituent, the substituents may be the same or different. In the formula (1), when r7 is a halogen atom, an alkyl group, an aryl group or a hetero-based group, the preferred range is the alkyl group, the aryl group or the heterocyclic group as the halogen atom of the above R1 to R6. The preferred ranges are each the same. The alkyl alkoxycarbonyloxycarbonyl carbonyl amine is an alkoxysulfonyloxycarbonyl imine group, and the amine is an alkoxy group. The substituent is unsubstituted or preferably a carbon alkyl group. In the formula (I), an amine group, an arylamine group, an amine group, an exact group, a sulfonium group (I), a carbene group, a aryl group, a aryl group, an aryloxycarbonyl group, an amine carbaryl group, a nitrile carbonyl group , in the formula (I), or in the unsubstituted heterocyclic group unsubstituted, in the formula (I), the number 1 to 12, more specifically, in the 'preferred imine group, the ureido group, the alkyl group, the alkoxy group 0, Preferred groups and aryl groups are preferably a nitrile group, a fluorenyl aryloxycarbonyl group, a particularly preferred one, preferably a substituted or a calcining group, an alkyl group, a more unsubstituted propyl group, and a different 1F sentence. Amine, carboguanamine, ureido, sulfonium sulfhydryl, especially preferably carbamide, amide amino group, more preferably carbamide, urea amide, especially carbamide, urea The above-mentioned R2 and R5, in the above-mentioned oxycarbonyl group, amine sulfhydryl group, alkylsulfonimide group, amine carbaryl sulfonyl group, amide group, alkyl sulfonyl group, alkyl sulfonyl group, sulfonate The mercapto group is more preferably an alkoxycarbonyl group, a benzylidene group, an amine formylsulfonyloxycarbonyl group or an aminecarbamyl group. As the above R3 and R4, the above-mentioned alkyl group, substituted or unsubstituted aryl group' is more preferably a substituted or unsubstituted. When R3 and R4 are -, and R is a non-alkyl group, the linear, branched or cyclic substitution or the like, for example, methyl, ethyl, n-55-201221520 propyl, cyclopropyl Base, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl and benzyl. More preferably, it is a substituted or unsubstituted alkyl group having a carbon number of 1 to 12, and more specifically, it may, for example, be a cyclopropyl group, an isobutyl group, a tert-butyl group, a cyclobutyl group or a cyclopentyl group. More preferably, it is a 2- or 3-stage substitution or a non-alkyl group having a carbon number of 1 to 12, and more specifically, an isopropyl group, a cyclopropyl group, an isobutylene group, a cyclobutyl group or a cyclohexyl group is exemplified. In the formula (I), when 'r3 and R4 represent an aryl group, the phenyl group which is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group is a substituted or unsubstituted phenyl group. When R3 and R4 represent a heterocyclic group, as the heterocyclic group, a 2-substituted or unsubstituted 2-thienyl group, a substituted or unsubstituted 4-pyridyl or unsubstituted 3-pyridyl group, a substituted or unsubstituted one is preferred. 2- to 2-substituted or unsubstituted 2-furyl, substituted or unsubstituted, substituted or unsubstituted 2- benzothiazolyl, substituted or unsubstituted, substituted or unsubstituted 1-pyrazolyl, Substituted or unsubstituted sino-1-yl, more preferably substituted or unsubstituted 2-thiazinyl, unsubstituted 4-pyridyl, substituted or unsubstituted 2-furantyl, unsubstituted 2 - Pyrimidinyl, substituted or unsubstituted pipyridyl. Second, the description is two. A metal atom or a metal compound of a pyromethylene group metal complex. The metal or metal compound may be a metal oxide containing a divalent metal atom, a divalent metal hydroxide or a divalent gold as long as it is a compound or a metal compound. For example, in addition to Zn, Mg, Si, Sn, Rh, to, Pd butyl, bond or cycloisopropyl, cyclohexyl substituted butyl, ketone, more preferably pyridine, pyridine, pyridine , 1 - ° m η sits benzotrisubstituted or substituted or compounded gold, bivalent gasification, Mo, 8-56-201221520 Μη, Pb, Cu, Ni, Co, Fe%, also contains A1C1, InCl a metal chloride such as FeCl 'TiCl2, SnCl2, SiCl2, or GeCl2, a metal oxide such as butadiene or VO, or a metal hydroxide such as Si(OH)2. Among these, Mg ' Si ' Pt ' Pd ' Mo ' Μη, which is a mixture of light, light resistance, and suitability, is more preferably Fe, Zn, Mg, Si, and most preferably Fe, Zn, and Cu. Co is especially good for Zn. The dipyridylmethylidene group which is formed by the compound represented by the above formula (I) shows a preferred aspect. That is, in the formula (1), each of R1 and R6 is an alkenyl group, an aryl group, a heterocyclic group, a nonane aryloxy group, a heterocyclic oxy group, a decyl group, an anilino group, a heterocyclic amino group, a carbon carbonylcarbonyl group, or an aromatic group. An oxycarbonylamino group, an arylthio group, a heterocyclic thio group or an alkylphosphino group, each of R 2 and R 5 , an alkyl group, an alkenyl group, an aryl group, a heterocyclic oxy group, an aryloxy group, a heterocyclic oxy group, , amidyl, fluorenylene, alkynyl, alkylthio, arylthio, sulfonyl or sulfonyl represents the stability of the 'R3 _ atom, alkyl, alkenyl, aryl, From the viewpoint of spectral characteristics and heat resistance, it is preferably Fe, Zn, Cu, Ni, Co, TiO, or VO Pt, Pd, Cu, Ni, Co or VO or V0 (V = 0). Among these, the aspect in which the compound is coordinated to the metal atom or the metal-based metal complex compound may be exemplified by a hydrogen atom, an alkyl group, a hydroxyl group, a hydroxy group, a cyano group, an alkoxy group or an alkoxycarbonyl group. An amidyl group, an amino group, an ureido group, a sulfoximine group, an alkane group, a sulfonylamino group, an azo group, an alkylthiosulfonyl group, an arylsulfonyl group or an oxygen independently a hydrogen atom, _ atomic group 'hydroxyl, cyano, nitro, alkanoyl, alkoxycarbonyl, aryloxycarbonyloxyamino, sulfonylamino, arylthio, alkylsulfonyl, aryl and R4 Each independently consists of a hydrogen atom, a group, a heterocyclic group, a decyl group, a hydroxy group -57-201221520, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a decyl group, a 7 oxo group, an amine carbaryl group. , anilino, carboguanamine, ureido, oxime imido, alkoxycarbonylamino, sulfonylamino, azo, alkylthio, arylsulfanylthio, alkylsulfonyl, The arylsulfonyl group, the amine sulfonyl group, the glycidyl group, and R are represented by a halogen atom, a dentate atom, an alkyl group, an aryl group or a heterofluorenyl group, and the metal atom or the metal compound is Zn, Mg, or S. i, clothing, Mo, Μη, Cu, Ni, Co, TiO or VO. Pd The following shows the aspect of the dipyrromethene-based metal complex compound. That is, in the above formula (I), RI and R6 are each independently a hydrogen atom, a group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a decyl group, an alkoxycarbonyl group, and a fluorene group. Base, amine group, heterocyclic amine group, carboguanamine group, ureido group, ruthenium imine, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, azo=alkylalkylsulfonyl group, The arylsulfonyl or phosphinylamino group means that R2 and hydrazine are each independently an alkyl group, an alkenyl group, an aryl 'heterocyclic group, a cyano group, a fluorenyl group, a decyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, Aminomethyl sulfonyl, quinone imine terpenyl, arylsulfonyl or sulfonyl, wherein R 3 and r 4 ^ independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. , cyano-indenyl, alkoxycarbonyl, amine, mercapto, carbenamide, ureido, fluorenylene, alkoxycarbonylamino, sulfonylamino, alkylthio, arylthio, *thio Or a sulfonyl group, an arylsulfonyl group or an amine sulfonyl group, which represents a V/nitrogen atom, a dentate atom, an alkyl 'aryl group or a heterocyclic group, and a metal or metal compound such as Zn, Mg or Si , Pt, Pd, Cu, %, or VO table The aspects. In the case where 'Co is coordinated to a metal atom or a metallized substance in a compound represented by the formula (I), the following shows a particularly preferable aspect. 〇-58- 201221520 In the formula (1), each of R1 and R6, ie, an atom, an alkyl group, an aryl group, or a heterocyclic group, is independently a gas A, a clothing group, an amine group, or a heterocyclic amine. Base, mercapto, ureido, oxime imine, alkane 4 carbamide, oxydecanamine, sulfonamide, alkyl sulfonyl, aryl, oligo, or phosphine The amino group means that R each independently is an alkyl group, an aromatic group, a terpenoid, a chaotic group, an oxycarbonyl group, an amine group, an alkane group, an alkane group or a group. The sulfonyl hydrazide 及+ and R4 are each independently represented by hydrogen® early ', 'R3 R7 as a gas atom, an alkyl group, an aryl group or a heterocyclic group, and a halogen atom, a sulfo group, an aryl group or a heterocyclic ring. The base represents a state in which the metal-derived compound is represented by Zn, Cu, 〜 or v 〇 (especially Zn). In particular, R3 = two in the general formula (1) is preferably a phenyl group from the viewpoint of excellent fastness. The reason for this is that (1) since each of R3 and R4 is a phenyl group, the spectroscopic system of the compound has a long wavelength, and when used in combination with a brewing cyanite material, etc., it overlaps with the spectroscopic (near 55 Onm) and becomes a star. The movement of the valley is easy (2) to improve the fastness of the compound itself by the presence of a bulky bulky substituent. Further, from the viewpoint of excellent solvent solubility, R2 and/or R5 in the formula (丨) is preferably 2,6-di-t-butyl-4-indolylcyclohexyloxycarbonyl. Among the compounds represented by the above formula (I), a compound represented by the following formula (Ia) is preferably compounded in a metal atom or a metal compound.

-59- 201221520 In the above formula (10), R丨, R2, and 4 represent a hydrogen atom or a substituent 'system with: 4 and each of R4 and R6 are synonymous, and a preferred gas (1) is Ri, Μ3, The halogen atom, the alkyl group, and the aromatic group are 〜, and the same applies. H7 is a group or a heterocyclic group. The R7 of the non-oxygen source t is synonymous with each other, and the preferred embodiment is also the same. The case where the metal atom or the metal compound of the above formula (1) is also a complex with the above-mentioned general formula, and the preferred embodiment is the same, in the case of the present invention, the two-degree ratio of each methylene-based metal is wrong. The compound represented by the following general formula (1)) is preferably a complex of a metal compound in a compound-compound. Metal atom bite R3 f#

In the general formula (I-1), Ri

The formula (I R2 , R3 , R' represents a hydrogen atom or a substituent. R7 represents a hydrogen atom and each of R6 is a monoalkyl group, an aryl group or a heterocyclic group. Ma represents a metal atom/α atom, and X1 represents a bondable to The base of Ma, χ2 indicates the base needed for the Zhongguang chelating compound. Furthermore, the 乂丨 and χ2 series can form a charge of J Ma, a ring of 6 or 7 members, and form a general formula (1). The r1 to r6 systems in 1) are synonymous with the general formula (1), and the preferred embodiment is also the same. R R R 6 -60 -

Ma in 201221520 represents a metal atom or a metal compound = ΓΓ position to a metal atom or metallization, and the preferred ": metal atom or metal compound is synonymous with ΪΓ1) R7 is a general formula (1) R7 is synonymous, and the preferred state is: X1 in the formula (M) can be as long as it can be bonded to the base of Ma. UB "Exports from water, alcohols (eg, sterol, ethanol, C Alcohol) bauxite and metal chelate" (1) Sakaguchi-. Ueno Jingping (1995 [3] (199Γ^) (^η1^° C°., Ud.)), the same [2] (1996) The same as the base of the compound described in the same year. Among them, from the viewpoint of production, #· &amp; ί ', 7, carboxylic acid compound, and alcohol are more preferably water or a carboxylic acid compound. The X-form of the sulfohydroxyl formula (Ι-ΙΐφΜ _mei m) does not require an acid group or the like in order to neutralize the charge of Ma. Wherein, the base group, the acid-lowering group, the phosphoric acid group, the /, and the k-position are preferably Λ ;; the base, the carboxylic acid group, and the quot; h is a halogen atom 鲼I group, more preferably a hydroxyl group, Carboxylic acid group. The χ1 and χ2 in the middle can also be interlocked with each other, and the 6- or 7-member ring. The formed 5 members, 6 members, and clothing, may be a saturated ring or an unsaturated ring. The ring system can be composed only of 6 lb. s., and the nitrogen atom ^, atom can be formed as a heterocyclic compound of atoms selected from the group consisting of oxygen atoms and sulfur atoms. In the invention, the methylene-based metal is mismatched to a complex of the group (1_2) or the compound represented by the formula (4) or a metal compound. -61 - 201221520

刖 R9, R 丨 base. R7 'aryl-pass' is preferably also represented by the same substituent or the same state as the aryl group or the general formula (I-2) in the general formula (1-2), R, R2 R3, R4, r5, r6, r8, R11, Rl2 and R13 each independently represent a hydrogen atom or a substituent and R each independently represents a hydrogen atom, a _ atom, a compound or a heterocyclic group. Ma represents a metal atom or a metal compound. The Ri to R6 system in the formula (Ϊ-2) is also the same as the case of Ri~ in the formula (I). The substituent represented by R8 to R1 3 in the formula (1-2) is synonymous with the substituent represented by R1 to R6 of the compound of the formula (j), and a preferred aspect thereof "(1) 2) When a further substituted group represented by R8 to R丨3 of the compound which is not present is used, when any one of the substituents R is substituted with two or more substituents, the substituents may be substituted. The R7 in the formula (1-2) is synonymous with R7 in the formula (1), and is preferably the same. R14 in the formula (1-2) represents a hydrogen atom, a halogen atom, an alkyl group, ', a clothing group. The preferred range of R is the same as the preferred range of the above R7 8-62-201221520. "When R14 is the base substituted by the town # „.. _ + j丞, it can be replaced by any of the foregoing, when Substituents substituted by substituents on 2 μ μ may be the same or different. In the general formula (1-2), Ma represents a metal or a metal compound. The same applies to the meaning of a metal atom or a metal compound in the case where the compound represented by the formula (I) is coordinated to a metal atom or a metal compound. In the general formula (1-2), R8 and R9 may be bonded to each other to form a saturated or unsaturated ring of f or 7 members, and R9 and R1 Q may form a saturated ring of 5, 6 or 7 members or not. The saturated ring, R11, is bonded to each other to form a saturated ring of 5, 6 or 7 members, and R12 and R13 may be bonded to each other to form a 5-, 6- or 7-ring or unsaturated ring. When a saturated or unsaturated ring is formed, 1 R2, R2 and R3, R4 and r5 or a saturated group R formed by R5 and R6, these are preferably the above compounds; Bonding and shape 1 and R12 may be saturated with a ring member and R1 is synonymous with a ring or an unsaturated ring, and preferred examples are also the same.

Stand for the base, aryl 3) -63- 201221520 base or heterocyclic group. Rare 8 and r9 each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group or a hetero

Cyclic amine group. Ma represents a metal atom or a metal compound. X3 represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, a fluorenyl aryl group or an aryl group), a nitrogen atom, an oxygen atom or a sulfur atom, and X4 represents NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a aryl group, a thiol group or a aryl group), an oxygen atom or a sulfur atom. Y1 represents NRc (Rc represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group or an arylsulfonyl group), a nitrogen atom or a carbon atom, and Y represents a nitrogen atom or carbon. atom. X5 represents a group which can be bonded to Ma, and a represents 〇, 1 or 2. 118 and Y1 can be bonded to each other to form a ring of 5, 6 or 7 members, and R9 and γ2 can be bonded to each other to form 5 members. Ring for 6 or 7 members. In the formula (1-3), r and R are respectively synonymous, and the preferred aspect is also the same. "Ma in the formula (1-3) represents a metal or a metal compound, which is the same as the above formula (I). The compound shown is coordinated to a metal atom or a metal compound. The metal atom or the metal compound in the body is also in the same range. % In the general formula (1-3), 'R8 and R9 each independently represent a linear, branched, or cyclic group having an alkane number of 1 to 36, *^^ more preferably 1 to 12, for example, a fluorenyl group. , ethyl, propyl, isopropyl, butyl, butyl butyrate, ^ ^ ' group, 2-ethylhexyl, dodecyl, cyclopropyl, its, cyclohexyl, ^ soil ^Adamantyl), alkenyl (preferably carbon number 2 to 24, preferably 2 to π, also alkenyl), such as vinyl 'allyl, 3-butene 64-201221520 Aryl (preferably having a carbon number of 6 to 36, more preferably a phenyl group, a phenyl group heterocyclic group (preferably a carbon 7 2: 8 = an example of a heterocyclic group) such as a sequenyl group, 2 ·=Γ~12 pyridine, 1-pyridyl, 2-benzoic, 2. The dense material from the present ketone, 1-imidazolyl, 1 - 咻 4 钍. sit small base), alkoxy (preferably, carbon number 36, more preferably f, a group 'e.g., methoxy, ethoxy, propyloxy,; -1, hexyloxy, 2-ethylhexyloxy, dodecyl Oxyoxy-oxyloxy group (preferably having a carbon number of 6 to ", more preferably an aryl group of 18"), such as a phenoxy group, a acetyloxy group, or an alkyl group (preferably a carbon number) Examples are alkylamino groups of 1 to 18, such as methylamino, ethylamine, more preferred amine, butylamino, hexylamino, 2, ethylhexylamine, di-aminoamine, and third Aminoamino 1 trioctylamino group, cyclohexylamino group-ethylamino group, N,N-dipropylamino group, N,N-dibutylamino group, &amp; ~ group-N-B Amino group), arylamine group (preferably having a carbon number of 6 to 36, more preferably an arylamine group of 6 to 18, such as a phenylamino group, a naphthylamino group, and an NR = ethyl-N- a heterocyclic amino group, or a heterocyclic amine group (preferably: a number of 〜24, more preferably a 1-1 amino group, such as a 2-amino-based η group, a 3-aminopyrazolyl group, 2—Aminopyridinyl, 3-aminopyridyl). In the formula (1-3), an alkyl group, an alkenyl group, an aromatic y y y group, a heterocyclic group, an alkoxy group, and an aromatic group represented by R 8 and R 9 . When the oxy group, the alkylamino group, the arylamino group or the heterocyclic amino group is a more substitutable group, any one of the substituents R may be substituted by two or more substituents. The substituents may be the same or different. In the formula (1-3), X3 represents NR, a nitrogen atom, an oxygen atom or a sulfur atom 'X4 represents NRa, an oxygen atom or sulfur Sub, R and Ra each stand out -65- 201221520, showing a linear atom, an alkyl group (preferably a carbon number * M ^ Μ Λ' Μ 36, more preferably a linear, branched or cyclic 1~12 Alkyl, for example Ί-Τ- « base, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, _ hexyl, 2-ethylhexyl, eleven, % A propyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, an alkenyl group, preferably an alkyl group (preferably having a number of 2 to 24, more preferably 2 to 19 -p, Μ. Vinyl, allyl, 3_U_yl), aryl fluorenyl 1 〇 4 丨 马 石 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 〇4 Φ ν+ . π violent), heterocyclic group (preferably a carbon number of 1 to 24, more preferably a heterocyclic ring of 1 to 12, which is a u ^ ^ 0 + a group, such as a 2-thienyl group, a 4-pyridyl group , 2_furanyl, 2-pyrimidinyl, fluorene, .. A t decyl, 2-benzazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriene..^ 1 9d s ·Base), sulfhydryl (preferably stone inverse 1~24, more wei 2~6^36*«· 尺佳 is 2 18 醯 base, such as acetyl group, trimethyl ethane group, 2 -ethylhexyl, benzoyl 1 hexyl), an alkyl group (preferably a carbon number M4, more preferably an alkyl group, such as an anthracenyl group, an ethyl 4 group, Isopropyl sulfhydryl, cyclohexylsulfonyl), arylsulfonyl (preferably an arylsulfonyl group having a carbon number of 6 to 24, more preferably 6 to fluorene, such as phenylsulfonyl, naphthalene Sulfosyl). The alkyl group, the alkenyl group, the aryl group, the heterocyclic group, the fluorenyl group, the decyl fluorenyl group and the aryl sulfonyl group of the above R and Ra may be further substituted by any of the aforementioned substituents R, when plural When substituted, the substituents may be the same or different. In the formula (1-3), γ1 represents NRc, a nitrogen atom or a carbon atom, γ2 represents a nitrogen atom or a carbon atom, and RC is synonymous with R in the above X3. In the general formula (1-3), R8 and γ1 may be bonded to each other, and R8, Y1 and a carbon atom together form a 5-membered ring (for example, cyclopentane, α is more than "I each β-determination, tetrahydrogen. Fu Nan, two Indole ring, tetrahydrogen, phenophene, 0 pirin, furan, thiophene, hydrazine, benzofuran 8-66 - 201221520 South benzo 11 phenophene), 6-membered ring (eg cyclohexane, piperidine, piperidine) Anthracene, morpholine, tetrahydropyran, dioxane, pentasulfinyl, dithiane, benzene, piperidine, piperidine, anthracene, quinoline, quinazoline) or a 7-membered ring (eg, cycloheptane) Alkane, hexamethyleneimine. In the formula (1-3), R9 and γ2 may be bonded to each other, and R9, γ2 and a carbon atom form a ring of 5, 6 or 7 members. The ring of the member, the 6 member, and the 7 member is, for example, a ring in which one of the rings formed by R8 and Υ1 and the atom is formed into a double bond. In the formula (1-3), when Rs and γ1 and R9 are When the ring of the 6-membered 6-membered member and the 7-membered member formed by the bonding of γ2 is a more substitutable ring, it may be substituted by the group described by any of the substituents R, and when substituted by two or more substituents The substituents may be the same or different. The 'X5' in the formula (1-3) The group bonded to Ma may be the same as χ1 in the above formula (M). a represents 〇, 1 or 2. When sa is 2, two X5 may be the same or different from each other. A preferred embodiment of the compound represented by the formula (Ι·3). That is, R to R, r7 and Ma are each a preferred form of a complex containing a compound represented by the formula (1) and a metal atom or a metal compound. Χ3 is NR (R is a gas atom or an alkyl group), a nitrogen atom or an oxygen atom, X4 is NRa (Ra is a hydrogen atom, an alkyl group or a heterocyclic group) or an oxygen atom, and is a nRc (Rc is a hydrogen source). Or a gas atom or a carbon atom, a γ2 nitrogen atom or a ruthenium atom is a group bonded via an oxygen atom, and R8 and R9 each independently represent an alkyl group, a heterocyclic group, an alkoxy group. a base or an alkylamine group, the ruler 8 and the γι may be bonded to each other to form a 5- or 6-membered ring, and r9# γ2 may be bonded to each other to form a 5-member, 6-membered ring, ... or i. 67- 201221520 The following is a better aspect of the compound represented by formula (I_3).

That is, each of RRR and Ma is a preferred embodiment of a compound containing a compound represented by the formula (1) and a metal atom or a metal compound. The XI X4 is an oxygen atom, the Y1 is a ruthenium, the γ 2 is a nitrogen atom, and the ruthenium 5 is via an oxygen atom. The bonded group, R8 and R9 each independently represent an alkyl group, an aryl group, a heterocyclic group, an alkoxy group or an alkylamino group, and the caliper 8 and γ1 may be bonded to each other to form a 5- or 6-member S'R9 and Γ2 can be bonded to each other to form a 5-member, 6-membered ring, and a is a pattern of 0 or 1. The molar absorption coefficient of the dipyrromethene-based metal-conjugate compound in the present invention is preferably as high as possible from the viewpoint of film thickness. Further, from the viewpoint of improvement in color purity, the maximum absorption wavelength is preferably from 52 Å to 580 nm, more preferably from 53 Å to 570 nm. Further, the maximum absorption wavelength and the molar absorption coefficient were measured by a spectrophotometer uv_24〇〇pc (manufactured by Shimadzu C〇rporati〇n). The refining of the dimethylene-based metal-based compound compound in the present invention is preferably not too high from the viewpoint of solubility. The following general formula (1-1), methylene metal complex compound I a - 5 1 , I a - 6 7 to I a 8 3, I a - A, τ 〇 A 丄 3 - 1 , 1-1 to 1-36, II-1 to 11-11, and the like. Specific examples of the two-sigma ratio 所示 shown in (1~2) and (la), etc. (exemplary compounds Ia_3 IIa-8, IIa-10~IIa-20)

Il-A). However, this invention is not subject to this 8 •68- 201221520

Compound number R*=Ff=i^=R'^ ;jn2n3«, p&amp;J» Hit 2 15 —Γ\ί—ΙΛν—ί%·, R?:=R!4 Ma :ia^3 —NH^彻^0« .......... —Chjj. Zn Ia*i4; Same as above _: Upper m week soil y==o --NHCOCHj Same as the same word on the same Zn as the mjb Cu. Fine. Ibid. Mk • ~.·.ν —Q.Ha lar$ -NHCCCHjOCHjCOQH: n± Same as: upper zn: Iai-9 same 4: m± servo mk Zn la-10 mm± —Ή' block.. ^ la-It m. Although sugar '· ^.3⁄4.. Zn .la-12 周上-^眺-Η cu la-l?: te ~ί?Η3- :3⁄4 laH:4. 'Same as the same soil. m Zn .la -15; ibid. · same as it~C3 with ..;k plus la-1:6 —HHGOCHi fixed r^W?s4H'eQOH Cu means H:7 ~NM2 m ~o: —Η Zn Ia-.i8' - V;. Same as above: Upper. Same as Cu' 1^-19. Same as upload) 1± v=〇: Jar2p Ma. Same as the main word, —¢^3.. Zfi fe-21. 岗.i. Μ ±: 茼i , Zn . la^-22 ^HC^HiOe'HjGOOM .同土,·~Η; m h-i3 · ',. - 11 Jt m.· m±. ,.: Ζή: -69- 201221520

Compound number r'=r6=r8=r'3 r^^r^r'2 r'=bm Ma la-24 &quot;WHCOCH2OCH2COOH CJjg(t) -COO-C^)*CH3 c5ift) Cu la-25 Ibid Same as the order of Zn fa-26 on the same as above H&quot;p Π30 between Ζή fa-27 qo〇H —MHCO^^ Same as above-ch3 —Η Cu la-28 Same as above ibid.*~ch3 Zn Ia,29 SO3H Same as above Cu la-30 Same as above C2Hs -ch2-6hc^h9 Same as above Cu ia-31 Same as above Zn la-32 Same as above Same as above Zh Ta-33 —mhs〇2ch3 Same as above-ch3 Same as Zn la-34 -ch2q-Q~n3s〇 2 Same as above, same as above Zn 8 -70- 201221520

Compound number Rl:Re=ft8=R,3 R2=R5=Rs=R,2 r3=r~r,&amp;=r&quot; R7=R “ Ma la-35 -gh2o-O&gt;~och3 cut (1) ~〇 *~ch3, 2π la-36 CHa 上上上上上上Ζη !a-37 chzgooh —M-SOaCHj Same as above as above Ζη la-38 —Cl Same as above I. Cu Ia-*39 —S~qH2COOH Same as above Ibid. Cu !a -40 CHj —S-0HCOOH Same as above Cm la-41 Same as above Ibid. v=d la-42 —SGjCH^ Same as above, V-0 la-43 Same as above-〇m± Cu fa-44 CH3 Ibid. Cu la-45 ~GH3f Same as above CH3 _Η Cu Ia-4$ Ibid. Same as above - gh3 Zn la-47 Same as above Same as above 4: Cu Ia-48 Same as above Same as above Ni!a-49 —〇4曜 Same as above and above Zn !a-&quot;5〇 Same as above, same as above, Pd Ia-SI —GHaCHjCOOH Same as above, same as above Zn -71- 201221520

Compound number r'=r6=r8=r'3 R?rR5=R9=R,? R3=R4rR?&lt;)=R&quot; r7=rm Ma fa-67 —NHg —CN —GH3 —H 2n la-68 —nhc〇ch3 Same as above. -CH3 2n la-69 ~CH3 Same as above Ibid 2n ia-70 Same as above~o Same as above · Zn ia-7t —C13H27 Same as above-CH3 ο Cu la-72 —NHj Same as above-cf3 Same as Cu la -73 -NHCOCH2OCH2COOH Same as above, above Cu ta-74 -ΝΗ(5〇~ώ&lt;^^4{^〇2 Same as above--όη3 Zn la-75 -QC〇-N(CH2CH2〇CH3)2 Same as above~C3H7(IS0 Same as above Zn !a-76 Same as above - 0 Same as above Zn Ja-77 Same as above ~cf3 Same as In la-78 ~nhcogh2och2cooh Same as above-Q-CO-fliCHiCH^CH^ Same as 2rt la-79 ~Q CJHoit) ^oo-/ ^ch3 c%0 ~-〇~°Η3 CH3 _ Zn ia-80 Same as above-C4H9(t). Same as above 2n ia-81 ~Ci3H^ Same as a Same as above Zn la-82 —nhgoch2gch2cooh —COOC^Hs S02N(CH2CH2 〇C2HS)2 Same as above Cu la-83 ~Q ch2cooh 5Ο2-Λ-€Η20ΟΟΗ C/UO) ^go-(Vch3 —ch3 Same as above Zn 8 -72- 201221520

Compound number '4· - :Λ·... . Λ.' . : 养铁:洛轳: ρ^_ρ4^ρί Ρ_ρ1 ΐ nk-n&lt;..r:K Μ 诚 ' _ 颂 颂 Ζ ;. Si? Itchy brewing &quot;Η lla-3

73 201221520

llaH3 I la-10

O 0 NC^rtVC0 hoocch^ W CH,

Ca^W

义育 CH3 CHj.CH3

lla-M

CHa-

COQ-&lt;&gt;-CHa Ming CH?CH2CH2COOH BuOOO ΌαΜ) / \/ hoocch2ch2-Ch2.

I la-15

Cv4Hs{1)

Wide COOK &gt;-ch3 /h3. \ /, ch3. (1) 201221520 llari6

Ma-19

CH3 CH3 CH3 V-coc CH3C〇-NH f\ h2o oocch3 I la-17

I la-18

75- 201221520 Η CHr 1-5

Pm ch3 ooc^A^^-ch(10))h

C4H9(t) d&quot;H2 xo-cdch3 -ch3 ch3-

p4H9&lt;t) Ο4^θ(0 |SJH 1-2 CHy

PaM) qoc

〇4H9{t) coo ch3

. Lake, i/h2. \ 〆 Λιη2 C4_ ch3

C^Hsft) OOGwHh/

bH2OCH2〇〇OH 201221520 1-9

〇αΗ3(Ϊ) C4H9&lt;0, Fe[ fsj ώ(Η9(〇 CHs H0

C4H9(t) ^ gH3 C^¥P ch3

l-U ,cqo V^043 nh2

CH3 w.../ ^ / v / \ ί _ C4H9W HN N c4H9(t) ch3 J-n ch3 〇4H9(t) ch3 ch3

COO-G2H5 C4H6(tj

G4H5(t)

C4H9(t) l-*5 CHS

:^V^Vycc &gt;-N zN«( &gt;7;. m- NH2 ^Zn^, NH2 C4H9^0** , 0 "GCH~C-CHa

1-12 p4_ C YH3 OOC^y^CH^^^^QO- _ (|ΤΝ,Ζ(\, C4H8(t) &gt;=N·&quot; ^O-C'Vi is called QH9(t).

CH3 C Yan? Bu Yi 6

:ZnC nh2 CH 疒 C_CM=C-CH3 C2H5OOC ^^Λ^ΟΟΟ P.Hs(t)

-77- 201221520 Ι-ί7

Η9 -21

CH3-

.C4HQO) Ρα^) ch3 ODOs ch3 ci_ a coo

1-23

CHj-c^oh CH2OCHse〇OH ζ) ζ) 〇Λ (0 CH3&lt;N&gt;, .-cf

C Lake ^O-H^VcHa 1-24 C4He(t) ch3- 夕〇 ΌΗ

NHS〇2CH3 -! P-&lt; ^ CHNHS02CH3 *0, ΛΪ_Ι όκ^ )-CH3

C4_ ^ 'CHNHS02CHj.

CH3&quot;〇t〇H 〇H -78- 8 201221520

1-26

CHa

1-27

1-28

-79- 201221520 !-32

〇4Η9(0)C^V^ 〇4Η9(0

Ηη3 1-35. 0Hr p4^s(0 r.n. QHa(t) e4H9(tj nJ~nxp^)TOT^yN,N/HC0CHj ^

CHj

NHCOCHj^HfiW Λ〇λ^Φ) m2 Ν &quot;Νη*·^ 切割 W \·‘· /^ C4H9W c义(t) CHy CH3 1-33

QHsiO

Γ-34 e4H9(t) —GOC,~. 4 off Nh2 CH3 (?0-NH

Ch5- ^(t) C4H8(t)

CH, °m wide COO—y-CH3 /ΝΛΗΟΟΟΗ3άί») X^HCOCH,^,) 'COO—CH3 ch3 ch3

C4h9(0

-80- 201221520

Compound No. ff : Ψ .黎:... 1IH -cm- -rCO.G:C^5 W- Μ Serve. Zhou forced m±. —^HSC^CHa,; Same as IE. Π-3 with i 痈士: ;·&gt;.周;fc.·.;·.〆 〆 fine Φ fiber: ir—4v :&quot;^Q 1 Vll ·, Λ t*l NHS〇2, CH| test _ ΜΆ -Ο .- . Miscellaneous m 1h lobes only ^OOPiiis Shang Shang: :Fresh• ····· . *., ··· ·· . i ~GH> pGH:2COCiH: marriage. Π-6; '.同龙'. .. .m .... ..._. Weng.. .:働.; .'two........ -81 - 201221520

Compound No. R1 re R3 R4 R9 X1 .11-7 ch3 -COOC2H5 o One CHs Η?0 Π-8 ~Q with ± Same as above Same as above; Π-9 &lt;&gt; nhso2ch3 —CN —ch3 —CH3 Same as above Same as above ΙΜ 0 nhso2gh3 Same as above m± nhso2ch3 Same as above H-11 Same as above o ~o —ch3 Same as above.

Compound No. R* R2 R3 R4 R7 R9 X' ΙΙ-Α One CHa: —COOC2H5 —CH3 —ch3 ch2cooh —CH3 h2o Next, the second ratio p of each of the above-mentioned general formula (I - 3) is shown. Specific examples of the compound of the complex (exemplified compounds ΙΠ-1 to III-103, III-A to III-C and IV-A). However, the present invention is not limited by these. 8 -82- 201221520

Compound number.w.:: compound. .number i$. :3irX \M ♦ ♦.· .* -m. 丨职' (4) -J&amp;k • Ιϊ ^*ν! 'r- ·· - 杏破翁- Turn over, _ϊ J Γ Γ 〇 〇 - - - - - - - - - - - - - - - - - 一 痛 痛 痛 痛 — — — — — — — — — — — — — — — — — — — ' . · * .·* ··::· 同:ϋ: 细. ·,·ί .···. .翻..〇...do m. :^=3⁄43⁄4 : scare / | ....: ^mmmk :.·«.« .' ····; «: · j- ·- .·,···* S:jt: .-.&gt; :1113⁄43⁄4 , V . ·. :; —eOrrQH-GQGH^ ..麟....., ♦ .,. .-y· 诵_ · ..... » \w\p :-3⁄4 Sharp H^cSck^Ns. .thief.. ··· 〆:v* ·. ...1!_ :m \.$p§ A bad HN sun dribbles] Chi. Gossip: sea f: * '.ν'*, f 4g. with Qin* * *, * i'* i 113⁄4 Debate '... ; ei4%H3 MM .&lt; ·\ * ·.* :H!r2 l 浐叫Γ Face:! 111-22;· - ..,- '', ·二乡瓣和泼' 同:土-·,τ - · 迦......Ί 狮·献:mh wm -ΐΡ^Η'5: » ' V - · ·· · ' · ~ tr&quot;' :战:...战摄-83- 201221520 ?%Ή.:

ΟΟΟ.*^^ Φ' ^φι-PL·^ #13⁄4. ·) ί=〇ί··: '::; ^b;·^;: 瘅: 'S; a compound number • if compound number • :;UI-2$ 111-26 一_; :矜臂((狰麟 lii-zr -纲_杂: -面_转. lfH3D .··,···:...... :.. : .···:..··., .·Μ ν · · · · · 辉 辉 辉 辉 辉 辉 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ « &lt;·· .*. -CHsNHso^Hv 9sHs, turn: for.... Secret. Exposure 8 -84- 201221520

Compound No. # φ Compound No. # Μ: :犹旁' Lion: One: 'Ilte37: NHS〇iC^3 Ibid IIHJS .. . . · · *. · ·· ····. . mh Edit $-p Lion k土•···.·: .· ;· ; , - K .· · · Face: f· ....·.. Itir42 'Warrior · Paradox with 4 shouts -85- 201221520

Compound number: R® R?;i Compound number 1Π-45: ......_...... 嫩 43⁄43⁄4 Ϊίίτ48 !^0 -Ο Tip φ as 3. One: 1Π-5〇: .. .. ... -CHiNHSO#^ ;inr5H :—3BNHS.〇i'CH3 at W52 -CH cold 02 cake 3 gh3 &quot;iCHNHSP2CH3. 0hi3 ' iii-P -dHNHSPiGHa 1 with the valve:~Q. ^ihsQjCh3 ;^^}3⁄4 ;ΙΠ^55; Nt4S02CH3- \\'Λ·· . ..·_,. .1··. 1 Net 8 -86- 201221520 c4_y

Wei 纠 Ί ·Μ=/ . W4, name. €;&quot; ^-

Compound No. ff Compound No. MfrbJ! 1CH3 m -CH3 J Tips CHV ψί -Ct^ m- .1IF59 Same as lff-60'1 , :^Q; ~COBCH% ·:. 1.·* · ::H Bu 61: /3^3⁄4 〇e oh yeah 2: mmm .: ibid. ΙΠ-63 .ip fresh in-64. -Q -87- 201221520

Compound No. R3 R4 R8 R9 111-65 —ch3 —CHa —COOC2H5 —OH3 —CH3 111-66 Same as above -chnhsq2ch3 ch3 -chnhso2ch3 ch3 1Π-67 Same as above Ibid.~^Q nhso2oh3 nhso2ch3 1J 卜68~〇 Ibid. Ch3 —ch3 111-69 〇-〇 Same as above Ibid. 111-70 —CH* 〇C4Hg(t) —COO&quot;^~V-CH3 C&amp;) Same as above-ch2nhsq2-^^-ch3 8 -88- 201221520 ^4HS( 1) ^ η # _V ?-N^v^N=1( C4H^'HW -N, ^ ! p%9

Γ QK H3C4 Compound No. R3 30 R3 R8 if ::III!H71 - 〇鹤-C〇rNGH;3, just Jli-7g. On the 'same. 〒3_娥-C0-N9gH:7as〇) Last week, 111-73 m± Age-CQNH-^~^ Same as above: Miscellaneous 74..: Same as: Upper 'Supper Γ7^ ch3 mM ©is: :Cooking up. mh -89- 201221520

Compound number 0 φ R?· •rv··. :R?&quot;lira; Μέί-ii *- - ····«- • · 111:-77: Drink _ 赖: ... so pick m _: Gas: turn, ..:. . . .:. t. throwing 1 . . . mm Ά, •JL,;..;:·· ...... fine&quot;-Q:i '- 1' ΐίίτδΐ Loss: Secret Jing _ Turn _.. . Comrade: , face ceramic fiber m difficult -90- 8 201221520

Compound No. If pr ·Γ\-· t .· - · 1 Follow 3 : t to __3.:: mfy ........ J..··. ..··:: · * :; *·: -· vv;' earn MM weaving: position: , / ί %JL 1晦 _:+: .· · · :·····...··· Pain is the same as _: Same as iE. _ . 5 ·ν r :· ;*: · , VV ··. 111-66 r. s ·. .,. · ..... /. .. ·······... ..'············ ms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Lion...··································································· · .. ·,·················································································

Compound braided iron ^ ^ ' III-90. ^?η3: • ../StJ' ~s^m -m «Γ Μ±: Same as above: One clock __喰.:/ί%;·υ· 1 *· M'fio:; \Άφ: batch m. one na miscellaneous 13⁄4 mm P.rt ΙΙΙ-93;, \ ψ CfHj J complement: the same as: Μ± :, just: .nw ΙΠ^95.' MJi-·土•^0HNH:S〇5〇H3. mk Same as above: 'Ibid rr'rQ Flying HSQ (4) Buddy mj' !\;· '.· Μ... ·' . . . ··· Γ !1 -92 201221520 &gt;=〇· £ &quot;&quot;&quot; % grain compound number; R?: embedded Ff; l_l -p : -p ^Hs;; ;-:6% 1 turn ^Ο^ι: W : :;~ C5r^1 LM ....... Μ-t:· M±. iiRoa 喰. Wi± Fresh, πι.^ιοι ::&quot;PM;-k. Survey. Outline (rat, face 3, paid) ? Touch 3 峨 .:3⁄4 i: ~Q ,r%........ 1 胆狮 -93- 201221520

Compound No. R7 R8 R9 A布 A ch2cooh —〇4Η9〇) A C4H9(t)

Compound Yang No. R3 R4 R5 R? R® H9 ΙΙΓ-Β —CH.+3 —:CH.3 -COOC2H5 ch2cooh one eH3 -ch3 8 -94- 201221520 R3 r7 R4

Compound No. R3 R4 R7 R8 R9 IIIH3 —ch3 —CH3 ch2c〇〇h —CH3 _CH3

Compound number R8 R9 W-A

-95-201221520 The dipyrrolidinium-based metal-conjugated compound obtained by the compound represented by the above formula (i) can be used in the specification of U.S. Patent No. 4,7,7,3,3,9, and the specification of No. 5,433,896. Japanese Laid-Open Patent Publication No. 2001-240761, the same as No. 2002-155052, Japanese Patent No. 3614586, Aust. J. Chem, 1 965, 1, 1,1835-1845, JH Boger et al, Heteroatom Chemistry, Vol. The method described in .i, N. 5, 389 (1990), etc. is synthesized. For the specific synthesis method, the descriptions of paragraph numbers [01 31] to [0157] of JP-A No. 2 - 2 9 2 9 7 0 can be referred to. Next, the general formula (II) will be explained.

In the above formula (II), A1 represents a 5-pyridyl group selected from the group consisting of oxazolone, barbituric acid, thiobarbituric acid, laurel, hydantoin, and thioacetamidine. Oxazolinone, rhodamine (rhodanine), and oxazolidine two g, the same. ratio. Sitting on σ set m known as diketone, hydroxy acridine, pyrazolopyridine_, tetrahydro"it2,4_dione, 3-oxo-2,3_dibenzobenzo (4). a compound of the group formed by the combination of 1,1-dioxide and 3-dicyanomethyl 2,3-dihydrobenzo[d]thiton-1,1·dioxide The acidic core coming. Among these, Α1 is preferably from 5-pyrazolone, isoxazolone, and barbituric acid Kd対. Dicarboxylic acid, indandione, and thiol. An acidic nucleus derived from bitten and pyrazolopyridone. -96- 201221520 L1, L2 and L3 represent methine groups. R33 and R34 each independently represent an alkyl group, an aryl group, an alkoxy group or a hydrogen atom. R35 represents a hydrogen atom, a decyloxy group, a chlorine atom, a fluorenyl group or a nitro group. Wherein R.sup.33 and R.sup.34 are each independently preferably a hydrogen atom, a substituted or unsubstituted hexyl group having a carbon number of i to 10 (eg, methyl, ethyl, propyl, arylethyl, methoxyethyl, a benzyl group, a carboxybenzyl group or the like, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (for example, a phenyl group, a p-dimethylamino group, a p-diethylamino-o-methyl group, 2, 4,6-trimethyl, p-hydroxybenzoyl, p-ethoxycarbonylphenyl, p-sulfonylaminophenyl, etc.). η represents 0 or 1. However, the substituent 'which is at least one of κ 键 bonded to Α1 and R33 to r35 has at least one selected from the group consisting of a sulfhydryl group, a sulfonamide, an oxonium, and an amidoxime group. One. Further, these groups are preferably two aryl groups bonded to the molecule. More preferably, it is a carboxyl group. Further, the car is preferably a compound of the above formula (II) represented by the following formula (Ila).

The general formula ®a) is the same as the general formula (II) in the above formula (Ila), R33 to R35, and l1 to l3, and the preferred embodiment is also the same. And -97-201221520 R is preferably a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms (for example, anthracenyl 'ethyl, butyl, tert-butyl, 2-oxyethyl, methoxyethyl, 2 substituted or unsubstituted aryl group (e.g., phenyl, anthracenylphenyl, methoxyphenyl, chlorophenyl, naphthyl, thiol) having a carbon number of 6 to 1 fluorene (e.g., ethyldifluoroindenyl) a phenyl group or the like, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms (for example, an anthraceneoxy group, an ethoxy group, a butoxy group, a decyloxyethoxy group, etc.), a substitution of a carbon number of 2 to 5 or An unsubstituted alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, 2-decyloxy 6 oxo, butoxy, etc.), substituted or unsubstituted aryloxycarbonyl having 7 to 12 carbon atoms (e.g., stupid) An oxycarbonyl group, a methoxyphenoxycarbonyl group, a gas phenoxycarbonyl group, a methylphenoxycarbonyl group, etc., a substituted or unsubstituted aryloxy group having a carbon number of 6 to 1 Å (for example, a phenoxy group, a phenoxyphenoxy group) Etc., a fluorenyl group having 2 to 5 carbon atoms (e.g., anthracenyl, propylidene, butyl, etc.), a hydroxy group, a cyano group, a fluorenylamino group having a carbon number of 2 to 1 (e.g., an ethylamino group, a benzyl group) Mercaptoamine, etc., urea group (eg A Alkureido group, ethylurea group or the like), an amine group (e.g., dimethylamino group, diethylamino group, phenylamino group, phenylphenylamino group, decyloxyphenylamino group, etc.), and the like. R is preferably a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (e.g., phenyl, p-phenylphenyl, 3' 5-dicarboxyphenyl, o-carboxyphenyl, phenyl, decyloxy). A phenyl group, a methylphenyl group or the like), a substituted or unsubstituted aralkyl group having 7 to 12 carbon atoms (e.g., a benzyl group, a 2-carboxybenzyl group, etc.). Specific examples of the compound represented by the above formula (II) are listed below. However, the present invention is not limited by these. 8 -98- 201221520

Sot Ri R« R* R» 1 r-CHi -^〇y&gt;-eo〇HHHH 2 -CH* n K If il 3 -CODC,iU n H If i! A —OGIU n 11 II 1! 5 n HH β 6 -OH μ HHH 7 -cxm u HHH 8 -CIU // K -CH, H 9 -ΟΟΟ^Η» u H -CHJ; H 10 // &lt;〇&gt; -au H 11 COOH n -au II \—^ COOH 12 -(Q^-cooh -CH, —CH> H 13 -au n -ώρο,Η» II H l\ -QU it -OOOCtHt -3⁄4 H 15 —0”, // —Cl TCjJU tl 16 -03⁄4. u HH OCSt 17 -OpOCtH» &quot; HH IB -cil, ft 11 II id &quot;CHj // HB Cl 20 -CH, ii HK au 21 -at it H -3⁄43⁄4 H 22 -αι» ^- (〇) COOH H -QU tl 23 -ax)C«!U -qu. -C.IU It Z4 u -CH, -ho, 25 -dL Fee COOH -(3⁄4 -CH* H -99- 201221520 4 3 CHa

COOH 4 8

Cx H* CH,

45 cm 4 4

S8 NHSO, CH&gt; o 5 9

eo〇H

COOH -100- 8 201221520 8 9 η

7 0

Next, the general formula (ΠΙ) will be explained. -101 - 201221520 R44 i%l&quot;;;, ,, ·▲· ..\.\ .· Ar*. · ·»

M m General formula (IE m) In the above formula (III), R41 represents a heterocyclic group, and r42 represents a hydrogen atom or a substituent. Re, r44, r45, r46, r47 and r48 each independently represent a hydrogen atom or an alkyl group. , alkenyl, alkynyl, aryl 'heterocyclyl, decyl, alkoxycarbonyl, aryloxycarbonyl, amidino, alkylsulfonyl, arylsulfonyl or sulfonyl. R43 and R44 They can be interlocked to form a ring of 5, 6 or 7 members. R45 and R46 can be interlocked to form a ring of 5, 6 or 7 members. R47 and r48 can be bonded to each other to form 5 members. Or a ring of 7 members. R41 is preferably a heterocyclic group having 1 to 36 carbon atoms, more preferably a heterovalent group having 2 to 24 carbon atoms. For example, pyrrole group, furyl group, thiophenyl group, benzophenone is preferred. 0 洛洛基, stupid and furanyl, benzothiophenyl, pyrazolyl, isoxazolyl, isomeric. all-base, carbazolyl, benzisoxazolyl, benzisothiazolyl, Sodium, oxazolyl, thiazolyl, benzimidazolyl, benzoxazolyl, benzoxyl, π-biti, 喧, 啥, 塔, 基, 基Pyridyl, pyridyl, porphyrin, hydrazine, quin Phytyl, quinoxalinyl, acridinyl, phenanthroline, hydrazine, carbazolyl, carbonitrile, fluorenyl, tris(s), 〇^·2β, 嗔. More preferably, it is 3 -17 fluorenyl, 4-pyrazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-oxazolyl, 2-thiazolyl, 2-benzimidazolyl, 2-benzoxazolyl, 2-benzothiazole-102-8, 201221520, 2-pyridyl '3'pyridyl, 4-pyridyl, 2-quinolinyl, 4-quinolinyl' 1 Quinolyl ' 3 -isoquinolyl, 3 -fluorenyl, 4 hydrazine, 2 -pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2 pyridinyl, 2 fluorenyl, &amp; Base, 8-mercapto, 3-3-triazolyl, 5-triazolyl, 3-oxadiazolyl, 5-diethyl. Sit-based, 3-indenyl. Sit-base, 5-sigh two. Sit-base. Also, Preferably, r43, R44, R45, R46, R47 and r48 each independently represent a hydrogen atom, an alkyl group, a dilute group, an aryl group, a heterocyclic group, a fluorenyl group, an amine mercapto group, an alkyl group, an aryl group, and an aryl group. In the case of a sulfonyl group or an amine sulfonyl group, it is more preferably a hydrogen atom, an alkyl group, an alkenyl group, an aryl 'heterocyclic group, an alkylsulfonyl group or an arylsulfonyl group. The case of the It is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or a pyridyl group. In the formula (ΠΙ), R is preferably a R41 system, a pyrazolyl group or a 4-pyrazolyl group. , 2-isoxazolyl, 4-imidazolyl, 5-oxazolyl, succinyl, 2-oxazolyl, 2-benzimidazolyl, 2-benzoxazolyl, 2-benzothiazolyl, 2_ Than base, 3+ group, 4 · pyridine group, 2 • porphyrin group, 4 啥 porphyrin group, ^ isoindolinyl group, 3-isoindolyl group, 3 · tower base, 4_ tower Respiratory, Milidinyl, 4, 4, η, 2, 2, _ D, listening group, 2 _. Acetin, 6-mercapto, 8-mercapto, 3-oxadiazolyl, 5-triazolyl, 3-oxadiazolyl, $-oxadiazolyl, 3-s-oxadiazolyl or 5-thiadipine Azyl, π is hydrogen, alkyl, dilute, alkynyl, cyano, aryl, decyloxy, alkoxy, diloxy, alkynyloxy, alkoxy, alkoxy Or an alkynyl group, R43, R44, R45, R46, R" and R48 are each independently, a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a decyl group, an alkoxycarbonyl group, an aryloxy group. a pigment represented by a few groups, an amine-based base, a base, an aryl group or an amine-based base. -103- 201221520 More preferably, it is a r4 1 system 3 -. ° ratio. Sit-base, 2-m. Sit, 4-° m., 5-imidazolyl, 2-oxazolyl, 2-thiazolyl, 2-benzopyranyl, 2-benzopyrene Azyl, 2-benzothiazolyl, 2-pyridyl, 3-pyridine, 4-pyridyl, 2-quinolinyl, quinolinolyl, isoquinolyl, 3 3-cyanoyl 4- 4- morphinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-° dimethyl, 2-pyridyl, 2-indenyl, 6-fluorenyl, 8-fluorenyl , 3-three saliva , 5-triazolyl, 3-oxadiazolyl, 5-oxadiazolyl, 3-thiadiazolyl or 5-thiadiazolyl, R42 hydrogen atom, alkyl, alkenyl, cyano, Alkoxy, alkoxy or alkylsulfonyloxy, R43, R44, R45, R46, R47 and R48 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a decyl group or an alkane a dye represented by an oxycarbonyl group, an aryloxycarbonyl group, an amine mercapto group, an alkyl group, an arylsulfonyl group or an amine sulfonyl group. Preferably, in the formula (111), the R4! _pyrazolyl, 4-pyrazolyl, 2-metenyl, 4-imidazolyl, 5-imidazolyl, 2-oxazolyl, 2-thiazolyl, 2-benzimidazolyl, 2-benzopyrene Azolyl, 2-benzothiazolyl, 3-. indenyl, 4-cyanophthyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-indolyl 3- 2 5 - triterpenoid, 3-dose 2-sodium, 5-sodium diazide, 3-thiadiazolyl or 5-thiadiazolyl, r42 hydrogen atom, alkyl or cyano group, r44 And r45, r46, r47 and r48 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, an aryl group, or an amine group. For the details of the pyrimidine azo compound represented by the above formula (III), reference is made to the description of the publication of JP-A No. WO 07-397. Specific examples of the pyrimidine azo compound represented by the formula (III) include the exemplified compounds (1) to (7 4) described in paragraphs [0028] to [〇〇48] of JP-A-2007-3 9478. The same compound 8 - 104 - 201221520 Next, the general formula (ιν) will be described.

In the above formula (IV), Ra 1 , Ra 2 , Ra 3 , Rb 1 , Rb 2 and Rb 3 each independently represent an argon atom or a monovalent substituent. Ra 2 and Ra 3 may bond each other to form a heterocyclic ring of 5 to 7 members. A2 represents a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. η represents 0, 1, 2 or 3, and when n is 2 or more, Rb2 and Rb3 which are present in plural plural may be the same or different.

The "monovalent substituent" represented by Ral, Ra2, Ra3, Rb1, Rb2 or Rb3 may be a substitutable group, and examples thereof include an aliphatic group, an aryl group, a heterocyclic group, a fluorenyl group, and an anthracene group. Base, mercaptoamine, aliphatic oxy, aryloxy, heterocycloalkyl 'aliphatic oxycarbonyl, aryloxycarbonyl, heterocyclic oxycarbonyl, amine mercapto, aliphatic sulfonyl, aryl Sulfonyl, heterocyclosulfonyl, aliphatic sulfonyloxy, arylsulfonyloxy, heterocyclopentadienyloxy, amine fluorenyl, aliphatic hydrazine, aryl amide , heterocyclic amine chain, amine group, aliphatic amine group, arylamino group 'heterocyclic amine group, aliphatic oxycarbonyl amine group, aryloxycarbonylamino group, heterocyclic oxycarbonyl amine group, aliphatic Sulfhydryl, aryl sulfhydryl, aliphatic thio, arylthio, hydroxy, cyano, sulfo, carboxy, aliphatic oxyamino, aryloxyamino, amine sulfhydryl Aminesulfonylamino, il-primogen-105-201221520, amidoxime-yl-fluorenyl, amine-formylamine sulfonyl, di-aliphatic oxyphosphinyl, diaryloxyphosphine oxide Base, etc. The substituent may be further substituted by other monovalent substituents. In the above, Ral, Ra2, Rb2, and Rb3 are preferably a hydrogen atom, an aliphatic group, an aryl group, a decyloxy group, a decylamino group, or an aliphatic oxy group from the viewpoint of the effects of the present invention. , an aliphatic sulfonyloxy group, an arylsulfonyloxy group, an aliphatic sulfonylamino group, an arylsulfonylamino group, an amine group, an aliphatic amino group, an arylamino group, an aliphatic oxycarbonylamino group And an aryloxycarbonylamino group, a heterocyclic oxycarbonylamino group, a hydroxyl group, a cyano group, a sulfo group, an amine carbylamino group, an amine fluorenylamino group, more preferably a nitrogen atom, an aliphatic group, In the case of an aryl group or an aliphatic oxy group. Further, Ra2^ can be bonded to each other to form a ring structure of 5 to 7 members. As a better Ru, carbon number! The alkyl group of ～12 is suitably used. For example, the methyl group may, for example, be an ethyl group, (1) a propyl group (isopropyl group), (1) a butyl group (t-butyl group), a hexyl group, a 2-ethylhexyl group or a dodecyl group. Wherein ' is preferably an alkyl group having a carbon number of i to 8 and particularly preferably an alkyl group having a carbon number of 4. Preferably, it is an aliphatic group or an aryl group, and β is preferably a hydrogen atom or an aliphatic group, more preferably a ruthenium group, and particularly preferably a case where Ra2 and Ra3 are bonded to each other to form a ring dance. . The ring structure at the time of forming the ring structure is preferably a ring of $ members to 7 members, and more preferably a ring of 5 members. Further, Rbl, Rb2, and Rb3 are particularly preferably argon atoms. Preferably, the hydrogen atom aliphatic group is Rbl or has a substituent, and the aliphatic group is synonymous with R or Rb3, and the aliphatic group may be an unsubstituted system and represented by the following Α2. The same is true for the preferred aspect of the benefit of the parental formula, which is unsubstituted or has a substituent. 8 -106- 201221520 From the standpoint of fastness, η is preferably 〇, i or 2, more preferably 〇 or 1, most preferably 0. When A2 in the above formula (IV) has a substituent, the substituents may be the same as those listed under the item "monovalent two groups" represented by Ral and Rb1 to Rb3. The basis. Preferred are heterocyclic group, mercapto group, nonyloxy 'mercaptoamine group, aliphatic oxy group, aryloxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, amine Mercapto, aliphatic sulfonyl, arylsulfonyl, heterocyclosulfonyl, aliphatic sulfonyloxy, arylsulfonyloxy, heterocyclosulfonyloxy, amidoxime, aliphatic Sulfonamide, arylsulfonylamino, heterocyclosulfonylamino, anthraquinone, aliphatic arylamino, aryloxy, arylamino, heterocyclooxyamino, aliphatic sulfin Alkyl, arylsulfinyl, hydroxy, cyanocarboxy, sulfonylamino, a halogen atom, an amine sulfonylaminomethyl sulfonyl group, an amine sulfhydryl sulfonyl group, and the like. Examples of the unsubstituted aliphatic group represented by A2 include, for example, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 2 carbon atoms in total, and an alkynyl group having 2 to 20 carbon atoms. Among them, an alkyl group having a total carbon number of i to 15 is preferable, and a group having a total carbon number of 1 to 1 Å is particularly preferable. Examples of the aliphatic group having a substituent represented by A2 include a substituted alkyl group having a total carbon number of 2 to 20, a substituted 7 group having a total carbon number of 3 to 2 Å, and a substitution of 7 to 20 total carbon atoms. Aralkyl group and the like. Among them, a substituted alkyl group having a total carbon number of 2 to 15 is preferable, and a substituted alkyl group having a total carbon number of 2 to 1 Å is particularly preferable. The aryl group represented by A may be a minor ring, and examples thereof include a phenyl group and a 4-methoxyphenyl group. Wherein, the aryl group having a total carbon number of 6 to 30 is preferred, and the aryl group having a total carbon number of 6 to 2 Torr is particularly preferably an aryl group having a total carbon number of 6 to 2 Å, more preferably an aryl group having a total carbon number of 6 to 丨5, particularly preferably 6 to 12 aryl groups. The heterocyclic group represented by A2 may also be a fused ring, preferably a substituted or unsubstituted heterocyclic group having a total carbon number of 2 to 30 in a 5- to 7-membered ring. Among them, the heteronuclear group described above is preferably a heterocyclic ring called an acidic core in the technical field of a cyanine dye or an oxonol dye. About the acid nucleus, in the coffee to edit

The Theory of the Photographic Process (4th edition, Macmillan, Inc., 1977, p. 198) is specifically described as pyrazol-5-one and pyrazolyl-3,5- which may each be substituted. Diketone, imidazoline _5-ketone, beta-urea urea, 2- or 4-thiobenzalazine, 2-iminoimidazole-4-enone, 2-oxazoline-5-one, 2 -thiazoline-2,4-dione, isoprotanin, lodanine, thiophene-3-one, thiophen-3-one-1,1-dioxide, porphyrin-2·one, hydrazine Bora-3-one, 2-oxocarbazole rust, 5,7-dioxo-6 7-dihydrogen plug. Sit and [3,2-a] ° ^ bite, 3,4 - dihydroisoindolene-4 ketone, 1 3_ bis- s- 4,6-dione (such as Meldrum's acid, etc.) ), barbituric acid, 2-thiobarbituric acid, coumarin-2,4-dione, oxazoline-2__, pyrido[l,2-a]pyrimidine-1,3-dione , pyrazolo[^弘... quinazolin pyrazole and ketone, 5- or 6-member carbene ring (for example, hexane _ 13 _ 嗣, pentane-1,3-dione, 茚a core of _i,3-dione), preferably pyrazole _5-ketone, barbituric acid, 2-thiobarbituric acid, 1,3-dioxane _4,6_two ketone. Further, it is preferably a residue of a compound called a color coupler (c〇1〇r coupler) in the technical field of silver salt photography. For example, pyrazolone, ih_flavor [1,2-b] can be mentioned. Specific oxytocin, 1H-indole [5,1-〇:][1,2,4]trisal, 1H-D-pyrazolo[U-bnUj]triazole, and the like. Among them, as A2, a heterocyclic group having a total carbon number of 2 to 20 from 5 members to 7 members is more preferable. 8 - 108 - 201221520 Among the above, A2 is preferably a group (A-1) (A-2) (A-3) (A-4) represented by the following (A-1) to (A-14). )

(A-5} (A-6) (A-7) (A-8)

W (A-10) (A-tt)

(A-12) (A-13) {A-14)

OR^® 1

In the above (A-1) to (A-14), R6 to R49 each independently represent a hydrogen atom or a substituent. The substituent herein is a group exemplified under the above-mentioned "monovalent substituent", and a preferred substituent is an aliphatic group, an aryl group, a heterocyclic group, a fluorenyl group, or the like. Mercaptoamine, aliphatic oxy, aliphatic oxycarbonyl, amine carbaryl, sulfonamide, aliphatic-109-201221520 Group hydrazine, aryl hydrazide, amine, aliphatic amine Base, trans group, cyano group, contiguous group, several groups. Two adjacent R6 to R14, R15 to R17, and R42 to R47, and R19 and R2G, R21 and R22, R23 and R24, R29 and R3Q, R31 and R32, and R35 and R36 are each within a possible range. They may also be bonded to each other to form a hydrocarbon ring or a heterocyclic ring of a 5-membered ring to a 7-membered ring. Further, Q1 in (A-9), q2 in (A-11), and Q3 in (A-14) each independently represent a non-metal atomic group required to form a 5-membered ring to a 7-membered ring. Specific examples of A2 include specific examples A1-1 to A14 - 25 described in paragraphs [0028] to [32] of JP-A-2008-179067. From the point of view, 'A is expressed in the above'. In the case of the effect (A-10), (Al 1), (A-14) of the effect (Al 1) of the present invention, it is preferable. . The following is shown in the above formula (IV), which is bonded by R ai v . ratio. Specific examples of the base of the sitting ring are B1 (M~uiU-o, Β11·1 ～1 1 -1 9). However, the present invention is not limited to the specific examples described below. In the following, 氺 represents a carbon atom in the above formula (IV), and the sarcophagus is at 0.

-110- 201221520 8ί(Μ Β10-2

Bt〇-5 Β10-6 ΗΝ

Β10-3 510-4

Β11-6 B1V7

Bt14 ΒΤ1-5

Β11-8 ¢11-9- Bi.Vlp

V/H&gt; 011*19

-111- 201221520 In the formula (IV), it is more preferred that the carbon group and the R group are bonded to each other to form a $~7 member ring, the Rb 1 group nitrogen atom, the R system and the hydrogen source m system. Hydrogen atom, a#, (a_10) ♦ (1) or () η system 〇 or 1, particularly preferably A system (A_ 11), η system, the skeleton of the pigment represented by the general formula (IV) may be The methine group serves as either a central symmetrical skeleton structure or an asymmetric skeletal structure. From the point of view of the strong axillary point, the azole skeleton structure of the azole ring system and the Ral bond enthalpy ring is the same. . In the compound represented by the above formula (IV), a compound represented by the following formula (IVa) is preferred.

In the above formula (IVa), Ral, Ra4, Rb1, Rb2 and Rb3 each independently represent a hydrogen atom or a monovalent substituent. A represents a substituted or unsubstituted aliphatic group, substituted or unsubstituted. An aryl group, or a substituted or unsubstituted heterocyclic group. Further, η represents 0, 1, 2 or 3, and when η is 2 or more, Hb2 and Rb3 which are present in the latter may be the same or different. The 玟ai, Rbl, Rb2, a and η in the general formula (IV) are synonymous with rb 1 , Rb 2, rb 3, a and η in the above formula (IVa), and preferred embodiments are also the same. . -112- 201221520 In the above formula (IVa), Ra4 represents a hydrogen atom or a monovalent substituent. The monovalent substituent represented by Ra4 may be a group which may be substituted, and examples thereof include the same substituents as those exemplified in the item of "monovalent substituent" represented by Ral to Ra3 and Rb1 to Rb3. The substituent may be unsubstituted or may be further substituted by the substituents listed under the item "monovalent substituent" represented by Ral to Ra3 in the above formula (IV). It is preferably an aliphatic group, an aryl group or a heterocyclic group, more preferably an alkyl group or an aryl group. The aliphatic group represented by the above Ra4 may be unsubstituted or substituted, and may contain an alkyl group, an alkenyl group or the like. The alkyl group which is unsubstituted or has a substituent is preferably an alkyl group having a carbon number of i to 25, and examples thereof include (indenyl)propyl (isopropyl) and 2-methyl-2-ethynylamino. Among them, an ethyl group, a 2-propionylaminopropyl group, and the like are preferably an alkyl group having 2 to 25 carbon atoms, particularly preferably a carbon group having 2 to 2 carbon atoms. The aryl group represented by Ra4 may be an unsubstituted or substituted aryl group having a carbon number of 6 to 3 Å, and more preferably a aryl group having a carbon number of 6 to 2 Å, for example, 4'. Butylated aminophenyl, 4-butylsulfonylamine, 4-nitrophenyl and the like. The heterocyclic group represented by R" may be unsubstituted or have a soil, and may, for example, be a 5-pyrimidinyl group. Among the compounds which are not represented by the formula (IVa), R/丨/ Particularly preferred aspect atom, = an anion having a number of 1 to 8, R "alkyl or aryl, Rbl is a hydrogen atom - 'Rb3 is a chlorine atom' 11 is 0 or 1; a preferred group Or carbon number, number 1 to 4 of the burning base, R "system carbon number 1 ~ 2.

2 芳 aryl, R 〇 or 1. A 'Rb2 and Rb3 are hydrogen atoms, η system, and the effect of improving the fastness of ruthenium. From the point of view of the dyes of the formula (IV) -113 to 201221520, the azole ring system represented by A is particularly preferred. Ral is bonded to the same azole skeleton structure as the azole ring. For details of the compound represented by the formula (iv), reference is made to the description of the Japanese Patent Publication No. 2008-179067.具体 χ χ 具体 具体 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Next, the general formula (V) will be explained.

In the above formula (V), R61, R62, R63 and R "each independently represent a hydrogen atom, an alkyl group which may be substituted, an aryl group which may be substituted or S〇2NH-R And r65 represents a hydrogen atom, an alkyl group which may be substituted, a group which may be substituted, ?3〇3Η or _s〇2NH_R. R represents an alkyl group, an alkoxyalkyl group, a hexyl group, a cyclohexyl group, an alkane The oxy group, the aryl group or the alkylcarbonyl fluorenyl group η represents an integer of 0 or more, and when n is 〇, the aryl group of R6 to R65 has a group of -s〇2NH-R as a substituent. The preferred R is an alkyl group having 1 or more carbon atoms, particularly a carbon number of 3 or more and 3 or less, and an alkoxy group having a total carbon number of 3 or more and 30 or less, and an alkyl group. The carbon number is 1 or more and 20 or less cyclohexylalkyl groups, etc., and these groups may be substituted by an appropriate substituent. 8 - 114 - 201221520 wherein, preferably, at least one of R61 and R62 or R63 and R64 is used. At least one aryl group having a carbon number of 丨~4 or an aryl group which may be substituted by one or two substituents, and further preferably, at least one alkyl group having 1 to 4 carbon atoms of R62 Or can be Or a substituent in which two substituents are substituted, at least one of R63 and R64 is an alkyl group having a carbon number of 丨4 or an aryl group which may be substituted by i(tetra)2 substituents. In either case, the alkyl group in r6i~ or The aryl group is preferably a hydrogen atom. Examples of the substituent aryl group include a methyl group, a trimethyl group, a mesogenic group, JO#, -so2nh-c6h5, etc. With respect to the above formula (V) / V, Gongyi...,- For details of the compound, reference may be made to the invention of the invention patent No. 3 3 8 7 5 4 1轳 0. ^ , . 唬 δ has been carried. Further, regarding the above formula (V) A specific example of the compound, ^87Sd1 is the same as the specific example described in the paragraph [0010] to "〇〇2fnd7 compound. 20" of Japanese Patent No. 338 41 唬.

Xing. Scale. jja times, J Ming formula (VI)

In the formula (VI), in the formula (Vi), "the carbon number of one chain is 2", an alkyl group having an alkyl group of 2 to 20 carbon atoms, an alkyl group of an alkyl group: a 12% hexyl alkyl group thereof The carbon number of the alkyl chain is 1... The carbon number of the ^^ carbon number of 2~12 is substituted by the alkoxy group, L-C0-0-L72 铋- L73-〇-C〇-t^ „ The alkylcarboxyalkyl group, the thiol group shown, the phenyl group substituted by the Hyun-115-201221520 group of the carbon number, or the alkyl group L7 substituted by the phenyl group with a carbon number of 2~2〇! Table 7 is not an alkyl group of 2 to 12, L72 represents an alkylene group having 2 to 2 carbon atoms, L73 represents an alkyl group having 2 to 12 carbon atoms, and [Μ represents an alkylene group having 2 to 12 carbon atoms. R, R73, R and R75 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group or a halogen atom. Examples of the alkyl group having 2 to 20 carbon atoms include ethyl, n-propyl, isopropyl, n-hexyl, n-decyl, n-decyl, n-dodecyl, 2-ethylhexyl, and 1,3-. Dimethylbutyl, 1-methylbutyl, i,5-dimethylhexyl and M,3,3-tetradecylbutyl and the like. Examples of the cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain include a hexylethyl group, a 3-cyclohexylpropyl group, and an 8-cyclohexyloctyl group. Examples of the alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain include a 2-ethylhexyl group, a 2-propylcyclohexyl group, and a 2-(n-butyl)cyclohexyl group. Examples of the alkyl group having 2 to 12 carbon atoms which are substituted by an alkoxy group having 2 to 12 carbon atoms include 3-ethoxy-n-propyl group, propoxypropyl group, and 4 propoxy group = butyl group. The 3-phenyl-n-hexyloxyethyl group and the 3-(2-ethylhexyloxy)propyl group are phenyl groups substituted with an alkyl group having 1 to 20 carbon atoms, and examples thereof include an o-isopropylphenyl group. &quot; ^ The alkyl group having 1 to 20 carbon atoms substituted by a phenyl group may, for example, be DLj-triethyl, benzyl or 3-phenyl-n-butyl. 'Ethyl diyl, 2-ethyldimethylhexyl, and alkyl propyl, n-hexyl, n-decyl, n-decyl, n-decene as L71 and [C 2 to 12 in [73] Base, 1,3 -didecylbutyl, 1-decylbutyl, 1,5-'H3-tetradecylbutyl, and the like. 8 - 116 - 201221520 Examples of the alkylene group having 2 to 12 carbon atoms in L72 and L74 include a dimethylene group and a hexamethylene group. Examples of R72 to R75 include a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, a n-butyl group, an isopropyl group, a second butyl group, a tert-butyl group, a carboxyl group, a fluorine atom, a chlorine atom, and a bromine atom. The iodine atom or the like is preferably a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, a n-butyl group, an isopropyl group, a second butyl group, a tert-butyl group, a fluorine atom or a chlorine atom. Specific examples of the compound represented by the above formula (VI) include

In the above formula (VII), Z1 and Z2 each independently represent an oxygen atom or a sulfur atom. R81, R82, R83 and R84 each independently represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a saturated aliphatic hydrocarbon group having a carbon number of 1 to 10 substituted by a hydroxyl group, and an alkoxy group having a carbon number of 1 to 8. a saturated aliphatic hydrocarbon group having a carbon number of 1 to 10, a saturated aliphatic hydrocarbon group having a carbon number of 1 to 10, and an aryl group having a carbon number of 6 to 20, which are substituted by a thioalkoxy group having a carbon number of 1 to 8 and 201221520. An aralkyl group having 7 to 20 carbon atoms or a fluorenyl group having 2 to 1 carbon atoms. R85 , R86 , R87 , R88 ' R89 , R1 IGa , r1 丨la and R1 12a each independently represent a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group having a carbon number of 1 to 1 fluorene, and a halogenation of 1 to 10 carbon atoms. a saturated aliphatic hydrocarbon group, an alkoxy group having 1 to 8 carbon atoms, a carboxyl group, a sulfo group, an aminesulfonyl group or a substituted aminesulfonyl group, and at least one of R85 to R89 and R110a to R1 12a represents a hydrazine-substituted amine sulfonate. The saturated aliphatic hydrocarbon group of the fluorenyl group R to R may be any of a linear chain, a branched chain, or a cyclic chain. The carbon number of the saturated aliphatic hydrocarbon group does not include the carbon number of the substituent. The carbon number is usually from 1 to 10 0', preferably from 2 to 8, more preferably from 3 to 6. The saturated aliphatic hydrocarbon group includes, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a second butyl group, a tert-butyl group, an ethylhexyl group (2-ethylhexyl group, etc.). Or an alkyl group, a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group or a cyclohexylalkyl group. Further, in the saturated aliphatic hydrocarbon group, a substituent such as a hydroxyl group or a carbon number 〜μμ is preferably a carbon ti~oxy group or a carbon number 88 (preferably a carbon number of 1 to 4) thioalkoxy group. Replace. Examples of the substituted saturated aliphatic hydrocarbon group include a hydroxyethyl group (2-hydroxyethyl group, etc.), an ethoxyethyl group U-ethoxyethyl group, and the like, and an ethylhexyloxypropyl group (3_(2). _Ethylhexyl hydrazide ~ propyl, etc.), mercapto thiopropyl (3-mercaptothiopropyl, etc.), etc. The aryl group of RS1 to R84 may be unsubstituted or may have saturated fat: transbasic a substituent of a courtoxy group, a thiol group, a terminus group or a vine group, etc. The carbon number of the above-mentioned square group is calculated by the carbon number of the substituent, y+^ is usually 6 to 20, and the car X is preferably 6 to 1 0. As such aryl groups, for example, a base, 2-, 3-118-201221520, 4-mercapto-phenyl, 2,3,4-methoxyphenyl, 2-, 3-, a substituted or unsubstituted phenyl group such as an oxycarbonylphenyl group (4-(COOC2H5)Ph group or the like), etc. The alkyl moiety of the aralkyl group (arylalkyl group) of R81 to R84 may be a linear chain. Or a branched form, the carbon number of the aryl group is different from the carbon number of the substituent, and is usually 7 to 20, preferably 7 to 10. As the benzene of the aryl group, etc. The alkyl group is represented by p 8 1 ό 8 4 〜 R The fluorenyl group can be unsubstituted or knotted. a substituent of a saturated aliphatic sulfonyl group, an alkoxy group, etc. The carbon number of the fluorenyl group is determined by the carbon number of the substituent, and the number is usually 2 to 1 Å, preferably 6 to 1 Å. It is an acetamyl group, a methionyl group, a methoxyphenyl fluorenyl group (for a decyloxy group, etc.). In order to increase the color density, in at least one of R81 to r84, the carbon number is sw. a base of 〜~u ^ i I (more than k is 3 or less) (eg thiol, B)

The base is selected from a hydrogen atom. TG is also based on the improvement of the solubility (oil solubility) in rS1 to r84 from the point of view of the solubility (oil solubility) of the TG, and the number of carbons is 6 or more, and the second V (preferably all). Should choose base). Is a substituted or unsubstituted aryl group (preferably a benzene R 8 5 -R 8 9 and ru α 1 i atom) (preferably fluorine, gas::: each independently represents a hydrogen atom, a tooth, a land, a Μ ^ . , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Substituted amine sulfonyl, r85~^9 ^ - N-substituted amine sulfonyl and at least -119- 201221520 2 a R85 ~ R89 of alkoxy, carboxyl, sulfo, sulfonyl 110 R112 a And any of the saturated aliphatic hydrocarbon groups which are not R11a to R-... _ and R81 to f, and Si is a linear, branched or cyclic fluorene. ～89 and number; (9) 'preferably 2 to 8, more preferably as an example with W to R", as in the case of the specific R of the aliphatic nicotine group. R85 to R89 and a saturated aliphatic hydrocarbon group of R11a to Rll2a It may be substituted by halogen, hydrazine or butyl W, and may be preferably substituted by a fluorine atom. Specific examples of the functionalized saturated aliphatic hydrocarbon group include a trifluoromethyl group, etc. R85 to R89* R11°a to R112, Alkoxy carbon number It is usually i~8, preferably 1 to 4. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a n-propoxy group, a n-butoxy group, and an isobutoxy group. , a second butoxy group, a third butoxy group, etc., an N-substituted amine sulfonyl group represented by R&amp;5 to R89 and RllGa to Rll2a, for example, an unsubstituted amine sulfonyl group, which may be of the formula _s〇 2NHRll3a is a base. In the formula, RlUa is a carbon number of 1 to 10 saturated aliphatic hydrocarbon group (including when a carbon number 丨 丨〇 丨〇 saturated aliphatic hydrocarbon group is bonded with a carbon number 丨 8 alkoxy group ^), carbon number It is an aryl group of 6 to 20, a teller system, and an aralkyl group having an inverse number of 7 to 20 or a fluorenyl group having a carbon number of 2 to 1 Å. r Π 3 a The R 7 舢 aliphatic hydrocarbon group may be any one of a linear chain, a branched chain or a cyclic group. The carbon number of the silk aliphatic hydrocarbon group is usually 10, and preferably the saturated aliphatic hydrocarbon group contains, for example, a methyl group. 6-, n-propyl, isopropyl, n-butyl, isobutyl, first butyl, ▲f-butyl (113,3-tetradecylbutyl, etc.), decylhexyl (H-based) Hexyl, i,5, dimethylhexyl, etc.), ethylhexyl (2_B Cyclohexyl, etc.), cyclopentyl, cyclohexyl, methylcyclohexyl (2-methylcyclohexane 8 -120-201221520, etc.), cyclohexylalkyl, etc. The platinum deduction of RU3a and the saturation of B^^ The group of the hydrocarbon group may be substituted by a substituent such as carbon number 8 (preferably a carbon number of 4 to an oxy group). As the substituted saturated aliphatic hydrocarbon group, a propoxypropyl group (3_(isopropyl isopropoxide) may be exemplified. Base) propyl, etc.).

The aryl group represented by Rn3a may be unsubstituted or may have a substituent of a saturated aliphatic hydrocarbon group or a trans group or the like. The carbon number of the above aryl group is usually 6 to 10 (10)', preferably A 6 to 10. Examples of such an aryl group include a substituted or unsubstituted phenyl group such as a phenyl group, a hydroxyphenyl group (such as a 4-hydroxyphenyl group), or a fluoroindolyl group (a tetrafluoromethylphenyl group). . The alkyl moiety of the aralkyl group represented by R113a may be either linear or branched. The aralkyl group has a carbon number of usually 7 to 20, preferably 7 to M. As the aralkyl group, a styl group such as a benzyl group, a phenylpropyl group (1_fluorenyl-3-phenylpropyl group), a phenylbutyl group (3-amino-1-phenylbutyl group, etc.) The alkyl group is representative. The fluorenyl group which R does not have may be unsubstituted or may be bonded to a substituent such as a saturated aliphatic hydrocarbon group or an alkoxy group. The carbon number of the fluorenyl group is usually 2 to (7), preferably 6 to 1 0. The above mercapto group is, for example, an ethyl ketone group, a ruthenium group, a methoxybenzylidene group (p-methoxybenzyl fluorenyl group, etc.). R85 to R89 and Ri10a to R&quot; 2a are preferably one N-substituted amine of R85 to R89 and RllQa to R 1 ' 2 a from the viewpoint of improving color density, oil solubility, light resistance and the like. The case of sulfonyl groups. Further, from the point of view of the oil, it is preferable to have one or two or more of R85 R and Rll〇a to R 12a, for example, in addition to the fluorene-substituted sulfonyl group. Is trifluoromethyl-121-201221520 Further, one of R85~H88 and one of R89 and R11〇a~ are N-substituted amine sulfonyl groups, and the rest are hydrogen atoms of disulfonamide' and R85~R88 One of them is an N-substituted amine sulfonyl group, one of R89 and R11 R 2a is a sulfo group, and the other is a combination of monosulfonamides of an argon atom. Next, the general formula (VIII) will be explained.

In the above formula (VIII), RW, R92 and R93 each independently represent a hydrogen atom, a halogen atom or a sulfonic acid group, and A3 represents any one of the following (a) to (d). 1 represents an integer of 1 or 2. R, R95 and R96 in the following (a) each independently represent an argon atom, a methyl group, a halogen atom 'sulfonic acid group or -S02N(R97)(R98), and R97 and R98 each independently represent a hydrogen atom and a carbon number. a lower alkyl group of 1 to 8 (e.g., an anthracenyl group, an ethyl group, a propyl group, etc.) or a phenyl group. At least one of R91 to R96 represents a sulfonic acid group. When 丨 is 2, the plural R91, the plural R92, and the plural R93 are each the same or different. 8 -122- 201221520

The details of the compound represented by the above formula (VIII) can be referred to in the description of JP-A-71-1683. In the specific example of the compound represented by the above formula (VIII), the structural formula (1) described in the pages (4) to (5) of the Japanese Patent Publication No. 7-1 1 3687 is exemplified. (9) The dye shown in the above dye compound is used together with the above-mentioned ruthenium compound, and the hue of the colored image is good, and from the viewpoint of obtaining a higher contrast, it is preferable that the ratio σ is 曱Basic system. ratio. The azo-based, methine-based, 11-dosage, °-by-dazole D-linone azo, ° ketone azo-based, barbiturate-based dyes. In the colored composition of the present invention, one type of dye may be contained alone, or two or more types of dyes may be used in combination. The content of the dye in the coloring composition (the total content in the case of two or more kinds) is preferably from 1 to 70% by mass, more preferably from 10 to 50% by mass, based on the total solid content of the coloring composition. When the content of the dye is from 10 mass to 123 to 201221520% or more, a good service is obtained: a color density of 1* / a dose of (for example, a color density suitable for liquid crystal display) is 50% by mass or less. It is advantageous to see the point. / 卜 The patterning of the halogen is good (polymerizable compound) The coloring composition of the present invention is a compound. The addition polymerization of the ethylenically unsaturated double bond as the polymerizable compound is preferably at least one polymerizable compound, for example, having at least one compound. Specifically, the polymerizable compound is selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Such a compound group is widely known in the industrial field, and it is not particularly limited in the present invention and can be used. Such may be, for example, a monomer, a prepolymer, a prepolymer (prep〇iymer), ie a dimer, a trimer and an oligomer (〇Hg〇), or a mixture thereof and a Any of the chemical forms of the polymer, etc. Examples of the monomer and the (co)polymer thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, Maleic acid, etc.) or its esters, guanamines, and the like (co)polymers, preferably esters of unsaturated carboxylic acids with aliphatic polyvalent alcohol compounds, and I do not know how to neutralize S and a steroid of a polyamine compound, and a (co)polymer thereof. Further, an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group or an unsaturated carboxylic acid decylamine Addition reactants with monofunctional or polyfunctional isocyanates or monofunctional or polyfunctional epoxys or the aforementioned unsaturated carboxylic acid esters or unsaturated carboxylic acid amides, with monofunctional or polyfunctional carboxylic acids Acid dehydration condensation reactants, etc. are also applicable. Also 'electrophilic with isocyanate groups or epoxy groups Unsaturated 8-124-201221520 and an alcoholic decyl alcohol, an alkylene olefin, a saccharide ester, or an unsaturated carboxylic acid amide, with a monofunctional or polyfunctional Addition reactants of a class, an amine, or a thiol; more preferably, an unsaturated carboxylic acid ester having a debonding substituent such as a dentate group or a benzenesulfonyloxy group or a carboxylic acid amide amine A monofunctional or polyfunctional alcohol, an amine or a sulfur-substituted reaction product is also suitable. Further, as another example, the unsaturated carboxylic acid may be substituted with an unsaturated phosphonic acid, styrene or vinyl group. Specific examples of the monomer as an ester of an aliphatic polyol compound and an unsaturated carboxylic acid, and examples of the acrylate include ethylene glycol diacrylic acid, diethylene glycol diacrylate, and hydrazine. Diol diacrylate, tetradecyl-alcohol dipropionate, propylene glycol diacrylate, neopentyl glycol acrylate, trimethylolpropane triacrylate 'trihydroxydecyl propane Ether, trihydroxydecylethane triacrylate, hexanediol dipropylene Acid ester, 1,4-cyclohexanediol diacrylate, tetraethanol monoacrylate, pentaerythritol diacrylate, pentaerythritol tripropyl sulfonium S, pentaerythritol tetrapropionate, dipentaerythritol diacrylate Pentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexa-propionic acid vinegar, tris(propylene oxyethyl) isocyanurate, polyester Acrylic acid oligomer, isoamyl cyanate modified triacrylate, etc.; among the methacrylates, for example, tetradecylene glycol dimethic acid vinegar, triethylene glycol dimercapto group Acrylate, neopentyl glycol diacetic acid vinegar, trimethylolpropane tridecyl acrylate, trimethylol dimethyl dimethacrylate, ethylene glycol dimercapto acrylate, hydrazine, 3-butyl Alcohol dimercapto acrylate, hexanediol dimercapto acrylate, penta-125-201221520 tetraol monodecyl acrylate, pentaerythritol tridecyl acrylate, pentaerythritol tetradecyl acrylate, dipentaerythritol dimethyl Acrylate, dipentaerythritol Acrylate, sorbitol tridecyl acrylate, sorbitol tetradecyl acrylate, bis [p-(meth) methacryloxy-2-phenyl hydroxypropoxy) phenyl] dimercaptomethane, double- [p-(methacryloxyethoxy)phenyl] dimethyl ketone; etc.; in the itaconate, for example, ethylene glycol diconconate, propylene glycol diconcanate,丨, 3-butanediol di-iconate, 1,4-butanediol diconic acid vinegar, tetramethylene glycol diconic acid vinegar, pentaerythritol diconcan acid vinegar, sorbitol tetra Examples of the crotonate include, for example, ethylene glycol dicrotonate, tetradecyl mono crotonate, pentaerythritol dicrotonate, and sorbitol four monocrotonate ( Sorbitol tetradicrotonate); and the iso-p-palmitate, for example, ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, etc.; For example, ethylene glycol dimaleate, triethyl alcohol-maleic acid s, pentaerythritol dimaleic acid vinegar, and sorbitol tetra are mentioned as other esters. For example, the aliphatic alcohol-based esters described in the Japanese Unexamined Patent Publication No. JP-A No. Hei 59-524 No. The vinegar monomer containing an amine group described in the Unexamined Patent Publication No. 65613, which is incorporated herein by reference, can also be used as a mixture. Further, as a specific example of the monomer of the aliphatic polyamine compound and the decylamine of the unsaturated carboxylic acid, there are methylene bis-acrylamide, methylene bis-methyl propylene hydride. Amine, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methyl acrylamide, diethylenetriamine tripropylene decylamine, benzodimethyl bis decyl decylamine , Benzyl dimethyl propyl amide, and the like. As an example of another preferable amide-based monomer, the structure having a stretched cyclohexyl group described in Japanese Patent Publication No. Sho 54.21,726 can be cited. In addition, the urethane-based addition polymerizable compound produced by the addition reaction of an isocyanate and a hydroxyl group is also suitable, and as such a specific example, for example, the pair described in Japanese Patent Publication No. Sho 48-4 1 708 A polyisocyanate compound having two or more isocyanate groups per molecule, and a vinyl group having a trans group represented by the following formula (Α), and having two or more polymerizable vinyl groups in one molecule A vinylamine phthalate compound or the like. CH2=C(R)C00CH2CH(R')0H (A) [In the formula (A), R and R each independently represent hydrazine or CH3]. With respect to these polymerizable compounds, the details of the structure, the use of the mixture, or the combination of the use amount or the amount of addition can be arbitrarily set in accordance with the coloring composition and the final performance design. For example, in the viewpoint of sensitivity, the structure of the winter 1 molecule having a large content of unsaturated groups is preferred, and most of the conditions are more than $2 functional. X 'in improving the strength of the colored cured film: in the point, it may be a trifunctional or more 'by further using a different functional number or a different polymerizable group (for example, acrylic acid acrylate, mercapto acrylic acid, benzene, In the case of an olefinic compound or a vinyl ether compound, a method of both the sensitivity and the strength of the sputum is also effective. Further, it is possible to use a phase of other components (for example, a photopolymerization initiator, a binder polymer, etc.) of -127 to 201221520 contained in the coloring composition. The choice of the (pigment) and the binder composition and/or the method of use are also redispersible, and the use of the compound of the polymerized 7 King Go' or the combination of two or more types, for example, by low purity, It improves the compatibility with the hard surface of the support and the like. It is also possible to choose a specific construction. In the viewpoint of the adhesion, the total solid content of the coloring composition (the total content of two or more kinds) is not limited by the viewpoint that the content of the specific compound is obtained by the effect of the present invention, and is more effective. The amount %, more preferably 15% by mass to 75 mass. It is 1 mass% ~ 8 ° quality 60 mass. /〇. . 'Excellently 20% by mass to ~ (Photopolymerization initiator) The coloring composition of the present invention is preferably an initiator. The photopolymerization initiator is not particularly limited as long as it is a photopolymerization agent, and is preferably selected from the viewpoints of the polyabsorption wavelength and the availability of the polymerizable compound. As a photopolymerization initiator, you may find at least one active halogenated ruthenium selected from the group consisting of a sulfonyl oxadiazole compound and a sulfhydryl-oxazide compound, 3 guana &amp; Substance, 3-aryl group substituted. "匕5, lophine chmer, diphenyl ketone I3S v, _ ljt + present ethyl ketone compound and its derivatives, pentylene - stupid - Iron mismatched person * a long-term salt, bismuth compound, etc. Specific examples of the photopolymerization initiator, Shuang 4 4 J cites the paragraph of 2004-295 1 16, Duan Luo [0070] ~ [00771 π &amp; + ^ ° own carrier. Among them, from the point of rapid polymerization, etc., it is preferred to employ a compound. -128- 201221520 As the above-mentioned ruthenium compound (hereinafter also referred to as "photopolymerization initiator"), there is no In particular, the monthly-deficient compound described in JP-A-2000-80068, WO02/100903A1, JP-A-2001-233842, and the like is exemplified. Specific examples thereof include 2-(0-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-butanedione and 2-(0-benzoinyl).肟)-1-[4-(phenylthio)phenyl]-1,2-pentanedione, 2-(0-phenylhydrazinyl)-1-[4-(phenylthio)phenyl -1,2-hexanedione, 2-(0-phenylhydrazinyl)-1-[4-(phenylthio)phenyl]-1,2-heptanedione, 2-(0 -benzylidene hydrazide)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 2-(0-phenylhydrazinyl)-1-[4-(fluorenyl) Phenylthio)phenyl]-1,2-butanedione, 2-(0-benzylidenehydrazide)-1-[4-(ethylphenylthio)phenyl]-1,2-butane Ketone, 2-(0-benzylidene fluorenyl)-1-[4-(butylphenylthio)phenyl]-1,2-butanedione, 1-(0-ethylindenyl)-1 -[9-ethyl-6-(2-mercaptophenyl)-9H-indazol-3-yl]ethanone, 1-(0-ethylindenyl)-1-[9-methyl -6-(2-methylbenzimidyl)-9H-indazol-3-yl]ethanone, 1-(0-ethylindenyl)-1-[9-propyl-6-(2- Methyl benzhydryl)-9H-indazol-3-yl]ethanone, 1-(0-ethylindenyl)-1-[9-ethyl-6-(2-ethylbenzoinyl) )-9H-carbazol-3-yl]ethanone, 1-(0-ethylindenyl)-1-[9-ethyl-6-(2-butylphenylhydrazine) Mercapto)-9H-carbazol-3-yl]ethanone and the like. However, it is not limited by these. In the present invention, the oxime compound is more preferably a compound represented by the following formula (1) from the viewpoints of sensitivity, stability over time, and coloration upon post-heating. -129- 201221520 〇

In the above formula (1), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of [~5. When η is an integer of 2 to 5, the plurals may be identical or different from each other. R is preferably a fluorenyl group from the viewpoint of sensitization of hydrazine, and specifically preferably an ethyl fluorenyl group, a propyl fluorenyl group, a benzoyl group or a tolyl fluorenyl group. As A, from the viewpoint of the rain sensitivity and the suppression of the coloring caused by the heating, it is preferably an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a second butyl group, or a tau group). a substituted alkylene group, an alkyl group substituted with an alkenyl group (e.g., a vinyl group, an allyl group), an aryl group (e.g., phenyl, p-nonylphenyl, diphenylphenyl, cumenyl, naphthyl) , anthracenyl, phenanthryl, styryl) substituted alkyl. The term "Ar" is preferably a substituted or unsubstituted phenyl group from the viewpoint of improving the sensitivity to suppress the coloring caused by the heating. When it is a substituted phenyl group, 'as a substituent' is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The X' is preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, and may have a substituent from the viewpoint of improvement in solvent solubility and absorption efficiency in a long wavelength region. Alkynyl group, alkoxy group which may have a substituent, aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, and an amine group which may have a substituent . -130- 8 201221520 Further, η in the formula (1) is preferably a whole drum of 1 to 2. In addition to the initiator of the present invention, other well-known photopolymerization initiators described in JP-A No. 2,295,116, the entire disclosure of which is incorporated herein by reference. &lt;Luo_9] The photopolymerization initiator may be used alone or in combination. In the above, the light-containing '5-initiator is a total content when the total solid content of the coloring composition is more than or equal to the above), and from the viewpoint of more effectively obtaining the effect of the present invention, it is preferably 3% by mass to 2 〇% by mass, more fruitful~ Π quality. /. The amount is preferably from 5% by mass to 18% by mass. 44 tons. (Organic solvent) The colored composition of the present invention may contain to . The organic solvent of the organic solvent is basically organic as long as it satisfies the coexistence of the coloring of each component, and is basically tempering or as a limitation for considering the solubility of the binder and the coating property. Solvent, in vinegar:: sex to choose. Acidic n-butyl vinegar, isobutyl lysate, and carboxylic acid pentane: ethyl acetate, isobutyl acetonate, butyl propionate, isoamyl isopropyl acetonate, acetonide, methyl lactate, lactic acid Ethyl alcohol, oxy, acetamidine 'butyric acid, butyric acid', oxyacetic acid, oxyacetic acid = class (9), such as: methoxymethyl ketone acetic acid, methoxy acetic acid, brewing, butyl /: ( Specifically, it can be exemplified by acetamidine; 73⁄4 分田*匕产#7 oxyacetic acid butyl vinegar, methyl ketone acetate, ethyl ethoxylate (for example: 3-methylpropionic acid formazan, 3_ In the oxy group: methoxy group, followed by vinegar, 3 曱 曱 曱 丙 、 | 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 131 - 201221520 Methyl propionate, ethyl 3-ethoxypropionate, etc.)), 2-oxypropionic acid alkyl (for example: 2-oxopropionic acid oxime, 2-oxopropionic acid B , 2-oxypropyl ester, etc. (specifically, decyl 2-methoxyoxypropionate, 2-methoxyethyl ester, propyl 2-methoxypropionate, bismuth 2-ethoxypropionate Ester, ethyl 2-ethylpropionate, etc.), methyl 2-oxo-2-mercaptopropionate, ethyl 2-oxy-2-propionate (specifically Ethyl 2-methoxy-2-mercaptopropionate ethyl ethoxy-2-mercaptopropionate, etc.), decyl pyruvate, propyl pyruvate acetonate, decyl acetate Ethyl acetate, ethyl 2-oxoate, ethyl 2-oxobutanoate, etc. Further, examples of the organic solvent include glycol dimethyl ether, tetrahydrofuran, and ethylene glycol. Monodecyl ether, glycol ether, thiol cellosolve acetic acid S, ethyl cellosolve acetate, glycol mono-f-ether ether, diethylene glycol monoethyl ether, diethylene glycol single Butyl propylene glycol monodecyl ether, propylene glycol monomethyl ether acetate, propylene glycol ether acetate, propylene glycol monopropyl ether acetate, etc. Examples of the ketones include mercaptoethyl ketone and a ring. Examples of the aromatic hydrocarbons include, for example, toluene, bis, etc., such as organic solvents, solubility from the above components, and when a soluble binder is contained. It is also preferable to mix two or more types in terms of solubility, improvement of a coating surface, etc. In this case, it is especially preferable to melt|dissolve by 3- methoxy-propionate, ethyl 3-ethoxypropionate, ethyl Fibrous agent Ethyl acetate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxymethyl ester, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl ester Propionate propionate oxonium group, 2-ester, butyl ethyl ethanediethyl ether, monoethyl 2-heptylene toluene oxy, lactobionate 8 -132- 201221520 alcohol acetate, A mixed solution of two or more kinds of propylene glycol methyl ether and propylene glycol. The content of the organic solvent in the coloring composition is selected from the soil vinegar vinegar, and the total solid content concentration in ^ is ίο f%%~8G1 The composition f is preferably 15% by mass to 60% by mass, the amount of %, and the other components are not damaged by the alkali-soluble binder. The colored composition of the present invention contains the above-mentioned invention. Within the scope of the effect, other components such as a crosslinking agent may be further included. - In addition to the solubility of the soluble binder _, there is no particular advantage. The alkali-soluble binder is not limited by the alkali solubility. It is preferably selected from the viewpoints of resistance to money and development. As a substance, and as a carboxylic acid poly-label, a special 59-53836 acrylic acid co-copolymer, a sample side-by-side viscous binder, preferably a linear organic polymer polymerizable in an organic solvent , can be used to visualize the aqueous solution. The linear organic polymer 'is exemplified by a side chain, for example, JP-A-59-44615, JP-A 54-34327, No. Sho-58-12577, Tegong Sho 54.25957, Special Kai-Zhao, Tekai-Zhao a methyl polymer, an acrylic copolymer, an itaconic acid copolymer, a crotonic acid maleic acid copolymer, a partially esterified maleic acid copolymer, or the like described in each of the publications of the Japanese Patent Publication No. 59-71-48, having a carboxylic acid in the same bond Acidic cellulose derivatives are suitable. ',上过者' as the soluble binder in the present invention, an acid anhydride added to a polymer having a hydroxyl group, or a polyhydroxyl stearic vinyl resin, a polyoxyalkylene resin, or a poly((methyl) ) 2-hydroxyethyl acrylate) -133- 201221520, polyvinylpyrrolidone or polyethylene oxide, polyvinyl alcohol, etc. are also suitable. Further, the linear organic high molecular polymer can be obtained by copolymerizing a monomer having hydrophilicity. Examples thereof include alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, glycerin (meth)acrylate, (meth)acrylamide, and N-methylol propylene oxime. Amine, grade 2 or 3 alkyl acrylamide, dialkylaminoalkyl (sub) acrylate, morpholine (meth) acrylate, N. vinyl, N_vinyl hexanone Amine, ethylene (four). Sit, vinyltriazole, methyl (meth) acrylate '(mercapto) acrylate, branched or linear (meth) acrylic propylene 'branched or linear (meth) butyl acrylate Or (meth) propylene as a hydrophilic monomer, a group containing an acid vine group, a quaternary salt base, an ethylene group and a salt thereof, a phenoxy hydroxypropyl morpholinate or the like. In addition, a monomer such as a tetrahydroindenyl group, a phosphoric acid group, a phosphorusoxy chain, an acryloxy chain, a sulfonic acid ethyl group or the like is also suitable. In order to improve the crosslinking efficiency, a soluble binder can also be used. The side chain has a polymerizable group, for example, a polymer containing an allyl group, a (methacryloyl fluorenyl group, a phenanthrenyl group, etc.) in the side chain is also applicable. As an example of the polymer containing a polymerizable group,枣屮古# 』 KS RESIST-l〇6 (KS RESIST-l〇6) (Osaka Organic Chemicals. . Another Mechanical Chemical Industry Co., Ltd.

Organic Chemical Industry Ltd, •1), CYCLOMER P series (Daicel and Poor Industry (Daicel)

Chemical Industries Ltd.)).顼 + ))) In addition, in order to increase the strength of the hardened film, alcohol-soluble nylon or 2,2_bipolar ^ ^ hydroxyphenyl)-propane and a mixture of soil oxygen and propylene burn are also applicable. 8-134-201221520 Among these various alkali-soluble binders, from the viewpoint of heat resistance, #又 is preferably a hydroxy styrene-based resin, a polyoxyalkylene-based resin, a propylene fluorene, and propylene. Amidoxime resin, acrylic acid/acrylamide copolymer (tetra) copolymer: From the viewpoint of development control, an acrylic laurel acrylamide resin or an acrylic/acrylamide copolymer resin is preferable. t is a list of the acrylic resin, preferably selected from the group consisting of benzyl hydrazide (meth) acrylate (meth) acrylate, (mercapto) acrylic acid, acetoacetate, (mercapto) acrylamide, and the like. The copolymer formed by the body, or the KS anti-surname agent 〇6 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the Secolo 4 P series (manufactured by DAICEL Chemical Industry Co., Ltd.). In the case of the imaging property, the liquid (four degrees), etc., the weight average molecular weight (the polystyrene conversion value measured by the GpC (gel permeation chromatography) method) is 1QQq~2x1g5. The polymer system is preferably, 2000~1&gt;&lt;1〇5's gang and "/上-&quot;. The system is better, 5000~5 x〗 〇 4 polymer is particularly good. ^ - Crosslinking agent: The crosslinking agent of Benqiming is supplemented with a crosslinking agent, and the hardness of the colored curing film obtained by hardening the colored composition can be further improved. The parent-linking agent is not particularly limited as long as it can be cured by a crosslinking reaction, and examples thereof include (4) an epoxy resin, (7) a hydroxy group, an alkoxymethyl group, and a decyloxymethyl group. a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one substituent selected, and (4) at least one substituent selected from a methyl group, an alkoxymethyl group and a methoxy group A substituted benzoquinone compound, a naphthene compound or a lysine compound. Among them, a polyfunctional epoxy resin is preferred. -135-201221520 For details of specific examples of the crosslinking agent, etc., the descriptions of paragraphs [〇134] to [01 47] of JP-A-2004-295 1 16 can be referred to. -Other Additives - Various additives such as a filler, a polymer compound other than the above, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a adhesion promoter may be blended as needed in the coloring composition. , antioxidants, UV absorbers, agglutination inhibitors, etc. As such an additive, those described in paragraphs [〇155] to [〇156] of JP-A-2004-2951 are mentioned. In the color composition of π + f, the sensitizer or the photosensitizer described in paragraph (4) 〇 78 of JP-A-2004-295 i16 can be found in the paragraph [〇〇81] of the publication. Thermal polymerization inhibitor. "In order to promote the alkali solubility of the non-exposed area, and further improve the imaging performance of the color composition, 轫 ° 竣 acid, t A ^ $ 曰 is preferably added to the composition of the organic hard (2) 夂The molecular weight is 10 〇Πιν·τ~, 00 or less of a low molecular weight organic carboxylic acid. Specifically, for example, ψ ^ a bovine decanoic acid, acetic acid, propionic acid, butyric acid, hydrazine, trimethylacetic acid _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Bismuth, azelaic acid, brazil acid, methyl sulphate, ethylmalonic acid, succinic acid ★ τ violent malonic acid, methyl succinic acid, tetramethyl succinic acid, citrine, etc. One,

Jg ^, 肪 知 know an enemy acid: C3 retinoic acid, g 酸酸, camphoric acid, etc., ^ Ma m S ^ 'dicarboxylic acid; benzoic acid, toluic acid, p-cumenecarboxylic acid, 2, 3 _ dimethyl hydrazine 4 monocarboxylic acid. w ^ Indigenous hydrazine of earthen carboxylic acid, a certain forest acid, etc., early retanning, phthalic acid, m-acid, 妁〇Λ 甲 夂 夂, p-benzoic acid Benzotriazine, homotricarboxylic acid, pyromellitic acid, aromatic tetracarboxylic acid, _ 136 - 201221520; phenylacetic acid, hydrogenated atropic acid, hydrogenated cinnamic acid, mandelic acid, benzene Other carboxylic acids such as succinic acid, atropic acid, cinnamic acid, cinnamic acid cinnamate, benzyl cinnamate, cinnaminoacetic acid, taronic acid, oleic acid. ~Preparation method of coloring composition - The coloring composition of the present invention is prepared by mixing the above-mentioned respective components and optional components as needed. Further, in the preparation of the coloring composition, the components constituting the coloring composition can be formed. The mixture may be blended in a batch, or may be sequentially blended after dissolving and dispersing the components in a solvent. Further, the order of input or the working conditions at the time of blending are not particularly limited. For example, all the components may be simultaneously dissolved and dispersed in a solvent to prepare a complex, and if necessary, each component may be suitably two or more solutions and dispersions, and they may be mixed at the time of application (at the time of coating). It is modulated as a composition. The coloring composition of the above-mentioned five-week system can be used by filtration using a filter having a pore diameter of Ο.ΟΙηηι~3·0μηι, a better aperture of μ5μηι~〇 5μπι, and the like. The coloring composition of the present invention is suitable as a liquid crystal display device (Hquid crysul display: LCD) or a solid-state imaging device (for example, C(:D(charge c〇upled device)') because it can form a hue and a comparatively excellent colored cured film. It is used for the formation of color pixels such as color filters used in CMOS (compound metal oxide semiconductor), and is suitable for use in printing inks, inkjet inks, paints, etc. It is particularly suitable for liquid crystal display devices. Use of coloring pixel formation-137-201221520 &lt;Color filter and its manufacturing method&gt; The color filter of the present invention is composed of a substrate and a dye compound on a δ-shaped substrate (ie, selection) a dipyrrolidino-based metal-based compound compound in which a compound represented by the above formula (I) is coordinated to a metal atom or a metal compound, and any one of the above formula (11) to formula (νπι) The coloring region of the compound in the group formed by the dye compound and the ruthenium compound. The colored regions on the substrate are formed by the respective pixels forming the color filter, such as red (R). ), a color film such as green (G) or blue (Β). The color filter of the present invention is formed by containing a predetermined dye compound and a ruthenium compound, so that the hue and contrast of the image are excellent, and it is particularly suitable. The color filter of the present invention can be formed by any method as long as it is a method of forming a colored region (colored pattern) which is cured by containing a dye compound and a ruthenium compound. It is preferred to use the present invention. The method for producing a color filter according to the present invention comprises the steps of: applying the coloring composition to a support to form a colored layer (also referred to as a colored composition layer); Α), the step (B) of forming a colored region (colored pattern) by exposing the colored composition layer formed in the step (Α) to a pattern (preferably by a mask) and developing the image. In the method for producing a color filter of the present invention, a particularly preferable aspect is a step (c) of irradiating the colored pattern formed by the step (B) with ultraviolet rays, and a step of exposing the ultraviolet to the step (C). The step of heat-treating the colored pattern ⑺). Further, a color filter can be produced by a method such as the transfer method described in JP-A-2009-1, 16078, or the ink jet method described in JP-A-2009-1 34263. 8 - 138 - 201221520 The following is a more detailed description of the color method of the present invention. -Step (A) - The colored composition of the present invention is applied by spin coating, cast coating, or co-coating on the production body of the color filter of the present invention, and is formed into a preliminary hardening (prebaking) as needed. Baked) The layer is dry. Examples of the support include, for example, liquid crystal display soda glass, alkali-free glass, borosilicate glass, and stone resin substrate. Further, on the support, the undercoat layer for improving the adhesion of the upper layer and the diffusion prevention of the substance. The colored composition of the present invention can be applied directly or on a plate by a coating method such as spin coating, slit coating, cast coating, or ink jet, to coat a film. The prebaking conditions are heated by using a c c to 130 ° C for about 0.5 minutes to about 15 minutes, and the color formed by the colored composition is appropriately selected according to the purpose. Preferably, the liquid crystal display device is in the range of 〇.2μηι~5.0pm, and more preferably in the range of 1·5 μηι to 3.5 μηι, preferably 〇2μιη~ preferably In the range of 〇.3μπι to 2·5μηι, which is preferably a method for producing a ruthenium color filter, first, a layered layer is colored by a coating method such as a support cloth, and the shai coloring composition device is used. The used ruthenium and ruthenium substrate used may be provided with a flat or other surface at the same time as the flat surface of the substrate, the roll coating, and the rod forming a colored composition of the atmosphere or the oven at 70°. The thickness of the composition layer is set in the color filter ^· is Ι.Ομηι~4.0μΐΏ. Further, in the range of the solid-state imaging 5·0μηι, the range of 3μιη to 1.5μιη -139- 201221520 Further, the rhinoceros of the coloring composition layer - the step (Β). The film thickness after the baking of the twisted material. Next, in the method of manufacturing the color stalk of the present invention, the coloring formed on the support is performed, for example, by a mask (Ph〇t0mask). ^ ^ ^ spoon" is used to expose light or radiation, preferably g line, h line, i line,

KrF first, ArF light, especially good for i line. When the i-line is used for the irradiation of light, the 鲈社* 2 ^ 季乂佳 is irradiated with an exposure amount of l〇〇mJ/cm2 to 10000 mJ/cm2. As the exposure light of the ', you can also use ultra-high pressure, high pressure: medium pressure, low pressure, various mercury lamps, chemical lamps - anaerobic lamp xenon lamp, metal halide lamp, visible and ultraviolet laser light source, fluorescent lamp, tungsten Lights, sunlight, etc. ~ Exposure step using a laser source ~ In the exposure mode using a laser source, an ultraviolet laser is used as the light source. The illuminating light is preferably an ultraviolet laser having a wavelength in the range of 3 〇〇 nm to 380 nm, more preferably an ultraviolet laser having a wavelength in the range of 3 〇〇 nrn to 36 〇 nrn. The point of the resistive wavelength of the resist is preferred. Specifically, a third harmonic (3 55 nm) of a Nd:YAG laser having a large power transmission and a relatively inexpensive solid-state laser, or XeCl (308 nm) and XeF (353 nm) of a pseudo-molecular laser may be employed. The exposure amount of the exposed object (pattern) is in the range of 1 mj/cm 2 to 1 〇〇 mj/cm 2 , more preferably in the range of lmJ/cm 2 to 50 mJ/cm 2 . If the exposure amount is "the circumference", it is preferable in terms of the productivity of pattern formation. 201221520 There is no particular limitation on the exposure apparatus. As a marketer, you can use CalliSt〇 (V Techn〇 (〇 gy c〇, Ltd.)) or EGIS (made by V Technology Co., Ltd.) or DF22〇〇G (manufactured by Dainippon Screen MFG. Co., Ltd.) and the like. Further, devices other than the above are also applicable. The exposed colored composition layer as described above can be heated. Further, in order to suppress oxidative fading of the color material in the colored composition layer, the exposure system can be carried out while flowing nitrogen gas inside the chamber. Next, the exposed coloring composition layer was developed with a developing solution. Thereby, a negative or positive color pattern (resist pattern) can be formed. The developer liquid may be a combination of various organic solvents or an alkaline aqueous solution as long as it dissolves the uncured portion (unexposed portion) of the colored composition layer and does not dissolve the cured portion (exposed portion). When the developing solution is an alkaline aqueous solution, the concentration is preferably adjusted to pH 11 to n, and more preferably to pH 5 $: 12.5. Examples of the above-mentioned aqueous test solution include gas oxidized sodium, potassium oxyhydroxide, sodium carbonate, sodium hydrogencarbonate, sodium methoxide, ethylamine, diethylamine, dimethylethanolamine, and tetraammonium hydroxide; An alkaline aqueous solution such as oxidized tetrazole, biliary test, sputum, pie, sputum, 8_two = -[5,4,〇]_7_undecene. : ', the dressing time is preferably 30 seconds to 300 seconds, more 3 seconds ~ 12 〇 and, like the temperature is better to grab ~ 4 (TC, better for calling. 乂 for imaging can borrow It is preferably washed with water by a liquid-coating method, a shower method, a spray method, or the like, and after development using an alkaline aqueous solution, -141 - 201221520, and then, in the method for producing a color filter or a light sheet of the present invention, If necessary, post-heating and/or post-exposure of the colored pattern formed by the development may be performed to promote hardening of the colored pattern. - Step (c) - In the method of manufacturing the color filter of the present invention, in particular The coloring pattern (pixel) formed by using the coloring composition may be subjected to post-exposure by ultraviolet irradiation. Step (D) - a coloring pattern after post-exposure by ultraviolet irradiation as described above is preferably Further, the heat treatment is performed, and the colored pattern can be further cured by a colored pattern formed by heat treatment (so-called post-baking treatment). This heat treatment can be performed, for example, by a hot plate, various heaters, an oven, or the like. Processing time The degree is preferably 1 〇〇 ° C to 300 ° C, more preferably 15 0 ° C ~ 25 0 ° C. Also 'heating time is preferably 10 minutes ~ 12 〇 shovel around. The color pattern thus obtained Forming a halogen in a color filter. In the production of a color filter for producing a halogen having a complex hue, the desired color number can be matched, and the above steps (A), (B), and optionally Step (C) or Step (〇) » Further, after the exposure and development of each (one color) single color composition layer is formed, the above step (C) and/or step (D) may be performed. , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 142-201221520 The color filter (color filter of the present invention) obtained by the method for producing a color filter of the present invention is excellent in hue and contrast by using the coloring composition of the present invention. The color filter of the present invention The sheet system can be used for a liquid crystal display element or a solid-state image sensor, and is particularly suitable for use in a liquid crystal display device. In the case of a liquid crystal display device, a dye is used as a colorant, and an image having excellent spectral characteristics and contrast can be obtained. <Liquid crystal display device> The liquid crystal display device of the present invention includes the above-described present invention. Color filter. The definition of the liquid crystal display device or the details of each display device is, for example, published in the electronic display device (Kogy〇 Chosakai Publishing Co., Ltd.) in 1990. )", "Display device (Ibuki Shunzhang, Industrial Book (share)" (Sangyo Tosho)

Publishing Co., Ltd.) is published in the first year of Heisei (1989). In addition, the liquid crystal display is described in, for example, "The next generation of liquid crystal display technology (Editor Uchida Natsuo, Industrial Research Association (share), issued in 994)". The liquid crystal display device which is not applicable to the present invention is particularly limited. For example, various types of liquid crystal display devices of the "next generation liquid crystal display technology" described above can be applied. The color filter of the present invention is particularly effective for a color TFT (thin film tranS1 St〇) type liquid crystal display device. The liquid crystal display device of the color IFT type has been incorporated in, for example, "Color Tft Liquid Crystal Display II (', Ky〇ritsu Shuppan Co., Ltd., 1996). Furthermore, the present invention is also applicable to a liquid crystal display device in which an ips (in-plane switching), an electric field driving method, an mva (multi-domain vertical alignment), and the like, and a viewing angle expansion, or an STN (super) Twist to -143 - 201221520 column), TN (twisted nematic), VA (vertical alignment), 〇CS (optical compensation expansion), FFS (fringe field switching), and R-OCB (reflective optical compensation bending). Further, the color filter of the present invention is also applicable to a bright, high-definition CO A (color filter array) method. If the color filter of the present invention is used to combine a liquid crystal display element with a conventional three-wavelength tube of a cold cathode tube, high contrast can be achieved, but a red, beta green, and blue LED light source (RGB_LED) is used as a backlight ( [Backiight] shows: a liquid crystal display having high color reproducibility with high brightness and high color purity. [Embodiment] Hereinafter, the present invention will be more specifically described by way of example, as long as it does not exceed the main 'as long as there is no special_dye compound_ embodiment. However, the present invention is not limited by the following examples. In addition, the "prescription" is based on the quality. (A-1) dyeing coarse. ^ Compound compound represented by the above formula (1_3): methylene metal metal is not a compound ΙΠ _9 〇 (A - 2) dye: a, +.』 (A- 4) Dyeing μ. Specific examples of the compound represented by the formula (Π) 46. Compounds represented by the following structural formula (4)

An exemplary compound of the dipyrromethene metal as shown by the dimeric formula (I-3) of the complex compound IV-A (A-3) Dyes: 1 (4) 8 -144- 201221520 (A-5) Dyes: a compound represented by the structural formula (5)

-145- 201221520 (A-8) Dyes: Compounds represented by the following structural formula (8)

N &gt; 〇 (8) (A-9) Dyes: compounds represented by the following structural formula (9)

Antimony compound - (A-1 0) dye: an antimony compound represented by the following structural formula (1) Ο \n (10)

〇 A 8 -146 201221520 (A-1 1) Dyes: an oxime compound represented by the following structural formula (1 1) 〇

(11) (A-12) Dyes: an anthracene compound represented by the following structural formula (12)

-147- 201221520 (A-1 3) Dyes: anthracene compounds represented by the following structural formula (1 3)

(13) (A-14) Dyes: an oxime compound represented by the following structural formula (14) CHs 』JL must h-ch2-ch3 C2H5

Ch3 ,ch-ch2-ch3 so2nh 〇2^ ^ &quot;CH3 (14)

:0 HN^i^S02NH C2H5 (A-l 5) Dyes: anthracene compounds represented by the following structural formula (15)

(15) 201221520 (A-1 6) Dyes: anthracene compounds represented by the following structural formula (16)

(16) (A-17) Dyes: a dipyrrole hydrazine compound represented by the following structural formula (17)

-149-

S 201221520 (A-18) Dyes: dipyrromethene metal complex compound represented by the following structural formula (18)

(18) (A-19) Dyes: dipyrrolidene fund represented by the following structural formula (19)

-150- 8 201221520 (A-20) Dyes: dipyrromethene-based compound represented by the following structural formula (20)

(A-21) Dye: a dipyrromethene metal complex compound represented by the following structural formula (21)

Iai) -151 - 201221520 Methyl gold (A-22) dye: dipyrromethene complex compound represented by the following structural formula (22)

(A-23) dye: a hydrazine compound represented by the following structural formula (23)

(23) CH3 8 -152- 201221520 (A-24) Dyes: anthracene compounds represented by the following structural formula (24)

(24) (A-25) Dyes: anthracene compounds represented by the following structural formula (25)

(25) (B-1) 14 parts of CI Pigment Green 58 and 3.4 parts of acrylic pigment dispersant and 82.6 parts of propylene glycol monodecyl ether acetate were mixed, and the pigment was sufficiently dispersed using a bead mill. Pigment dispersion. (B-2) mixing 12.8 parts of CI Pigment Blue 15:6, 7.2 parts of acrylic pigment dispersant and 80.0 parts of propylene glycol monodecyl ether acetate, and using a bead mill to sufficiently disperse the pigment Dispersions. (C-1) Photopolymerizable compound: KAYARAD DPHA (Nippon Kayaku Co., Ltd.); dipentaerythritol pentaacetic acid vinegar and dipentaerythritol hexapropylene Mixture of acid S) -153- 201221520 (D-1) Adhesive resin: benzyl methacrylate/methacrylic acid (solid content 40.0% by mass) (D-2) binder resin: benzyl methacrylate Ester/mercapto-acrylic acid/epoxypropyl methyl acrylate acid adduct with methyl acrylate (30/33/37 [mole ratio], solid content 45.0% by mass propylene glycol monomethyl Ether acetate solution) (ugly-1) photopolymerization initiator: 2-(benzophenoxyimino)_1_[4_(phenylthio)phenyl]-1 -octanone (E-2) light Polymerization initiator: 2-(ethyloxyimino)-4-(4-chlorophenylthio)-1·[9-ethyl-6-(2-mercaptophenyl)--9H- Oxazol-3-yl]-i-butanone (E-3) photopolymerization initiator: 2-(dimethylamino)-2-[(4-indenylphenyl)indolyl]-1-[4 -(4-merinyl)phenyl]_ι_butanone (E-4) photopolymerization initiator: 2-trimethylsulfonyl-5-(4-styryl)styryl-1-indole-3, 4-Diazole (E-5) photopolymerization initiator: 2-( Phenyl)-4,5-diphenylimidazolyl dimer (F-1) photopolymerization initiation aid: 4,4,-bis(diethylamino)diphenyl ketone (F-2) Photopolymerization initiation aid: 2-mercaptobenzothiazole (F-3) photopolymerization initiation aid: 4-oxazolidinone, 3-cyclohexyl-2-(cyclohexylimido)-5[[4 -(Diethylamino)phenyl]indenyl], and the compound (D45) described in JP-A-2009-262523 &gt; (F-4) Photopolymerization initiation aid: 2-mercapto- 5-(2,-ethyl)hexylamino benzoyl benzoate

(F-5) Pyrolysis-type radical generator: 2,3-dimethyl-2,3-diphenylbutane (NOFMER BC-90, Nippon Oil & Fats Co., Ltd. (n〇F

Corporation) 201221520 (F-6) Additive; 1,2-Epoxy-4-(2-oxiranyl)cyclohexane of 2,2-bis(hydroxymethyl)-1-butanol Adduct (EHPE-3 1 50, manufactured by Daicel Chemical Industries Ltd.) (Gl) Solvent: propylene glycol monodecyl ether acetate (G-2) solvent: 3-ethoxypropionic acid Base (H-1) surfactant: MEGAFACE 781-F (manufactured by DIC Corporation) Synthesis Example of Dye Compounds ~ The following compounds (1 3) are shown below. Synthetic method.

<Synthesis of Compound (13B)> I4 〇 mL of chlorosulfonic acid was added to a 500 mL flask, and the mixture was heated to 40 C. Add 30 g of compound (13A) [CERES Blue RR-J by Lanxess K.K. Corporation] a little bit in a while. After the addition, the reaction solution was stirred at 70 ° C for 1 hour' and then cooled to room temperature. Prepare a mixture of l〇〇g salt, 500 mL of water, and i.5 kg of crushed ice in a separate beaker, and carefully drip the reaction solution into it. After the dropwise addition, the resulting suspension was stirred for 3 minutes and filtered to obtain 158 g of a wet crystal of compound (13B). &lt;Synthesis of Compound (13)&gt; In a 500 mL flask, 14 7 g of 2-ethylhexylamine, 26 g of triethylamine, and 200 mL of toluene were added. Among them, while mixing, a small amount of -155-201221520 was added little by little to the wet crystal of this compound (1 3B). After the addition, the tax was mixed for 1 hour, and 500 ml of ethyl acetate was added thereto. To the resulting solution, 'sodium sulfate as a dehydrating agent was added and filtered, and the resulting solution was concentrated. This was refined by gel column chromatography (hexane/ethyl acetate) to give 21 g of compound (1 3). 1H NMR (300MHz, in CDC13) of the obtained compound (13): δ(ρρηι)=1 1.89 (2H, s), 8.44 (2H, dd), 7.80 (2H, dd), 7.14 (2H, s), 6.44(2H,d), 4.30-4.50(2H,m),3.23-3.42(2H,m),2.64-2.9 7( 1 2H,m), 2.3 0-2.64(4H5m), 1.00-1.46(30H, m), 0.68-0.92 (1 2H, m) The following compound was also synthesized by the same method as the above-mentioned compound (1 3). 8 anthracene compound represented by the aforementioned structural formula (14)

-156 201221520 The awakening compound represented by the aforementioned structural formula (24)

The brewing compound represented by the aforementioned structural formula (25)

NMR (300MHz, in CDC13) of the above compound (14): δ(ρρπ〇=1 1.8 8(2H, s), 8.44 (2H, dd), 7.80 (2H, dd), 7.12 (2H, s), 6.41(2H,dd),4.23-4.31(2H,m), 3.20-3.40(4H,m),2.3 3-2.8 9(12H,m),0.97-1.5 5(22H,m),0.60-0.8 9 (6H,m) 1H NMR (300MHz, in CDC13) of the above compound (24): 5 (ppm) = 12.14 (0.5H, s), l 1.74 (1H, s), 1 1.60 (0.5H, s), 8.3 8-8. 45(2H,m) , 7.79-7.84(2H5m), 7.25-7.23 (0.5H,m), 7.1 1-7.18( 1.5H,m), 6.98-7.02(0.5H,m), 6.44-6.52( 1.5H,m)s4.3 7-4.42 (2H5m), 2.76-2.91(4H,m), 2.70(6H,t),2.5 2-2.64(6H,m),2.1 〇-2.2 6 (6H, m), 1.06-1.42 (1 8H, m), 0.73-0.92 (12H, m) -157- 201221520 1H NMR (300MHz, in CDC13) of the aforementioned compound (25): δ(ppm)= 1 2,1 3 (0.5H,s),l 1.75(1 H,s),l 1.59(0.5H,s),8.35-8.47 (2H,m),7.77-7.90(2H,m),7.25- 7.23 (0.5H, m), 7.08-7.20 (l. 5H, m), 6.95-7.02 (0.5H, (1), 6.43-6.49 (1.5H, m), 4.25-4.40 (2 H, m), 3.20-3.35 (2H,m),2.7 1( 6H,t),2.58(6H,t), 2.10-2.28(6 H, m),1.35-1.50 (4H,m),1.00-1.12 (6H,m ), 0.76-0.90 (6H, m) (Example 1) - Coloring Modification of the product 1 - The components in the following composition are mixed to prepare the coloring composition 1. &lt;Composition&gt; • The above (A-1) • ·· 4.7 parts by mass • The aforementioned (A-1 2) ... 2.3 parts by mass • The above (B-2) • ·· 42.1 parts by mass • The above (C-1) .·· 103.4 parts by mass • The above (D-1) • · .212.2 parts by mass (solid content conversion value: 84.9 mass) (Part 1) • The above (E-1) • · · 2 1 · 2 parts by mass • The above (F-1) • · · 3.5 parts by mass • The above (G-1) • ·· 71.9 parts by mass • The above (G_2). .. 3.6 parts by mass • The formation of the above (H-1) coating film _ • . · 〇·〇 6 parts by mass, followed by glass (# 1737; manufactured by C〇rning Inc.) In the spin coating, after the coloring composition 1 obtained above was applied, the volatile component was volatilized at 1 ° C for 3 minutes to form a film 1 of the composition of 8' - 158 - 201221520. After cooling, the colored composition film 1 was irradiated with an i-line 波长 wavelength of 365 nm]. The light source on the i-line is irradiated with parallel light using an ultra-high pressure mercury lamp. The amount of irradiation light was 500 mJ/cm2. Subsequently, post-baking was carried out at 180 C for 20 minutes to obtain a blue composition film 1 having a film thickness of 2 μm. The chromaticity ' under the C light source was measured as χ = 0·1 5 y = 0.09 ° using a microscopic spectrometry apparatus OSP-SP200 manufactured by Olympus Corporation (Example 2) except In the first embodiment, '(A-1) is changed to (A_2), and the ratio of (Α·2) to (Β-2) is adjusted to x = 0.15 y = 〇.〇9, and the embodiment! Similarly, a blue composition film 2 was obtained. (Embodiment 3) Except that in Embodiment 1, (A-1) is changed to (A_6), and the ratio of (Α·6) to (Β-2) is adjusted to x = 〇.15 y = 〇.〇 In the same manner as in Example i except for 9, a blue composition film 3 was obtained. (Example 4) A blue composition film 4 was obtained in the same manner as in Example 1 except that (A-12) was changed to (A_1〇) in Example 1. (Embodiment 5) Except that in the first embodiment, '(A-ι) is changed to (A_2), (A12) is changed to (A-1), and (A-2) and (B-2) are The blue composition film 5 was obtained in the same manner as in Example 1 except that the ratio was adjusted to χ = 〇丄5 y = 0.09. (Example 6) Except that in Example 1, (A-1) was changed to (A-6), (A_12) was changed to (A-11), and (A-6) and (B-2) were changed. The blue composition film 6 was obtained in the same manner as in the example ί except that the ratio was adjusted to χ = 〇i5 y = 〇.〇9. -159-201221520 (Example 7) A blue composition film 7 was obtained in the same manner as in Example 2 except that the amount of (A-1 2) added in Example 2 was changed from 2.3 parts by mass to 5.0 parts by mass. (Example 8) A blue composition film 8 was obtained in the same manner as in Example 2 except that (A-12) of Example 2 was changed to (A-13). (Example 9) A blue composition film 9 was obtained in the same manner as in Example 2 except that (A-12) of Example 2 was changed to (A-14). (Example 10) A blue composition film 10 was obtained in the same manner as in Example 2 except that (A-12) of Example 2 was changed to (A-15). (Example 1 1) A blue composition film 11 was obtained in the same manner as in Example 2 except that (A-12) of Example 2 was changed to (A-1 6). (Example 12) In addition to changing (A-2) of Example 2 to (A-17), (A-12) was changed to (A-14), and (E-1) was changed to (E-2). A blue composition film 1 2 was obtained in the same manner as in Example 2 except for the above. (Example 1 3) In addition to changing (A-2) of Example 2 to (A-18), (A-12) was changed to (A-13), and (E-1) was changed to (E-). In the same manner as in Example 2 except for 2), a blue composition film 13 was obtained. -160- 8 201221520 (Embodiment 14) In addition to changing (A-2) of Example 2 to (A-19), (A-12) is changed to (A-15), and (E-1) is changed. A blue composition film 14 was obtained in the same manner as in Example 2 except for (E-2). (Example 15) In addition to changing (A-2) of Example 2 to (A-20), (A-12) was changed to (A-16), and (E-1) was changed to (E-2). A blue composition film 15 was obtained in the same manner as in Example 2 except for the above. (Example 16) A blue composition film 16 was obtained in the same manner as in Example 2 except that (A-2) of Example 2 was changed to (A-21). (Comparative Example 1) A blue composition film A was obtained in the same manner as in Example 2 except that (A-12) of Example 2 was not added. (Comparative Example 2) A blue composition film B was obtained in the same manner as in Example 14 except that (A-15) of Example 14 was not added. (Example 17) [Preparation of colored composition 1 7] The components in the following compositions were mixed to prepare a coloring composition 17 . &lt;Composition&gt; • The above (A-3) . . . 4.1 parts by mass. The above (A-12) ··1.7 parts by mass • The above (B-1) . . . ·22·3 parts by mass • The above (C -1) . . . 103.4 parts by mass 201221520 . The above (D-1) ... 212.2 parts by mass (solid content converted value: 84.9 parts by mass) • The above (E-2) .·· 21.2 parts by mass • the above (F -1) • · · 3.5 parts by mass • The above (G -1) • · · 7 1.9 parts by mass. The above (G-2) • .· 3.6 parts by mass. The above (H-1) ... 0.0 6 parts by mass The coating film was formed in the same manner as in Example 1 to obtain a colored composition film 17. The chromaticity under the C light source was measured using a microscopic spectrometry apparatus OSP-SP200 manufactured by Olympus Co., Ltd., and the crucible was x = 0.30 y = 0 · 5 7 . (Example 18) Except that (A-3) of Example 17 was changed to (A-4), the ratio of (A-4) and (B-1) was adjusted to x = 0.30 y = 0.57, and Example 17 Similarly, a green composition film 18 was obtained. (Example 19) Except that (A-3) of Example 17 was changed to (A-5), the ratio of (A-5) and (B-1) was adjusted to x = 0.30 y = 0.57, and Example 17 Similarly, a green composition film 19 was obtained. (Example 20) Green was obtained in the same manner as in Example 1 except that (A-3) of Example 17 was changed to (A-7) and (A-12) was changed to (A-1 0). The composition film 20 is formed. (Example 21) (A-8) and (B-1), except that (A-3) of Example 17 was changed to (A-8) and (A-12) was changed to (Al1). The ratio is adjusted to x = 0.30 8 -162- 201221520 y = 0.57, invite 2 i. In the same manner, a green composition film was obtained (Example 22). Similarly, the tube y 丨 ("rate adjustment == A-3" was changed to ^. Similarly, it was obtained: 〇.30 y = 〇 In addition to 57, the green composition film 22 was judged in the same manner as in the examples. (Comparative Example 3) The green composition film C was obtained in the same manner as in Example 18 except that (A-1 2) of Example 18 was not added. (Comparative Example 4) In the same manner as Example 20 except that (Α-10) of Example 20 was not added, a green composition film 〇 was obtained. (Comparative evaluation of shell size) :: Each of the composition films obtained above was evaluated by the following method. The evaluation results are shown in Tables i to 2 below. The obtained composition film was sandwiched between two polarizing films, and a color brightness meter (TopconC〇rp〇mi〇n type / BM-5A) was used to measure the two polarizing films. When the polarization axis is parallel and the vertical value is 'the brightness when the polarization axes of the two polarizing films are parallel divided by the brightness when it is vertical', the obtained value is obtained as a comparison. The higher the contrast ratio, the more it can be used as a color calender for liquid crystal displays. The brightness was measured by using a microscopic spectrometry apparatus OSP-SP200 manufactured by Olympus Co., Ltd., and evaluated by the γ value. The higher the γ value, the better the performance as a color filter for liquid crystal displays. -163- 201221520 Table 1] Dye compound 蒽醌 compound versus Y value Example 1 A-1 A-12 25100 10.8 Example 2 A-2 A-12 23600 11.0 Example 3 A-6 A-12 27100 10.5 Example 4 A-1 A-10 24000 9.8 Example 5 A-2 A-11 23600 10.8 Example 6 A-6 A-11 23600 10.3 Example 7 A-2 A-12 26400 10.1 Example 8 A-2 A- 13 24100 11.1 Example 9 A-2 A-14 25200 11.0 Example 10 A-2 A-15 23900 11.3 Example 11 A-2 A-16 23600 11.0 Example 12 A-17 A-14 21900 11.4 Example 13 A-18 A-13 22300 11.6 Example 14 A-19 A-15 26500 11.2 Example 15 A-20 A-16 20600 10.4 Example 16 A-21 A-12 23700 10.9 Comparative Example 1 A-2 — 13200 10.8 Comparative Example 2 A-19 - 9800 10.2 8 - 164 - 201221520 Table 2] ------- Example 17 - Dye Compound 蒽醌 Compound _ Comparative Y value A-3 A-12 42100 60.8 Example 18 A- 4 A-12 38400 60.5 Example 19 A-5 A-12 35900 60.3 Example 20 A-7 A-10 38300 59.8 Example 21 A-8 A-11 41600 61.2 Example 22 A-9 A-12 39900 60.3 Comparative Example 3 A-4 - 18900 60.6 - 1 k 匕 Comparative Example 4 A-7 - 16200 60.9 As shown in the above Tables 1 to 2, in the examples in which the dye compound was used together with the gamma compound, the contrast was greatly improved while maintaining the Y value. (Example 2 3) A blue composition film 23 was obtained in the same manner as in Example 8 except that (E-1) of Example 8 was changed to (E-3). Further, the contrast and the brightness were measured by the above method. (Example 2 4) The blue composition film 24 was obtained in the same manner as in Example 8 except that (E-1) of Example 8 was changed to (E-4). Further, the contrast and the brightness were measured by the above method. (Example 2 5) - In addition to (Ε-1) 21·2 parts by mass and (F-1) 3.5 parts by mass of Example 8, it was changed to (El) 19.7 parts by mass of '(Ed)】 (f_2) 2. 〇-165-201221520 parts by mass, (F-3) 1.5 parts by mass, a blue composition film 25 was obtained in the same manner as in Example 8. Further, the contrast and the brightness were measured by the above method. (Example 26) The (E-1) 21.2 parts by mass and (F-1) 3.5 parts by mass of Example 8 were changed to (Ε-1) 18·0 parts by mass, (Ε-5)1.3 mass. A blue composition film 26 was obtained in the same manner as in Example 8 except that (Fl) 1.4 parts by mass and (F-4) 4.0 parts by mass. Further, the contrast and the brightness were measured by the above method. (Example 27) (A-2) and (B-2) except that (A-2) of Example 26 was changed to a 98:2 (mass ratio) mixture of (A-2) and (A-22). The ratio is adjusted to x = 0.15 y = 0.09, and (C-1) 103 _4 parts by mass is changed to (Cl) 101.3 parts by mass, (F-5) 2.1 parts by mass, and (Dl) 212.2 parts by mass is changed to (D-2) A blue composition film 27 was obtained in the same manner as in Example 26 except that 188.7 parts by mass and (F-6) 23.5 parts by mass. Further, the contrast and the brightness were measured by the above method. 8 Table 3] Dye compound 蒽醌 compound vs. Y value Example 23 A-2 A-13 24300 11.1 Example 24 A-2 A-13 24800 10.8 Example 25 A-2 A-13 24200 10.6 Example 26 A- 2 A-13 24400 10.9 Example 27 A-2 A-22 A-13 24600 10.8 -166 - 201221520 The blue composition obtained from the example of .8, 2 3~2 7 is regarded as the blue composition. twenty three~? 7, he Tianye

▲ 27 Using this blue composition, in the same manner as in the formation of Example J:::, 'coating by the spin coating method to make the volatilization into a knife, the amount of irradiation light at the time of exposure was 60 mJ/cm 2 , Close to the gap (pr〇xlmity gap) is 2〇〇μιη 'Exposure through a striped patterned mask' 0.045% potassium hydroxide-based imaging solution (trade name; cdk Fujifilm Electronic Materials Co., Ltd. ElectroGnies Materials C〇_ (manufactured by Ltd.)) A developing solution diluted 1⁄2 times with pure water was used for development, and a good halogen pattern which was not observed by an optical microscope was observed. After 30 minutes of post-baking at 3 ° C, the sem was observed and the prime cross section was observed. From the vertical view, a cis-conical shape of the alizarin was observed. — (Example 28) [Production of Blue Photosensitive Transfer Material] A slit nozzle was used on a polyethylene terephthalate film temporary support (support for PET 35) having a thickness of 75 μm. The coating liquid for a thermoplastic resin layer formed in the following formulation Η1 was dried. Next, the coating liquid for an intermediate layer formed by the following crucible P1 was applied and dried. Further, the colored composition 8 obtained in Example 8 was applied and dried. In this manner, a thermoplastic resin layer having a dry film thickness of ΐ5ΐμηι, an intermediate layer having a dry film thickness, and a photosensitive blue colored layer having a dry film thickness of 2.3 μm were provided on the temporary support. The final pressure-sensitive protective film (thickness polypropylene) The film "produces" a temporary support, a thermoplastic resin layer, an intermediate layer (oxygen barrier film), and a blue colored layer as a transfer material. This is regarded as a blue photosensitive transfer material 8. -167- 201221520 • · &quot; . 1 copy • 6.36 copies • · 52.4 copies

(Coating liquid for thermoplastic resin layer: Prescription Η 1) • Sterol I: Propylene glycol monomethyl ether acetate. • Mercaptoethyl g. • Methyl methacrylate/acrylic acid 2. Ethyl· · 5.83 parts of hexane vinegar / benzyl methacrylate / methacrylic acid copolymer (copolymerization ratio (mole ratio) = 55 / 11.7 / 4_5 / 28.8, molecular weight = 100,000, glass transition temperature (Tg) and 70 °C) • Styrene/acrylic acid copolymer (copolymerization · .13.6 parts ratio (mole ratio) = 63/37, average molecular weight = 10,000, Tg and loot:), • 2, 2-double [4- (Mercapto propylene oxy group) · 9.1 parts of ethoxy) phenyl] propylene (manufactured by Shin-Nakamura Chemical Co., Ltd.) • 糸3⁄4^ · · · 0 · 5 4 parts (40 parts of C6F13CH2CH20C0CH = CH2, 55 parts of H (〇ch(C H3)CH2)7OCOCH = CH2 and 5 parts of H(0CHCH2)70C0CH = CH2 copolymer, average molecular weight: 30,000, mercapto ethyl ketone 30 mass ° / 〇 solution 'Daily Ink Chemical Industry Co., Ltd. (DIC Corporation), trade name: MEGAFACE F780F) (coating solution for intermediate layer: prescription P1) 8 -168 - 201221520 • PVA-205 · · · 32.2 parts (Polyvinyl alcohol, manufactured by Kuraray Co., Ltd., saponification degree = 88%, degree of polymerization: 550) • Polyethylene. More than ° ° ketone..· 1 4 · 9 parts (ISP 曰 公司 (ISP Japan Ltd.), K-30) • Steaming water · · · 524 parts • methanol ... 429 parts by The shower was sprayed with a glass cleaner liquid adjusted to 25 on the non-test glass substrate for 20 seconds, and washed with a rotating brush having nylon wool, and washed with pure water spray. Then, spray the sulphur coupling solution (Ν-β (aminoethyl) γ-aminopropyltrimethoxy oxane 〇 3 mass / hydrazine aqueous solution by a shower, trade name: ΚΒΜ 603, Shin-Etsu Chemical Industry ( (manufactured by Shin-Etsu Chemical Co., Ltd.) for 20 seconds, washed with pure water spray. This glass substrate was heated at 1 Torr for 2 minutes in a substrate preliminary heating apparatus. The obtained decane coupling treated glass substrate 'removed the protective film from the blue photosensitive transfer material 8 produced by the above-described production method, and the surface of the blue colored layer exposed after being removed is in contact with the surface of the decane coupling treated glass substrate. The way to superimpose 'using laminat 〇r' (Hitachi Plant Technol〇gies (Ud) spoon arnic II type) 'Yu Jing} 〇〇. The glass substrate which was heated for 2 minutes was laminated at a rubber roll temperature of 13 (rc, line pressure of 1 〇〇 N/cm, and conveyance speed of 2.2 m/min. Next, a 1 ρ Ε temporary support was applied to the thermoplastic resin layer. Κ4, 灿, the interface of the day is stripped to remove the temporary support of pet. Stripped PET temporary support _ feet, _ _, and after the body 'use the proximity type exposure machine with ultra-high pressure mercury lamp (曰立高划_ 4 + t ° Technology Electronic Engineering (shares) (Hitachi High- -169- 201221520

(Technology Corporation)), the glass substrate and the reticle (the quartz exposure reticle with image pattern) are vertically erected, and the distance between the exposure mask surface and the blue coloring layer is set to 2 〇〇 μιη, The pattern exposure was performed at an exposure amount of 40 mJ/cm 2 . Next, a triethanolamine-based imaging solution (containing 3% by weight of triethanolamine, trade name: T-PD2 (Fuji film (manufactured by FUJIFILM)) diluted 12 times with pure water (in parts of Dingcher and n parts) The liquid of the mixture of pure water) was spray-developed for 3 seconds at a flat nozzle pressure of 3 (TC &amp; 1 MPa to remove the thermoplastic resin layer and the intermediate layer. Then, on the upper surface of the glass substrate, The mouth is owed to the emptiness, the 7th team 4 occupies 1 person to remove the liquid, and the pure water is sprayed by the sprayer for 1 sec to clean the pure water spray and blow the air to reduce the substrate. The liquid is then retained. Then, sodium carbonate/sodium bicarbonate-based imaging solution (trade name: T_CD1 (made by Fujifilm)) is diluted 5 times with pure water (with 1 part of T-CD1 and ^ pure water) The ratio of the mixture)), at 3〇t:, the sprayer pressure is determined: 〇 'lMPa '3 sec development is washed with pure water. Connect 2, use a cleaning solution containing surfactant (trade name: T-SD3 (manuscript film) (diluted by pure water 10 times the liquid), in the 33t dragon: two cone nozzle pressure spray 2 ° seconds 'more by The soft nylon hair of the 3 疋 刷 矣 矣 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所 所~ The desired blue pixel pattern is measured by the stylus-type thick blue pixel case of the amine (10) system. The film thickness is 2.24μηι. 8 -170- 201221520 Next, After exposure to an exposure amount of 2000 mJ/cm 2 in the atmosphere, post-baking treatment was carried out at 240 ° C for 50 minutes to obtain a substrate in which blue colored ruthenium was formed. The coloring pixels were observed by an optical microscope, and the result was observed. The development residue was confirmed to be a good pixel pattern. (Example 2 9) Except that in Example 28, instead of the pattern exposure of 40 mJ/cm 2 , the exposure amount of l〇〇mJ/cm 2 was comprehensively performed. In the same manner as in Example 28, except for the exposure, a blue coloring film was formed. Dye compound 蒽醌 compound versus Y value * Example 29 A-2 A-13 24200 11.0 Further, in the above embodiment, 'we use A- 1 0 to A-1 6 is described as a case of a ruthenium compound. In the present invention, it is important to have a -9,1 0 _ ketone structure in the structure, and the same result is obtained in the case of using other brewing compounds other than A -1 〇 〜 A 1-6. (Example 3 0) The blue composition film 3 was obtained in the same manner as in the second embodiment except that (A-12) of Example 2 was changed to (a_23). (Example 3 1) The blue composition film 31 was obtained in the same manner as in the implementation of the correction 2 except that (A_12) of the second embodiment was changed to (A_24). (Example 3 2) The blue composition film 3 2 was applied concentrically to Example 2 except that (A·12) of Example 2 was changed to (A-25). -171-201221520 Table 5] Dye compound 蒽醌 compound vs. Y value Example 30 A-2 A-23 23500 10.7 Example 31 A-2 A-24 24500 11.0 Example 32 A-2 A-25 25000 11.0 As described above As shown in Table 5, in Examples 30 to 32 in which a dye compound and an anthracene compound were used, it was possible to further improve the contrast while maintaining a high Y value (1 1.0 or more). Further, in the case of using a ruthenium compound having a linear structure in which the alkyl group bonded to the S02NH group is a linear structure (Examples 10, 1 1 and 3 0), the alkyl moiety bonded to the S02NH group has a branch. In the case of the ruthenium compound of the chain structure (Examples 8, 9, 3, and 32), the higher Y value and contrast were exhibited. [Simple description of the diagram] None. [Main component symbol description] None. 8 -172-

Claims (1)

201221520 VII. Patent application scope: 1 · A coloring composition for a color filter containing: a pyrrole ylene group selected from a compound represented by the following formula (I) coordinated to a metal atom or a metal compound a compound of the group of the metal complex compound and the dye compound represented by any one of the following formulas (II) to (VIII), and a brewing compound; In the formula (I), R1, R2, R: the formula (I) R5 and R6 each independently represent a hydrogen atom or a substituent; and R7 represents a hydrogen atom, a halogen atom, or a halogen group. In the formula (II), A1 represents a radical selected from the group consisting of 5-°. Lin Ketone, different from today. Take ketone, barbituric acid, thiobarbituric acid, lodanine, carbendazim, thioacetate, and sit. Dingdione, 11 than α-dikedione, indane copper, ketone ketone, D ratio saliva. Ratio D-butanone, 1,2,3,4-tetrahydroindenyl-2,4-dione-173- 201221520, 3-oxo-2,3-dihydrobenzo[d]thiophene-1, An acidic nucleus derived from a compound of the group consisting of a dioxide and a 3-dicyano-indenyl-2,3-dihydrobenzo[d]thiophene-1,1-dioxide; L 1 , L2 and L3 represent a methine group; R33 and R34 each independently represent an alkyl group, an aryl group, an alkoxycarbonyl group or a hydrogen atom; R35 represents a hydrogen atom, a methoxy group, a gas atom, a fluorenyl group or a nitro group; η represents 0 or a substituent having at least one bonded to A1 and R33 to R35, having at least one selected from a carboxyl group, a sulfonylamino group, and an aminesulfonyl group in the molecule; FM: General formula (melon) In the formula (III), R41 represents a heterocyclic group; R42 represents a hydrogen atom or a substituent; and R43, R44, R45, R46, R47 and R48 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group. a heterocyclic group, a fluorenyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amine fluorenyl group, an alkylsulfonyl group, an arylsulfonyl group or an amine sulfonyl group; R43 and R44 may be bonded to each other to form a 5-member, Ring of 6 or 7 members; R45 and R46 can be interlocked to form a ring of 5, 6 or 7 members; R47 and R48 can be interlocked to form a ring of 5, 6 or 7 members; 201221520 In the general formula (IV), Ral, Ra2, Ra3, Rb1, Rb2 and Rb3 each independently represent a hydrogen atom or a monovalent substituent, and Ra2 and Ra3 may be bonded to each other to form a 5 to 7 member. a heterocyclic ring; A2 represents an aliphatic group, an aryl group or a heterocyclic group; n represents 0, 1, 2 or 3, and when η is 2 or more, plural Rb2 and Rb3 may be the same or different; R655 In the formula (V), R61, R62, R63 and R64 each independently represent a hydrogen atom, an alkyl group, an aryl group or -S02NH-R; R65 represents a hydrogen atom, an alkyl group, an aryl group, -S03H or -S02NH- R, wherein R represents an alkyl group, an alkoxyalkyl group, a cyclohexyl group, a cyclohexylalkyl group, an alkoxy group, an aryl group or an alkylcarbonyloxy group; η represents an integer of 0 or more, but when η is At 0, at least one of R61 to R65 represents an aryl group having -S02NH-R as a substituent; -175- 201221520 In the formula (VI), R71 represents an alkyl group having 2 to 2 carbon atoms, a cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain, and an alkylcyclohexyl group having an alkyl group having a carbon number of 丨4. a base group of 2 to i 2 substituted with a carbon number of 2 to 12, and a base group of L71-0-C0-L74 represented by l71-c〇-〇-l72- - an alkoxycarbonylalkyl-alkyl substituted phenyl group, or a phenyl group substituted with a phenyl group having a carbon number of 丨~2〇; L" represents an alkyl group having 2 to 12 carbon atoms; and 172 represents a carbon number of 2 〜12的 alkyl; L73 represents an alkyl group having 2 to 12 carbon atoms; [Η represents a carbon number of 2 to 12, and the alkyl groups HR73, R74 and R75 each independently represent an atmosphere atom and a carbon number of 1 to 4; , around the base or i atom. Re1 ^ f by carbon number 2 0 General formula (VH) 矣p *π In the general formula (VI1), Ζ and Ζ2 are each 彳_.r8丨, RS2, r83 R 地 standing surface non-oxygen atom or sulfur atom, and R4 each independently represents a hydrogen atom, carbon Number of workers ~ (7) of saturated aliphatic hydrocarbon groups, hydroxyl groups to know the fat family of a certain family, protect the number of rabbits 1 to 1 0 saturated alkaloids, the number of alkoxygens 1 to 8 of alkoxy, the saturated fat a hydrocarbon group, &quot; instead of a carbon number of 1 to 10 1 to 10, a saturated aliphatic claw 70 oxy group substituted carbon number two group anthracene 6 to 2 fluorene aryl group, carbon number 7 201221520 〜 20 aralkyl group or a fluorenyl group having 2 to 10 carbon atoms; R85, R86, R87, R88, R89, R11Ga, Rllla and R11a each independently represent a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group having a carbon number of 1 to 1 Å, and a carbon number of 1 to a functionalized saturated aliphatic hydrocarbon group of 10, an alkoxy group having 1 to 8 carbon atoms, a carboxyl group, a sulfo group, an aminesulfonyl group or an N-substituted aminesulfonyl group; at least one of R85 to R89 and R11Qa to R112a Represents an N-substituted amine sulfonyl group; In the formula (VIII), R91, R92 and R93 each independently represent a hydrogen atom, a halogen atom or a rhein group; and A3 represents any one of the following (a) to (d); An integer of 1 or 2; when 1 is 2, the plural R91, the plural R92, and the plural R93 may each be the same or different; in the following (a), R94, R95 and R96 each independently represent a hydrogen atom, a group, a halogen atom, a sulfonic acid group or -S02N(R97)(R98), R97 and R98 each independently represent a hydrogen atom, a lower alkyl group having 1 to 8 carbon atoms or a phenyl group; and at least one of R91 to R96 represents a sulfonate. Acid base; -177- 201221520 (d) 2. The coloring composition for a color filter according to the first aspect of the invention, wherein the oxime compound is a compound represented by the following formula (IX): 〇 NR11aR12a\ General formula (5) In the formula (IX), the ruthenium 113 and 11123 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, but Rlla and R12a do not simultaneously represent a hydrogen atom; η 11 represents 1 to 4 An integer of NR11aR12a may be the same or different when η11 is an integer of 2 to 4. 3. The coloring composition for a color filter according to the second aspect of the invention, wherein the compound represented by the formula (IX) is a diamine sulfonium compound represented by the following formula (X): 8 - 178 - 201221520 In the formula (X), R21a and R22a each independently represent an alkyl group or an aryl group. 4. The coloring composition for a color filter according to the third aspect of the invention, wherein the compound represented by the formula (X) is a diamine fluorene compound represented by the following formula (XI): r^31a The formula (乂丨) each independently represents an alkyl group or a halogen atom; and R35a and R36a each independently represent an alkyl group, an alkoxy group, an aryloxy group, a sulfo group or a salt thereof, an aminosulfonyl group, an alkoxysulfonate.醯, or phenoxysulfonyl; η31 and η32 each independently represent an integer of 0 to 2, and when η31, η32 are 2, plural R35a, R36a may be the same or different -179-201221520 5 The coloring composition for a color light-emitting sheet of the fourth aspect of the invention, wherein the compound represented by the formula (XI) is awake by a diamine group represented by the following formula (XII) or the following formula (XIII) Compounds selected from the compounds: In the formula (XII), R41a, R42a, R43a and R44a each independently represent an alkyl group or a halogen atom; and R45a, R46a, R47a and R48a each independently represent an alkyl group, a sulfo group or a salt thereof, or an aminosulfonyl group. Any one of R45a and R47a and any of R46a and R48a represents a sulfo group or a salt thereof, or an amine-based continuation base; 8 -180- 201221520 In the formula (XIII), R51a, R52a, R53a and R54a each represent an alkyl group or a halogen atom; R55a and R56a are each an independent group or an alkyl group; and R57a and R58a each independently represent hydrogen; and each of L51a and L52a; The divalent linking group is independently represented, and each independently represents an oxygen atom or a -NH- group. 6. The color filter of the first aspect of the invention is further characterized in that it further contains a polymerizable compound and a photopolymerization initiator. The color filter of claim 1 is characterized in that the total content of the ruthenium compound is 50% by mass or less of the dye compound. 8. A color filter having: a substrate, and A colored region formed by the coloring composition of any one of the above claims 1 to 7. 9. A method of producing a color filter, comprising: independently representing a hydrogen atom or an alkyl group L53a L54a color composition, color composition, total amount of material used for color filter on a substrate -181 - 201221520 The color filter of any one of claims 1 to 7 is coated with a coloring composition On the support, forming The step of coloring the layer and the step of exposing the formed colored layer to a pattern to develop a colored region. A liquid crystal display device comprising the color light-emitting sheet of claim 8 of the patent application. 1 1. A liquid crystal display device comprising a color filter produced by the method for producing a color filter according to claim 9 of the patent application. 12. A type of enthalpy represented by the following formula (XIV) Compound: RX'1y^CH3 RX2 Ο ΗΐνΓ人, /, S02NH / General formula (XIV) w He X4 , X3 , Y Ο HN RX1 RX1 plus Liao 丄 so2nh ' ch3 CH I RX2 , RX3 In the formula (XIV), RX1 each independently represents a methyl group or an ethyl group; RX2 each independently represents an alkyl group having 1 to 10 carbon atoms; and RX3 each independently represents an alkyl group having 1 to 10 carbon atoms; Base; X4 each independently represents 0 or 1 - 182- 8 201221520 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None ° 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: