TW201213310A - Dyes and colored compositions - Google Patents

Abstract

The colored composition of the present invention comprises certain type of dye and solvent and optionally includes at least one species selected from the group consisting of a free resin, a polymerizable compound, and a polymerization initiator.

Description

201213310 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a dye and a colored composition comprising the dye and a solvent. • [Prior Art] As a color filter for color filters included in display devices such as liquid crystal display panels, electroluminescence, and plasma display panels, dyes have been used. As such a dye, for example, a compound of the formula (ΠΙ-2), C.I. Solvent Yellow 162 (Patent Document 1), and Oilfast Yellow 1151 (Patent Document 2) are known. NH-SO- ;Ό~'

HO Ν=Ν

HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为The solution obtained by the money may be precipitated by a dye if it is stored for a long period of time, and the storage stability may not be sufficient. The present invention provides the following [^~[ Π]-type dyes, which contain at least two compounds represented by formula (1), b2'n-!-I one-to-one (1) t! Ο 156704.doc 201213310 sarcophagus z z&l can be independently represented Substituents: the number is a divalent aliphatic nicotine group of the group 16, and the aliphatic hydrocarbon group may be substituted by -CO- or -0_; the R knife independently represents an atom and may have a substituent. Carbon number is ~16! The valence-saturated hydrocarbon group or the carbon group which may have a substituent is 2 to an anthracene group; and the A1 and A2 which may have a substituent having a carbon number of 6 to 14 each independently represent a divalent aromatic hydrocarbon group; and B and B2 are each independently And a 2-valent aromatic hydrocarbon group having a carbon number of (2)* or a carbon number of 3 to 14 which may have a substituent, and a -CH2- contained in the valent heterocyclic group It can also be via -(^-substitution). m such as the dye of (1) where B丨 and b2 each independently represent the group represented by formula (8),

Ο K-CN (II) [In the formula (II), R4 represents a hydrogen atom or a monovalent saturated hydrocarbon group which may have a substituent; R represents a carbon number which may have a substituent of 丨~i 6 I-valent saturated hydrocarbon group]. [3] The dye according to [1] or [2], wherein at least two of the compounds represented by the formula (1) are one or more compounds represented by the formula (I_A) and two or more formulas (1 B') a mixture obtained by reacting the indicated compound, BMl=N-Ai-|-lzi-ΟΗ α-Α) Χ1-§_,.1-4_Χ2 156704.doc -4- 201213310 [Formula (IA) and Formula (I_B) |] 'R〗, A〗, z丨, and L, which have the same meanings as described above; X1 and X2 each independently represent a halogen atom]. [4] A coloring composition comprising the dye according to any one of [1] to [3] and a solvent. [5] The coloring composition according to [4], which further comprises at least one selected from the group consisting of a resin, a polymerizable compound, and a polymerization initiator. [6] A color 泸 'light sheet formed using a coloring composition as in (4) or [5]. [7] A display device comprising a color calender as in [6]. [Embodiment] The dye of the present invention contains at least two compounds represented by the formula (1) (hereinafter sometimes referred to as "compound (I)"). B2-N=N-A2-SN-Z2_〇_§_,i_2 〇71 J1 ° ^〇c LC-〇-2i~NS-A1-N=N-B1 (I) Ο [山式(一)中Ζ 2 and 2 each independently represent an aliphatic hydrocarbon group which may have a substituent of 16 16 and an aliphatic hydrocarbon group which may be contained in the aliphatic hydrocarbon group by -CO- or substitution. R m independently represents a gas atom, a monovalent saturated nicotinyl group having a carbon number of 1 to 16 or a substituent having a carbon number of 2 to 18 which may have a substituent. Further, a divalent aromatic hydrocarbon group having a carbon number of 6 to 14 which may have a substituent is also independently indicated. B1 and B2 are independently 妯 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The ring group '-CH2_ contained in the heterocyclic group may also be substituted by -CO-]. The carbon number of the divalent aliphatic hydrocarbon group having a carbon number of 1 to 16 and not including z1, Z2 and L does not include the carbon number of the substituent, and the number is preferably 2 to 10, more preferably 2 to 8 Å. Examples of the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include a methylene group, an exoethyl group, an internal diyl group, a butyl group, a pentanediyl group, a hexamethylene group, a heptadienyl group, and a fluorene group. Alkanediyl having a carbon number of 1 to 16 such as a group, a tetradecanediyl group and a hexadecanediyl group; -ch2=ch2-, _ch2-c(=ch2)-, -(CH2)2-C(=CH2 ) · An alkene group having a carbon number of 1 to 16 or the like. The _cH2_ contained in the divalent aliphatic hydrocarbon group having a carbon number of 1 to 16 may also be substituted by _c〇- or -〇-, and the divalent aliphatic hydrocarbon group having a carbon number of 丨16 may also be subjected to _ #(四)^ Replace. As Z and Z2, it is preferred that -CH2 can also be substituted with -o-, the alkyl group having a carbon number of 18, more preferably {Η" or a carbon number of 〜? As a preferred group, -(CH2)3-, ·γΗ2)2_〇-(CH2)2·, i-(CH2)2_〇(CH2)2 〇 (ch仏 and Preferably, _ as L1' may also contain _C(=CH2)-, the carbon number of which is alkane-based, and more preferably an unsubstituted alkanediyl group having a carbon number of 1-8. More preferably, the unsubstituted carbon number is 4 to 8 alkanediyl groups. Preferred examples include -(TM2)", (CH2)44CH2_c(=ch2)_. The monovalent saturated hydrocarbon group of 1 to 16 may be any of a linear chain, a branched chain or a ring. The carbon number of the saturated hydrocarbon group does not include the inverse number of the substituent, and the number of the number of the substituent is 16, which is preferably More preferably, it is 1 to 4. 156704.doc 201213310 The monovalent saturated hydrocarbon group having a carbon number of 1 to 16 may, for example, be methyl, ethyl, n-propyl, isopropyl or n-butyl. Isobutyl, t-butyl, tert-butyl, methylbutyl (1,1,3,3-tetramethylbutyl, etc.), methylhexyl (1,5-di.methylhexyl) Equivalent), ethylhexyl (2-ethylhexyl, etc.), cyclopentyl, cyclohexyl, methylcyclohexyl (2-methylcyclohexyl, etc.), cyclohexylalkyl, etc. The hydrogen atom may be substituted by an alkoxy group having a carbon number of hydrazine or a carboxyl group. The aliphatic hydrocarbon group substituted by an alkoxy group having a carbon number of 8 may be exemplified by a propoxypropyl group (3 isopropyl group). An oxypropyl group or the like, an alkoxypropyl group (3-(2-ethylhexyloxy)propyl group, etc.), etc. As the saturated hydrocarbon group substituted by a carboxyl group, a 2-carboxyethyl group, 3 _carboxypropyl, 4-carboxyl, etc. The argon atom contained in the fluorenyl group having 2 to 18 carbon atoms of R1 and R2 may be substituted by a carboxyl group or an alkoxy group having a carbon number. The carbon number is counted by the number of carbon atoms of the substituent, and the number is preferably from 2 to 18, more preferably from 6 to 1 Torr. Examples of the fluorenyl group which may have a substituent include, for example, an ethyl fluorenyl group and a benzoic acid group. a mercapto group, a methoxybenzylidene group (p-methoxybenzylidene group, etc.), etc. As R1 and R2, a hydrogen atom, an alkyl group having a carbon number of 4 and a carbon number of 2 to 5 are preferable. It is better to hydrogen The atomic group, the f group, and the ethyl group. The divalent aromatic group having a carbon number of 6 to 14 which may have a substituent as shown in Tables A and A2 may be a phenyl group or a naphthalene group, and preferably a benzene group. The carbon number of the aromatic aromatic group does not include the carbon number of the substituent. Examples of the substituent which the aromatic hydrocarbon group may have include a tooth base, a carbon number of 1 to 8, and a carbon number. 1 to 8 of the oxy group, the exact group, the contiguous group, the amine stone yellow base and the N-substituted amine sulfonyl group, etc. I56704.doc 201213310 As a _ ke group, it can be exemplified: fluorine group, gas group, secret and 峨The base or the like is preferably a fluorine group, a gas group and a bromine group. Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a butyl group, an isobutyl group, a second butyl group, and a third butyl di-n-butylene. Preferably, the carbon number is 丨. The alkyl group of ~4, more preferably a methyl group and an ethyl group, is a methyl group. Examples of the alkoxy group having a carbon number of 1 to 8 include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, and a second butoxy group: a third group. The oxy group, the pentyloxy group, the hexyloxy group and the like are preferably an alkoxy group having a carbon number of 4, more preferably a methoxy group and an ethoxy group, and particularly preferably a methoxy group. As the substituted amine sulfonyl group, a _s〇2Nhr6-based h2Nr0r7 group can be mentioned. R6 and R7 are in the form of a saturated hydrocarbon group having a carbon number of a substituent or a fluorenyl group having a carbon number of 2 to 16 which may have a substituent. The sulfhydryl group having a carbon number of the substituent of 16 and a carbon number of 2 to 16 which may have a substituent may be the same as the above. And the monovalent aromatic hydrocarbon group having a carbon number of 6 to 14 which is represented by ruthenium and osmium 2 may be a naphthyl group or the like. The carbon number of the aromatic smog group does not include the carbon number of the substituent. The number of carbon atoms which may have a substituent in Β1 and Β2 is "the oxime heterocyclic group", and the group represented by the following formula may be mentioned.

[R represents a hydrogen atom or an organic group]. Examples of the organic group include the same group as R4 described below. 156704.doc 201213310 A monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms and a hydrogen contained in an iridium heterocyclic group having 3 to 14 carbon atoms. The atom may also be substituted with an aliphatic fumes/alcohol group, an amine group or an N-substituted amine group via a base or a slit. Further, the hydrogen atom of the above aromatic group 3 may be substituted with a pendant oxy group. The -CH2· contained in the above heterocyclic group may also be substituted by _co_. 9 is an N-substituted amine group, and examples thereof include a benzyl group and a _s〇2Nr8r9 group. Μ and R9 each independently represent a carbon atom which may have a substituent as a valent aliphatic hydrocarbon group or may have a substituent having a carbon number of 3 to 14 valence. The carbon number which may have a substituent is a valent aliphatic nicotyl group, and the carbon number which may have a substituent is 3 to 14iHf heterocyclic group, and the same as those exemplified as the above heterocyclic group. A B1 and B2 are preferably a group represented by the formula (Π). HO R4 (II)

R5 CN

In the formula (II), R4 represents a hydrogen atom or a monovalent saturated nicotinyl group having a carbon number of 1 to 16 which may have a substituent. R5 represents that the carbon number which may have a substituent is a valence saturated nicotine group]. Based on the formula (8). (4) The ketone ring may be of the _ type or a mother alcohol type. The money as a table is 1 to η and a hydrocarbon group, which may be the same as described above.乍 is & 疋 基 基 butyl (m3 tetramethyl butyl, etc.), methyl hexyl (1,5-di-hexyl, etc.) 'ethylhexyl (2-ethylhexyl, etc.), ^ base Cyclohexyl W-based cyclohexyl #), silk-propyl (3_(2•ethylhexyloxy I56704.doc 201213310) propyl, etc.), etc., branched-chain saturated hydrocarbon group β is preferably a fluorenyl group as R5. The compound represented by the formula (1_1) to the formula (118) is exemplified as the compound (I)'. In the table, A1, Α2, 汐 and , represent the binding bond β of the binding bond on the right side.

156704.doc • 10 - 201213310 [Table 3] 1-3 A1 z1 zl h3c RJ R0' R4 R4 -c4h9 -c4h9 —ch3 _ch3 R1 R2 L1 VH3 VH3 —(CH2)8 — 0 0 Z2 side Z1 side [Table 4 ] 1-4 A1 A" z1 Zz ch3 ch3 RJ RJ. R4 R4, -C4H9 -c4h9 —ch3 —ch3 R1 R2 L1 ——H —H —(CHJa—Z2 side Z1 side [Table 5] 1-5 A1 kL Z1 zl ch3 ch3 ch3 ch3 RJ RJ. R4 R4' -c4h9 -C4H9 —ch3 —ch3 R1 R" L1 —H —H —(CH2)4—z2 side z1 side 156704.doc -11 - 201213310 [Table 6] 1-6 A1 z1 Zz ch3 ♦ ch3 <lr ch3 ch3 RJ Ry r R4 xh3 xh3 —ch3 _ch3 R1 L1 —H —H —(CH2)8 — z2 side z1 side [Table 7] 1-7 A1 Az z1 τι Ch3 ch3 ch3 ch3 RJ Ry rr xh3 xh3 —ch3 _ch3 R1 R" L1 —H —H ——(CH2)4 — z2 side z1 side [Table 8] 1-8 A1 A" z* τι ch3 ch3 ch3 RJ RJ r xh3 ^V^^CH3 xh3 -c2h5 -c2h5 R1 R" L1 —H —H —(CH2)8—z2 side z1 side•12- 156704.doc 201213310 [Table 9] 1-9 A1 z1 zl ch3 ♦ ch3 ♦ ch3 ch3 RJ R3 R4 R4. r〇H3 0 ^ch3 o —ch3 —ch3 R1 R2 L1 —H —H —(ch2)4— z2 z1 side [Table 10]

1-10 A1 Az z1 zl ch3 Or ch3 4 ch3 ch3 RJ Ry R4 r .CH3 0 r〇H3 s·^^\^CH3 0 —CH3 —ch3 R1 R" L1 —H —H —(CH2)8— Z2 Side Z1 side [Table η] I-ll A1 A1 z1 Zz Let o- R11 Ru Rli RH —ch3 —ch3 —ch3 —ch3 Ri V —H —H —(0^2)2 — z2 side z1 side •13· 156704.doc 201213310 [Table 12] 1-12 A* Αζ Ζ1 ZL h3c h3c R11 R1' R1J R14 —^^och3 —^^~och3 -C4H9 -C4H9 R1 L1 —Η —Η ——(CH2)4— ζ2 Side ζ 1 side [Table 13] 1-13 A1 z1 ZL h3c Service H3CO Order R"R" Rlj R14 -Q-co2c2h5 -c3h7 -C4H9 R* L1 VHs 〇VCH3 0 —(CH2)8 — z2 side z1 side [Table 14] 1-14 A1 A2 z1 zl ch3 ch3 Good R" Ru R, J R14 —^^·〇〇η3 -^^·〇〇η3 -C4H9 -c4h9 R1 L1 丫ch3 0 丫ch3 0 ch2 Z2 side Z1 side -14- 156704.doc 201213310 [Table 15] 1-15 A1 z1 τι ch3 4 ch3 Ru R12 R1J R14 —^^~och3 -Q-OCH3 -C4H9 -c4h9 R1 L1 丫ch3 0 丫ch3 〇ch2 z2 side z1 side [Table 16]

N=N

—A2 —LLzLO-Uo—H -A1—Ν=Ν

1-16 A1 Az Z1 τι ch3 ch3 ----- ch3 R11 Ru Ru R14 ~^]^OCH3 -^^~och3 -c4h9 -C4H9 R1 Rz L1 —H —H —(CH2)8—Z2 side Z1 side [Table 17] 1-17 A1 z1 τι Cl Cl R1 R" Rn Rlb —H ——H —ch3 —ch3 L1 —(CH^ — z2 side z1 side -15- 156704.doc 201213310

—?—L1—ΰ—O—Z1-f!|—I—A1—N=N

HR17 R19HN

[Table 18] 1-18 A1 z1 ZL ch3 ch3 Rw R18 R,y R^u O) R1 Rz L1 —H —H —(CHja− Z2 side Z1 side-o- •A1—N==N /)— NHR21 - Hey!

HQ

HO •o—z1 ^=\ R22HN—))—N=N- Ν-Λ

OH

[Table 19]

1-19 A1 A" z1 zl ~〇- tone R1 R^1 Rzz —H —H —H —H L1 ——(CH^e — z2 side z1 side 16· 156704.doc 201213310 [Table 20]

Preferably, B1 and B2 are the base of the phase @--J, and it is more preferable that the Α丨 and A2, R1 and R2, Z1 and Zk 刖 ^ are the same skeleton base. The production of the compound (I) is easy. : at least two kinds of compounds (1) contained in the dye of the present invention, preferably 疋=containing two or more groups of the formula (1) selected from the group consisting of v, 八2, Ri, r2, ZZ and L a m compound of at least one compound having a different structure; more preferably a mixture of two or more compounds selected from the group consisting of at least one of the mutually different structures, and further More preferably, it is a mixture containing two or more compounds in which only L1 is a structure different from each other. 156704.doc 201213310 wherein, the compound represented by the formula (I_6) and the compound represented by the formula (IV) are preferably a mixture of the compound represented by the formula (IV) and the compound represented by the formula (IV). 〇: 9〇~89: ii, better 3 please ~70:30. When the content ratio is within the above range, the solubility in an organic solvent is excellent. The compound (I) can be obtained by a compound represented by the formula (Ι·Α) and a compound represented by the formula (Ι-A,) and a compound represented by the formula (Ι_Β) in a solvent at 〇~150°c. Manufactured by reaction. R1 〇 H~°-*Zi-^~f-A1-N=N-B1 d-A) Ο R2 Ο N Guide A N ·Ν— B2 (Bu A,)

O (rB) 〇〇R31-CU-(!i-R32 [in the formula (IA), the formula (I_A·), and the formula (I_B), z, z2, z3, r1, r2, A, and B2 are represented by the above The same meaning and R knife independently represent _〇r33 or a halogen atom. r33 represents a monovalent aliphatic hydrocarbon group having a carbon number of 1 to 16.] R 1 and R 32 are preferably a halogen atom, more preferably a gas. The compound represented by the formula (IB) can be exemplified by dimethyl malonate, isobutyl butyrate, dimethyl adipate and diethyl suberate, and propylene dioxime ' T - , dioxin, hexamethylene chloride, octane oxime, bismuth oxime, etc. Relative to the compound represented by formula (Ι-A) and formula (Ι·Αι) 1 Moer, the amount of compound represented by the formula (Ι-Β) is better than that of 〇5~3 莫's better 〇·5~1 莫耳. Further, in solvent I56704. Doc •18- 201213310 In the case of water, the use of the compound represented by formula (IV) is relative to the total amount of the compound represented by formula (IV) and the compound represented by formula (ί_ Α '). The amount is preferably 06 to 3 moles. When the compound represented by the formula (Ι-Β) has a ratio of r31 and r32 of seven, it is preferred to add a known acid catalyst. Examples of the acid catalyst include sulfuric acid and p-toluene continuous feeding. (4) In terms of the total amount of the compound represented by the formula (I, the wall surface k compound and the compound represented by the formula (1_A'), the acid catalyst is preferably used in an amount of 0.01 to 2 mol. Formula (I_A) The reaction between the compound represented by the compound and the compound represented by the formula (i_a.) and the compound represented by the formula (IV) is carried out in a solvent. As the solvent, for example, water '·i, di-D-burning, etc. are preferred. (especially ring-shaped); chloroform, methylene chloride, carbon tetrachloride, dichloroethane, dichloroethylene, trichloroethylene, perchloroethylene, dichloropropane, chloropentene, In the second desert = hospital, etc.; (4), methyl isobutyl ketone, cyclohexanone and other steroids: carbon, aromatics such as benzene, f benzene, xylene; N, N_: methylformamidine Alkyl amide such as amine, N,N-dibutylformamide, N,N-dimethylacetamide or N-methyl- dydenone, or two or more solvents may be used in combination. The compound represented by the formula and the total amount of the compound represented by the formula (Ι_Α,)] The mass of the solvent is preferably a difenium mass fraction, more preferably 2 to 10 parts by mass. Type (Ι-A) The reaction between the compound represented by the compound and the compound represented by the formula (Ι_Α,) and the compound represented by the formula (Ι-Β) may be carried out in air dried by using calcium chloride or the like, but is preferably Under nitrogen or argon gas production., Yixiong 156704.doc •19·201213310 The reaction temperature is preferably 0~〗 5Gt, more preferably] G~i3 (rc. The reaction time is preferably 1 ～25小时, more preferably 3 to 15 hours. The compound represented by the formula (1-8), the compound represented by the formula (Μ), and the order of addition of the compound represented by the formula (IV) are not particularly limited, but are preferably. The compound represented by the knee B) is added (dropwise) to a solution containing the compound represented by the formula (IV) and the solvent represented by the formula (IV). In the case of using an acid catalyst, it is preferred. The compound represented by the formula (I_B) is added (dropwise) to a solution containing a compound represented by the formula (IV), a compound represented by the formula (I_A.), an acid catalyst, and a solvent. The compound obtained as a target compound is obtained in the obtained reaction mixture (1) The method is not particularly limited, and various known methods can be employed. For example, the reaction mixture can be purified by extraction with an organic solvent, and the reaction mixture, the organic solvent and water are mixed to dissolve the compound (1) into the organic phase. Analyze 'and use the solvent separation funnel to separate the solvent to remove the compound' to obtain the compound (1). The extraction temperature is preferably 10~50C, more preferably 20~3 (rc. Preferably, the mixture is mixed with G. 5 to 4 hours. The extracted compound (1) can be washed with an aqueous water solution, an acidic aqueous solution, etc., and then dried. Further, it can be visually recrystallized. Further purification is carried out by a known method. As the aqueous test solution, a known test substance can be used by dissolving it in water. The range of the hydrogen ion concentration of the alkaline aqueous solution is preferably 〜12, ® jj. 0 ^ More preferably 9 to 11. The basic substance is not particularly limited, and examples thereof include sodium carbonate, potassium carbonate, sodium acetate, sodium oxysulfide, potassium hydroxide, hydroxide, and ammonia. 156704.doc -20· 201213310 As the acidic water-soluble I solution, it is possible to use a known acid substance dissolved in water. The range of the hydrogen ion concentration of the acidic aqueous solution is preferably from pH 〇 to 6 ′, more preferably from 1 to 5. The acidic substance is not particularly limited, and examples thereof include ammonium chloride, oxalic acid, acetic acid, hydrochloric acid, and sulfuric acid. The dye of the present invention is preferably a mixture obtained by reacting one or more compounds represented by the formula (J_A) with two or more compounds represented by the formula (I_B), and more preferably A mixture obtained by mixing the compound represented by (I_A) with two or more compounds represented by the formula (IB). 11~ν==ν''α1-|-ν-ζ1-〇η α-Α) xU_x2 α.Β>) [Formula (Ι-Α) and formula (Ι_Β,) in 'R1, Αι, ζ! And L丨 indicate the same meaning as above. X and X each independently represent a halogen atom]. Examples of the compound represented by the formula (I-B') include a propylene dioxane gas, a dimethyl dioxane gas, a dioxinsium gas, a octanedioxane chloride, and a fluorene dioxane gas. Examples of the combination of the compounds represented by the two or more formulas (I_B,) include: propylene dioxime and hexamethylene chloride, butyl dioxane and hexanthene, butyl dichloride, and dioxin. The second (four) and bismuth chlorinated dichloride, hexamethylene oxime and octane oxime chlorine, hexamethylene oxime and ruthenium dichloride, etc., are preferably dioxane and ruthenium dioxide. ^, a total amount of the compound represented by the formula (I_B,) of two or more formulas (I_B,) is preferably 0.5 to 3, based on the total amount of the compound represented by the formula (Ι_Α). Moor, better is oh Moer. Furthermore, in the case of solvent 156704.doc •21· 201213310 When it contains water, it is relative to! In the case of the above-mentioned formula (ia), the total amount of the substance is 1 or more, and the total amount of the substance is preferably 0.6 to 3 moles. . The reaction of a compound represented by one or more formulas (Ι-A) with two or more compounds represented by the formula (^) is carried out in a solvent. As the solvent, the same as described above can be cited. The amount of the solvent used is preferably a U mass part, more preferably 2 to 10 parts by mass, based on the total mass parts i of the compound represented by the above formula (i_a). The reaction of a compound represented by the above formula (1) A) with two or more kinds of compounds represented by the cutting of B,) can also be carried out in air dried by gasification or the like, but preferably nitrogen. It is carried out under the environment or in a chlorine atmosphere. The reaction temperature is preferably 〇, and more preferably (d). The time is preferably 25 hours, more preferably 3 to 15 hours. '····················· Two or more compounds represented by the formula (I_B.) are added (dropwise) to the solution of the compound and the solvent. The method of obtaining the dye of the present invention from the reaction mixture obtained in the above manner is not particularly limited, and various known methods can be employed. For example, the dye of the present invention is purified by extraction with an organic solvent, and the reaction mixture, the organic solvent and water are mixed to dissolve the machine phase of the present invention, and it is separated by a separatory funnel or the like. The organic phase is subjected to solvent distillation, and the dye of the present invention is purified by the stomach. It is preferred to stir the organic phase to 156704.doc -22·201213310 at preferably 10 to 5 (TC, more preferably 20 to 30 ° C for about 5 hours). The purified invention after extraction The dye may be washed with a hydrazine aqueous solution, an acidic aqueous solution, or the like, and then dried. Further purification may be carried out by a known method such as recrystallization as needed. 'As the above alkaline aqueous solution, a known basic substance can be used. The range of the hydrogen ion concentration of the alkaline aqueous solution is preferably P(tetra) to 12, more preferably 9 to U. As the basic substance f, there is no particular limitation: for example, carbonic acid Sodium, potassium carbonate, sodium acetate, sodium argon oxide, potassium oxyhydroxide, oxyhydrin, ammonia, etc. As the above acidic aqueous solution, it is possible to make a known acid to be the same. The range of the hydrogen ion concentration of the acidic aqueous solution is higher. Preferably, the compound is not limited, and examples thereof include ammonium chloride, oxalic acid, acetic acid, hydrochloric acid, sulfuric acid, etc. ^Compound (1) can be obtained by formula (4) a compound represented by the formula (1) and a formula (1, The compound shown is subjected to coupling reaction: and can be produced, for example, in an aqueous solvent under 2Q to thief to produce a compound (1). ΝΞΝ- ® H-B1 ο 〇-Ζ1-Λ-| _Αι^νΞΝ χ- (I_C) Ο

(ID Η-β2 (Bu D,) U(2I-C) and (I_D), z1, z2, U, r1, r2, a1, a2, b, and β2 represent the same meaning as described above. I56704.doc •23·201213310 χ indicates an inorganic anion or an organic anion. As the above inorganic anion or right oxime to the secondary organic cation, it can be expected: fluoride ion, chloride ion, chasing f- 4^1 13⁄4& 7 , on the shoulder Compound ions, mothium ions, peroxy acid ions, hypo-acid ions, ch3-coct, Ph_eo «-& *, L〇〇4, preferably exemplified by vapor ions, bromide ions, ch3- Coo, the dye of the present invention exhibits high solubility and high spectroscopic concentration, and thus can be used in a fiber material, a liquid crystal display device or the like which performs color display by using reflected light or transmitted light. Further, the dye of the present invention is tested. The absorption spectrum has a maximum absorption in a wavelength band of 400 to 450 nm, and thus is preferably used as a yellow dye. It is preferred that the coloring composition of the present invention contains a coloring agent containing the dye of the present invention (hereinafter sometimes referred to as "Colorant (A)") and solvent, further including resin (B), polymerizability The compound (C) and the polymerization initiator (D). The coloring agent (A) may further contain a dye and/or a pigment (A_2) different from the compound (I), in addition to the compound (1). A dye different from the compound (I) can be exemplified by the Colour Index (published by The Society of Dyers and Colourists) as 'Solvent, Sol, Basic, Reactive. , Direct, Disperse, or Vat compound, etc. More specifically, the following dye index (CI) number dyes are mentioned, but it is not limited to these. CI Solvent Yellow 25 , 79, 81, 82, 83, 89; CI acid yellow 7, 23, 25, 42, 65, 76; CI · reaction yellow 2, 76, 116; 156704.doc -24 · 201213310 CI direct yellow 4 ' 28, 44, 86, 132; CI disperse yellow 54, 76; CI solvent orange 41, 54 '56, 99; CI acid orange 56, 74, 95, 108, 149, 162; CI reaction orange 16; CI direct orange 26; CI Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218; CI Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289; CI acid violet i〇2; CI solvent blue 35, 37, 38, 44, 59, 64, 67, 70; CI acid blue 40, 45, 78, 8〇, 83, 9〇, 1〇〇, i7i, i85 CI confirmatory blue 65, 140; CI reaction blue 15, 38; C.1. Disperse blue 143; CI direct blue 86, 87; C · I. Solvent Green 1, 5; CI Acid Green 3, 5, 9, 25, 28; CI Alkaline Green 1; C-Ι. Reduction Green 1; C. I · ® 黑 Black 5 8 , 60 1 〇7; ci solvent black 27 and so on. * The corpse sentence Yanbei uses the right 嫱 New W + ; The organic pigments and inorganic pigments commonly used in the dispersal anti-money agent are usually θ..., machine yan, which can be listed as gold 156704.doc -25- 201213310 Specific examples of the metal compound such as an oxide or a metal-substituted salt include a metal oxide or a composite metal oxide such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc or cerium. Further, examples of the organic pigment and the inorganic pigment include those classified as Pigment in the Colour Index (published by The Society of Dyers and Colourists). More specifically, the following dye index (C.I.) number of pigments may be mentioned, but it is not limited thereto. CI·Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 1〇9, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173 and 180; CI pigments dial 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71; CI pigment red 9 '97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264; CI Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38; CI Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64, and 76; CI Pigment Green 7, 10, 15, 25, 36, and 47; CI·Pigment Brown 28; C.1 - Pigment Black 1 and 7, etc. The content of the colorant (A) is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and still more preferably the solid content of the coloring composition. It is 10 to 50 mass ° / 〇. Here, the solid content component means the total of the components other than the solvent in the coloring group 156704.doc • 26·201213310. In the case where the colorant (4) further contains a dye and/or a pigment different from the compound (1), the total amount of at least two of the sigma (I) groups is liberalized with respect to the colorant (VIII) of 3 to 80% by mass. The content is preferably from 3 to 5% by mass, more preferably from 3 to 5% by mass. With respect to the toner (4), the content of the pigment (Α·2) is preferably 20 to 97 〇 = the amount % 'more preferably 3 〇 to 97% by mass, and even more preferably 5 〇 Μ Μ Preferably, the colored composition of the present invention comprises a resin (8). The resin (8)' is not particularly limited to $, but is preferably a soluble resin, and the soluble resin contains a structural unit derived from (meth)propionic acid. Here, (meth)acrylic acid means acrylic acid and/or mercaptoacrylic acid. Examples of the resin (Β) include a copolymer of [Κ1] to [Κ4]. [Κ1] a monomer (a) having a cyclic ether having 2 to 4 carbon atoms (hereinafter sometimes referred to as (a) j ) and at least 1 selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides The copolymer of (b) (hereinafter sometimes referred to as "(8)"). [K2] (4) and (b) and a monomer (c) copolymerizable with (4) (but different from (4) and (8)) (hereinafter sometimes referred to as "(〇") copolymer. [K3] (b) and ( Copolymer of c) [K4] A resin obtained by reacting the copolymer of (b) and (c) with (a). The resin (B) is preferably a resin comprising a structural unit derived from (4). Since the resin (B) contains the structural unit derived from (a), the reliability of heat resistance, chemical resistance, and the like of the obtained coloring pattern can be further improved. (a) For example, it means a ring having a carbon number of 2 to 4. An ether (for example, selected from the group consisting of Ethylene B. 156704.doc • 27-201213310 alkane ring, propylene oxide ring, and IV.E, Fengtiannan 5 coat (butylene oxide ring): >, One type) is a polymerizable compound having a polymerizable group in addition to a cyclic ether. (a) It is preferred to have a cyclic ether having a carbon number of 24 and a double bond of an ethylenic carbon-carbon bond. More preferably, the right octagonal monomer has a cyclic ether having a carbon number of 2 to 4 and a (meth) acryloxy group. Further, in the present specification, the term "(meth)acrylic acid" is Indicated from acrylic acid and methacrylic acid The expressions of at least "(meth) thin base" and "(mercapto) acrylate vinegar" of the group have the same meaning. (a) For example, a single one having an epoxy group (4)) (hereinafter referred to as (a1)"), a monomer having an oxypropylene group (a2) (hereinafter referred to as (a2)"), a monomer having a tetrahydrofuranyl group (4)) ( Hereinafter, it is sometimes referred to as "(a3)"). The monomer (al) having an oxirane group is a polymerizable compound having an oxirane group and a polymerizable group other than the ethylene oxide. (4)) A monomer having a structure in which a epoxidation of a woman is oxidized (hereinafter referred to as "(al-Ι)")), and a structure having a structure in which a cycloolefin is epoxidized Body (al-2) (hereinafter sometimes referred to as "(al 2)"). As (al), a monomer having an oxirane group and an ethylenic carbon-carbon double bond is preferred, and a monomer having an oxirane group and a (fluorenyl) propylene fluorenyloxy group is more preferred. Examples of (al-Ι)' include: (fluorenyl) glycidyl acrylate, (fluorenyl) β-f-glycidyl acrylate, β-ethyl glycidyl (meth) acrylate, glycidyl vinyl ether , o-vinylbenzyl glycidyl ether, m- 156704.doc • 28 - 201213310 alkenyl-based glycidyl ether, vinyl-glycidyl glycidyl ether, α-methyl-o-vinyl-based glycidyl α·?-yl-m-vinylphenol glycidyl ether, (X-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidoxyfluorenyl)styrene, 2,4-double (glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tri (glycidoxymethyl)styrene, 2.3.5-bis(glycidoxymethyl)styrene, 2,3,6 tris(glycidoxyfluorenyl)styrene, 3,4,5- Tris(glycidoxymethyl)styrene, 2.4.6-tris(glycidoxymethyl)styrene, etc. As (al-2), for example, vinylcyclohexene monooxide , 丨, 2_ epoxy-4-vinylcyclohexane (for example, Ce丨i〇xide 2〇〇〇; manufactured by Daicel Chemical Industries, Inc.), (mercapto)acrylic acid _ 3,4-epoxycyclohexyl Ester (for example, CyCi〇mer A400; manufactured by Daicel Chemical Industries Co., Ltd.) '(Meth)acrylic acid_3,4_epoxycyclohexyl ruthenium (for example, Cyclomer M100; manufactured by Daicel Chemical Industries Co., Ltd.), formula ( a compound represented by BU) and a compound represented by the formula (B1_2).

In the formulae (B1-1) and (B1-2), Ra and Rb each independently represent a hydrogen atom or an alkyl group having a carbon number of 1 to 4, and a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. . X and X independently of each other represent a single bond, * - Rc-S-, 156704.doc -29-201213310 *-Rc-NH-.

Re represents an alkanediyl group having a carbon number of 1 to 6. * indicates the bond with 〇]. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl 'n-butyl group, a second butyl group, and a third butyl group. Examples of the hydroxyalkyl group include a hydroxymethyl group, a hydrazine-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and a hydrazine-hydroxyl-1-yl group. Ethyl, 2-ylpyridylethyl, fluorenyl-butylidene, 2-hydrylbutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like. R1 and R2 are preferably a hydrogen atom, a mercapto group, a hydroxyindenyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a mercapto group. The alkanediyl group may, for example, be a methylene group, an ethylidene group, a propylenediyl group, a butyldiyl group, a pentanediyl group or a hexamethylene group. Preferred examples of X1 and X2' are: a single bond, a methylene group, an ethylidene group, a *-CH2-indole- (* represents a bond to a bond of 0), and a *_CH2CH2_fluorenyl group, and more preferably, Single button, *_CH2CH2-Oj. The compound represented by the formula (B1-1) may, for example, be a compound represented by the formula (B1-1-15), and preferably a formula (B1_M), a formula (B1-1-3), or a formula. (Bl-1-5), a compound represented by formula (B1-1-7), formula (B1-1-9), formula (B1-1-11) to formula (B1-i-15), more preferably The compounds represented by the formula (B1-1), the formula (B1-1-7), the formula (B1-1-9) or the formula (B1-1-15) are listed. 156704.doc •30_ 201213310

Ο II

HjC =CH~C~*Ο HjC =CH -C —O —CH2 Η2〇=ΟΗ*Ό—〇—〇2η4 H2C=CH*'C—Ο—C2H4-O CH3〇H2〇=C—co ch3 o Η2〇=〇·—C—〇—CH ?h3o I II H2C=C—C — 0—〇2H4

(Bl-1-7) H2j CHjOH 〇 (Bl-l-U) H2c=H〇 -O (Β1-1-Π) »c=c

o II

H2C=CH-C—0—C2h4 H2C=CH-C *~〇—〇2H4 - CH30 *C-〇~C2H4-S CH30 I 11 u H2C=C-C-〇-c2H4-|i c2H5o . 丄 II —Q

9H3 ο u ^ I η. 2. —C C~O—C2H4^〇

C2H4OH O I 11 H^C—C—C—〇

-O (B1-1-15) The compound represented by the formula (B1-2) may, for example, be a compound represented by the formula (B1-2-1) to (B1-2-15), and is preferably listed. Formula (b1_2, 〇 (B1-2-3), (B1-2-5), (B 2:7), (B1_2-9), (B1-2-11)~ The compound represented by B1-2-15) is more preferably represented by the formula (B1-2-1), the formula (Bb2-7), the formula (B1-2-9) or the formula (B1-2_15). Compound 156704.doc -31 - 201213310 ο ϊ H2C=CH-C-〇

(B1 2-1) HjC^HCOC^-s Field^2-3) SH \ H2C=CH-C-〇-C2H4-K •o ιι H2C=CH-b—Ο—CHj Ο II II H2C =CH - 0 — 〇—(^Η4 (Bl-2-5) H2C =CH -c -o ~C2H4~〇

CH3〇 (Bl-2-15)

(Bl-2-8)

H2C=C-C-O-C2H4-S

CH2OH 〇 H2O o c —〇 H2〇=C C2H4OH 0 II —C-0 H2C =C —C-〇-. Outside _〇

The compound represented by the formula (8) and the formula (B1_2) are each used alone. Moreover, these can also be mixed at any ratio. In the case of mixing, the mixing ratio is expressed by the formula (Β1·1): the molar ratio of the formula (B1_2) is preferably 5:95 to 95:5. More preferably, 1〇: 9〇~9〇: 1〇, and even more preferably 20:80~80:20. = monomer having a propylene-acrylic group (IV) means a polymerizable compound having a polymerizable group of a epoxidized propylene-based material Τ'. Preferred oxime has an epoxy propylene group and an ethylene carbon-carbon double bond. The monomer 'better is propylene oxide group and (body. Qing)' can be cited as: ... methyl propyl core; Li 156704.doc • 32· 201213310 oxypropyl, 3-methyl-3-propene oxime Oxymethyl methacrylate, 3-ethyl 1-methylpropenyloxymethyl epoxy, 3-ethyl-3-methyl propylene oxide, 3-methyl- 3-methylpropenyloxyethyl propylene oxide, % mercapto-3-propanyloxyethyl epoxide, 3_ethyl_3_methylpropoxy Ethyl Epoxy Propylene, 3-ethyl·3_acryloxyethyl epoxide, etc. The monomer (a3) having a tetrahydrofuran group means a polymerizable compound having a tetrahydrofuranyl group and a polymerizable group other than the tetrahydrofuranyl group. Preferred as (a3)' is a monomer having a tetrahydrofuranyl group and an ethylenic carbon-carbon double bond, and more preferably a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group. Specific examples of (a3) include tetrahydrofurfuryl acrylate (for example, Viscoat V#15®, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and mercaptopropionate tetrahydrofurfuryl ester. (a) is preferably (al) in terms of improving the reliability of heat resistance and chemical resistance of the obtained color pattern. Further, in terms of excellent storage stability of the coloring composition, it is more preferable (a). Specific examples of (b) 'specifically' include unsaturated monooleic acids such as acrylic acid, methacrylic acid, crotonic acid, o-ethylenebenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-ethyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrogen Unsaturated dicarboxylic acids such as phthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimercaptotetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; 156704.doc -33- 201213310 Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hepta-2 _ene, 5-carboxyl_5•methylbicyclo[2.2.1]hept-2-ene, 5-carboxyethylbicyclo[2 2hept-2-ene, hydroxycarboxy-6-roylbicyclo[2.2.1 a bicyclic unsaturated compound containing a carboxyl group such as hept-2-ene, 5-carboxy-6-ethylbicyclo[221]hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3·vinyl Phthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyl Anhydrous carboxylic acid such as tetrahydrophthalic anhydride or 5'6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (bicycloheptene dicarboxylic anhydride); succinic acid mono[2] - (fluorenyl) propylene methoxyethyl] ester, phthalic acid mono [2-(methyl) propylene oxyethyl] ester and other unsaturated carboxylic acids of 2 or more polyhydric carboxylic acids [(曱Alkyl acryloxyalkyl] ester; an unsaturated acrylic acid such as α-(hydroxyindenic)acrylic acid having a hydroxyl group and a carboxyl group in the same molecule. Among the β-Xuanzhu, 'acrylic acid, methacrylic acid, maleic anhydride and the like are preferable in terms of the aspect of the copolymerization reactivity or the solubility in the alkaline aqueous solution. Examples of (c)' include, for example, (fluorenyl) decyl acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, and (meth) acrylate. Tributyl acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, lauryl (meth) acrylate, stearyl methacrylate , (fluorenyl) cyclopentyl acrylate, cyclohexyl (meth) acrylate, 2-mercaptocyclohexyl (meth) acrylate, tricyclo 156704.doc • 34 · 201213310 [5· 2·1·〇'癸_8_yl ester (referred to as (meth)acrylic acid in the technical field as a customary name), dicyclopentyloxyethyl (meth)acrylate, ( A soil) g-iso-isobornyl ester, (p-) propylene glycolate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, (f-) naphthyl acrylate, (meth) acrylate such as benzyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, (meth) propyl Hydroxy (meth) acrylates such as 2-hydroxypropyl acrylate; maleic acid monoethyl ketone, diethyl fumarate, itaconic acid, diethyl vinegar, etc.; 2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2_2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2- Alkene, 5-hydroxyindenylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2. 1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxyl Methyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2.-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[ 2.2.1] hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-fluorenylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.丨]heptyl-2-ene, 5-hydroxyindolyl-5-fluorenylbicyclo[2.2.1]hept-2-ene, 5-t-butoxycarbonyl Bicyclo[2_2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2·2·1]hept-2-ene, 5-phenyloxycarbonylbicyclo[2.2.1]hept-2-ene , 5,6-bis(t-butoxycarbonyl)bicyclo[2 2 1;1hept-2-ene,5 , 6-bis(cyclohexyloxy)-bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds, 156704.doc -35· 201213310 N-phenylmaleimide, N-ring Hexylmalanimine, N-membered maleimide, N-butylenedimino-3-maleimide benzoate, N-butanediamine-4-mer醯iminobutyrate, N-butylenediamine-6-maleimide caproate, N-butylenediamine-3-maleimide propionate, N- (9-Acridine) Dicarboxyimine derivatives such as maleimide; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxy Styrene, acrylonitrile, mercaptopropyl nitrile, ethylene ethylene, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2, 3-dimercapto_ι,3-butadiene, and the like. Among these, in terms of copolymerization reactivity and heat resistance, preferred are styrene, fluorene-benzo-maleimide, Ν_cyclohexylmaleimide, Ν_^ jima 醯Imine, bicyclo [2.2.1] hept-2-ene, and the like. It is preferred that in the resin [Κ1], the ratio of the structural unit derived from each compound is in the following range among all the structural units constituting the resin [Κ1]. Structure derived from (a) single το : 6〇~98 mol% (more preferably 65~95 mol%) From (b) structural unit: 2~4〇mole% (better is 5~35 Moer

Toward 0

156704.doc -36 - 201213310 Specifically, a method is exemplified in which a specific amount of (a) and (b), a polymerization initiator, a solvent, and the like are charged into a reaction vessel to replace oxygen with nitrogen, thereby deoxidizing Under the sputum: mixing, heating, and insulation methods. Further, the polymerization initiator, the solvent and the like used herein are not particularly limited, and can be used in any of the usual users in the field of S. For example, examples of the polymerization initiator include an azo compound (2,2·-azobisisobutyronitrile, 2,2,-azobis(2,4-dimercaptophthalonitrile), etc.) or organic The peroxide (such as benzoquinone) may be used as a solvent to dissolve each monomer. As the solvent of the photosensitive resin composition, the following solvents and the like may be used. Further, the obtained copolymer may be directly used as a solution after the reaction, or a solution which is concentrated or diluted, or a solid (powder) may be used by a method such as reprecipitation. In particular, as the solvent in the polymerization, the reaction solution can be used as it is by using the solvent (D) described below, whereby the production steps can be simplified. It is preferred that in the resin [K2], the ratio of the structural units derived from the respective compounds is in the following range among all the structural units constituting the resin [K2]. From the structural unit of (a) · 2 to 95 mol% (more preferably 5 to 8 〇 Mo Er 0 / 〇) From the structural unit of (b): 2 to 40 mol% (better It is 5 to 35 moles/〇). The structural unit derived from (c): 1 to 65 mol% (more preferably, the ratio of the structural unit of the moor resin [K2] is within the above range, The storage stability, the developability, the solvent resistance of the hardening pattern, the heat resistance, and the mechanical strength tend to be improved. The resin [K2] can be produced, for example, in the same manner as the method described in the production method of the resin [Kl]. Doc •37-201213310 Specifically, the following methods can be used: a specific amount of (4), (b) and (4), a polymerization initiator and a solvent are added to a reaction vessel, and oxygen is replaced with nitrogen to carry out mixing and heating under deoxidation. The method of the heat preservation may be carried out by directly using the solution after the reaction, or by using a concentrated or diluted solution, and may also be taken out as a solid (powder) by a method such as reprecipitation. It is preferred that in the resin [K3], the ratio of the structural units derived from the respective compounds is constituted. All structural units of the fat _ are in the following range: (b) 2 to 40 mol%, more preferably 5 to 35 mol% (c) 60 to 98 mol%, more preferably 65 to 95 m The square resin [K3] described in the method for producing the ear % can be produced, for example, in the same manner as the resin [κ] method. The resin [Κ4] can be obtained by the following methods: obtaining the (9) and (4) urethane, and (4) The method of the above-mentioned method of producing a mixture of (b) and (4) is carried out in the same manner as the method described in the production method of [K1]. In the case, it is preferred that (4) of the structural units derived from the respective compounds are in the following ranges in all the structural units of the copolymers of the structures (10) and (4). (b) 5 to 50 moles, more preferably 1 to 45 moles Ο) 50 to 95 moles. /. More preferably, it is a group derived from (c) of the above copolymer and/or a part of the carboxylic anhydride and the carbon of (4) in the above copolymer of 55 to 9 〇 〇 〇 〇 〇 二The number is 2~4: Reaction 衣 156704.doc -38- 201213310 After the manufacture of the copolymer of dust (b) and (4), the gas atmosphere in the flask is replaced by air gas into air' and loaded into the flask: (4), relative to the combination of (4) ~ (4). The total amount of the reaction catalyst (for example, tris(diamine)methylphenol), etc., and the total amount of (4) to (c), which is 0. GG 1 5 minus 5%, is 0.001. 5 mass% of a polymerization inhibitor (for example, hydroquinone or the like), for example, is reacted at 6 to 130 ° C for 1 to 10 hours, whereby a resin [Kg can be obtained. The reaction conditions such as the charging method, the reaction temperature, and the time can be appropriately adjusted in consideration of the amount of heat generated by the production equipment or polymerization. Further, similarly to the polymerization conditions, the amount of heat generated by the production equipment or polymerization can be considered, and the addition method or the reaction temperature can be appropriately adjusted. In this case, the amount of use of (a) is preferably 5 to 80 mol%, more preferably 10 to 75 mol%, and even more preferably 15 to 7 mol%, relative to (b). ear%. When the ratio is in this range, the balance between storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity is improved. 0 The resin (B) 'specifically: (fluorenyl) Acrylic acid _3,4_epoxycyclohexyl decyl ester / (meth) acrylic acid copolymer, acrylic acid _3, 4 epoxide tricyclo [5.2 · 1 · 02 '6] oxime ester / (fluorenyl) Acrylic copolymer and other resins [K1]; (fluorenyl) glycidyl acrylate / benzyl (meth) acrylate / (meth) acrylate copolymer, glycidyl (meth) acrylate / styrene / (fluorenyl) Acrylic acid copolymer, 3,4-epoxytricyclo[m.o2,6]nonyl acrylate/(meth)acrylic acid/fluorene-cyclohexylmaleimide copolymer, 3-mercapto-3- Resin such as (meth) propylene methoxymethyl propylene oxide / (meth) acrylate / styrene copolymer [K2]; benzyl (meth) acrylate / (meth) acrylate copolymer, styrene / ( Methyl) propylene 156704.doc -39- 201213310 Resin such as acid copolymer [Κ3]; (meth) benzyl acrylate / (fluorenyl) acrylate copolymer addition (f-based) glycidyl acrylate resin , Yin Ji) A resin made of trimethyl decyl acrylate/styrene/(fluorenyl) acrylate copolymer with (meth) methacrylate, (tri) decyl (meth) acrylate / (meth) acrylate A resin such as a resin obtained by adding a (sub)acrylic acid glycidyl ester to a benzyl ester/(f-)acrylic acid copolymer [K4]. Among them, preferred are resin [Κ1] and resin [Κ2], more preferably resin [Κ1], and more preferably acrylic 3,4_epoxytricyclo[5 21 〇2,6]decyl ester. /(Mercapto)acrylic copolymer. The polystyrene-equivalent weight average molecular weight of the resin (Β) is preferably 5,000 to 35,000, more preferably 6 〇〇〇 to 3 〇 〇〇〇, and still more preferably 7^0 (9) to 28, 嶋. When the molecular weight is in the above range of 0, the hardness of the coating film is increased, the residual film ratio is also improved, the solubility of the unexposed portion to the developer is good, and the resolution tends to be improved. Ία 疋 W fat (ϋ) acid value is more than - eight than 叼疋 ο υ ~ 1 _35, into: better is 70 ~ 135. Here, the acid value and the value measured by the oxidation of the medium W § resin (8) = oxidation (four) (mg) can be determined, for example, by titration using a potassium hydroxide aqueous solution. Compared with =7 with two things: the shape of the object into the "word" tree _ the content of the quality. / 0, more preferably 丨 3 ~ 6 enamel is 17 ~ 55 皙 。. / from + negative ' and then better The content of the right resin (B) is in the above-mentioned manner, and the tendency of the image and residual film rate of the 珉 珉 案 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The human ochre composition contains a polymerizable person polymerizable compound (C) if it is a chemistry port #(c). It can be used as a living initiator (9) by irradiation light. 156704.doc 201213310 f active active radical, acid The compound to be polymerized is not particularly limited, and examples thereof include a compound having a polymerizable carbon-carbon unsaturated bond. The polymerizable compound (c) is preferably a compound having three or more polymerizable groups. More preferably, it is a s material having three or more (meth) propylene oxime groups. Examples of the polymerizable compound (c) include pentaerythritol tetraacrylate, pentaerythritol tetradecyl acrylate, and dipentaerythritol pentaacrylate. Ester 'dipentaerythritol pentadecyl acrylate, dipentaerythritol hexaacrylate vinegar, two The above-mentioned polymerizable compound (C) may be used singly or in combination of two or more kinds thereof. The polymerizable compound (C) is used for the solid content of the coloring composition. The content is preferably from 5 to 65% by mass, more preferably from 1 to 6 % by mass. It is preferred that the coloring composition of the present invention comprises a polymerization initiator (1), a poly-starting agent (D), A compound capable of starting polymerization of a polymerizable compound (C) by generating an active radical, an acid or the like by the action of light or heat. As a polymerization initiator (D), it is preferred to generate a radical by ultraviolet rays. Examples of the active radical generator include an acetophenone compound, a benzoin compound, a benzophenone compound, a thioxanthone compound, a triterpenoid compound, an anthraquinone compound, etc. Examples of the acetophenone compound include, for example, the above-mentioned acetophenone compound. Diethoxyphene-, 2-N-morpholinyl+(4-methylsulfanylphenyl)_2-methylpropanone, 2-hydroxy-2-methyl-1-phenyl Propane ketone, benzoin dimethyl ketal, 2 hydroxy-2-indenyl-l-[4-(2-hydroxyethoxy) An oligomer of phenyl]propanone, hydroxycyclohexyl phenyl ketone, 2, thiol 2·methyl succinyl (4 benzylidene) phenyl] propyl ketone-1- ketone, etc., preferably It is listed as 2_义吗琳基. Bu (4) A I56704.doc -41 - 201213310 thiopyristylphenyl)-2-mercaptopropylamine·ι_ketone, etc. As the above-mentioned benzoin compound, for example, benzoin And benzoin methyl ether, benzoin B light, benzoin isopropyl, benzoin isobutyl ether, etc. f as the above diphenyl hydrazine compound, for example, dimercapto ketone, o-benzinobenzoic acid vinegar, 4 benzene Benzophenone, 4-benzylidene-mungyl-diphenyl sulfide, 3,3,,4,4'-tetrakis(t-butylperoxycarboxy)dibenzophenone, 2,4,6 - Tridecyl benzophenone and the like. Examples of the above thioxanthone compound include 2-isopropyl thioxanthene, anal isopropyl thioxanthene, 2,4·diethyl thioxanthone, and 2,4-dithiazolone. - gas-4-propoxythioxanthone and the like. Examples of the compound of the above-mentioned well 11 include 2,4-bis(trichloromethyl)-6-(4-decyloxyphenyl)-1,3,5-tri-π well, 2,4_double (Trichlorodecyl) 6 (4-methoxynaphthyl)-1,3,5-trin, 2,4-bis(trichloroindenyl)_6_(4-methoxystyryl)-1 , 3,5-three tillage, 2,4-bis(trimethylmethyl)_6_[2_(5-methylfuran-2-yl) vinyl]-1,3,5-three tillage, 2,4-double (three gas sulfhydryl)_6_[2_(furan-2-yl)vinyl]-1,3,5-three tillage, 2,4-bis(trimethylmethyl)_6_[2_(4-diethylamino) _ 2-Methylphenyl)vinyl]-l,3,5-three tillage, 2,4-bis(trichloroindenyl)-6-[2-(3'4-dimethoxyphenyl) Vinyl]-1,3,5-three" well and so on. Examples of the ruthenium compound include a ruthenium fluorenyl ruthenium compound, and specific examples thereof include N-benzyl methoxy 丨 ( (4 phenyl thioalkyl phenyl) butane-1- Keto-2-imine, N-benzylideneoxy. Gasoline phenylsulfanylphenyl)octane-1-one-2-imine, N-acetoxyethyl_6_(2_mercaptobenzylidene)-9H-carbazole-3- Ethyleneimine, N-acetoxyethyl-6-{2-methyl-4-(3,3-dimercapto-2,4-dioxolylmethoxy)benzene A 156704.doc -42- 201213310 fluorenyl}-9H-carbazol-3-yl]ethene _1_imine and the like. Examples of the living radical generating agent different from the above include 2,4,6·dimercaptobenzylidene diphenylphosphine oxide, 2,2,_bis(o-phenyl)-4'4 ''5,5'-Tetraphenyl-1,2'-biimidazole, 1〇_butyl·2_chloroacridone, 2_ethyl onion, diphenylethanedione, 9 nose phenotype , lyrics, phenyl ethyl decanoate, ferrocene compounds, and the like. Examples of the acid generator include 4-hydroxyphenyldimethylhydrazine-p-methyl sulphate, 4-hydroxyphenyldimethylnickel hexafluoroantimonate, and 4·acetoxyphenyl dioxime. Base oxime benzenesulfonate, 4_acetoxyphenyl-methyl-benzyl hexafluoroantimonate, triphenyl nickel oxime sulfonate, tripentyl hexafluoroantimonate And diphenyl(tetra)toluene acid salt, diphenylsulfonium hexafluoroate salt, etc., or nitrobenzyl tosylate, benzoin tosylate, and the like. Further, among the above-mentioned compounds which are active radical generating agents, a compound which generates an acid while generating an active radical may be used. For example, a tri-cultivation compound may be used as an acid generator. The content of the polymerization initiator (D) is preferably 0.1% by mass based on the total amount of the resin (B) and the polymerizable compound (c), more preferably "% by mass". When the content of the initiator is within the above range, the sensitivity is improved and the exposure time is shortened to improve the productivity. The coloring composition of the present invention may further contain a polymerization initiator (f). (F) is usually used in combination with a polymerization initiator (D) which is a compound or a photosensitizer which is used in the polymerization which promotes polymerization of a polymerizable compound which starts polymerization by a polymerization initiator. The auxiliary (F) may, for example, be an amine compound or an alkoxy fluorene 156704.doc • 43-201213310 compound, a thioxanthone compound, etc. Examples of the above amine compound include triethanolamine, methyldiethanolamine, and triisomeric. Propylamine, methyl 4-didecylaminobenzoate, heart dimethylaminobenzoic acid ethyl s, 4·dimethylamino benzoic acid isoam@|, benzoic acid _2 bis fluorenyl Aminoethyl ester, 4-didecylamino benzoic acid 2-ethylhexyl ester, n, n-methyl-p-toluidine 4,4-bis(dimethylamino)benzamide (commonly known as rice/, ketone) 4,4-bis(monoethylamino)benzophenone, bis(ethylmethylamino) A benzophenone or the like, among which a 4,4'-bis(diethylamino)benzhydryl network is preferred. For example, the product "EAB_F" (manufactured by Hodogaya Chemical Industry Co., Ltd.) may be used. Commercially available polymerization starting auxiliaries. Examples of the alkoxy ruthenium compound include 9,1 fluorinated onion, 2-ethyl-9,10-dimethoxyanthracene, and 9-diethoxylated onion B: _ 9,10 - Diethoxy hydrazine, 9,1 〇 _ dibutoxy fluorene, 2 - ethyl -9, 1 〇 dibutoxy fluorene, and the like. The above thioxanthene compound can also be used as the polymerization starting assistant (f), and specifically, the same as above can be mentioned. In the case of using the polymerization initiator (7), it is preferably 001 to 10 moles, more preferably 0.01 to 5 moles, based on the polymerization initiator (D) of Si Mo. The coloring composition of the present invention comprises a solvent (E). Examples of the solvent (8) include 'acetic acid solvent (solvent having -coo-), solvent other than vinegar solvent (having a solvent without a coffee), (iv) a solvent (having a solvent of -COO-), and a vinegar solvent. Other than the same solvent (having a solvent of 156704.doc 201213310, -〇- and -CO-), an aromatic hydrocarbon solvent, a guanamine solvent, a dimethyl sub-grinding or the like. Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactic acid, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetonate, amyl formate, and isoamyl acetate. , butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl acetate, ethyl acetate, ethyl acetate, ring Hexanol acetate, γ-butyrolactone, and the like. Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethyl ether. Glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl hydrazine, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3_decyloxy-indole-butanol, 3_decyloxy-3-methylbutanol, tetrahydrofuran , tetrahydropyran, hydrazine, 4 • dioxane, monoethylene glycol dioxime ether, diethylene glycol diethyl ether, diethylene glycol decyl ethyl ether, diethylene glycol dipropyl ether, diethylene Dibutyl ether, anisole, phenethyl ether, methyl anisole, and the like. Examples of the ether vinegar solvent include decyloxyacetate, decyloxyacetate, butyl oxyacetate, ethoxyacetate, ethoxyacetic acid, and 3-methoxypropionic acid. Methyl ester, ethyl 3-methoxypropionate, decyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, decyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl vinegar, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, decyl 2-methoxy-2-mercaptopropionate, 2-B Ethyl oxy-2-mercaptopropionate, 3-decyloxybutyl acetate, 3-methyl-3-methoxybutylacetic acid vinegar, propylene glycol monoterpene ether acetate, propylene glycol monoethyl ether Acid ester, 156704.doc -45- 201213310 Propylene glycol mono (tetra) ethyl (tetra), ethylene glycol monomethyl ether acetate, ethylene glycol monoethylamine, monoethylene glycol monoethyl ether acetate, diethylene glycol single Butyl ether acetate and the like.乍 is a cold agent' can be enumerated: 4_hydroxy_4_methyl-2pentanone, acetone, 2-form 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-ketone , cyclopentanone, cyclohexanone, isophorone and the like. The alcohol solvent 'is exemplified by methanol, ethanol, propanol, butanol, hexanol, ethylene glycol, propylene glycol, glycerin or the like. Examples of the aromatic hydrocarbon solvent include benzene, toluene, diphenylbenzene, and tristimene. The guanamine solvent may, for example, be N,N•dimethylmethanamine, n,n-dimethylacetamide or N-decylpyrrolidone. These solvents may be used singly or in combination of two or more. Among the above solvents, in terms of coatability and dryness of the coloring composition, it is preferred that the boiling point at 1 atm is 12 〇β (: above, 18 〇 or less, more preferably propylene glycol) Single W acetate vinegar, propyl ether. machi-r, - The content of the solvent (8) in the coloring composition is preferably 70 to 95% by mass with respect to the coloring composition. More preferably, it is 75 to 90% by mass. The coloring composition of the invention may further comprise a surfactant (〇). The surfactant (9)' may be selected from the group consisting of a polyoxo-based surfactant, a surfactant, and an oxygen-based interface having a fluorine atom. At least one of the group consisting of active agents. As the above (4) (4) interface activity, _, can be used to cut the oxygen institute key 156704.doc • 46- 201213310 surfactant, etc. Specific examples: Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Polyether Modified Shishing Oil SH8 4 00 (trade name: manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Jap an Contract Society). The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain, etc., specifically, Fluorad (trade name) FC430, Fluorad FC43 1 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (trade name) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac R30 (manufactured by DIC Corporation), Eftop (trade name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.) , Surflon (trade name) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Precision Chemical Research Co., Ltd.), and the like. Examples of the above-mentioned polyoxo-based surfactant having a fluorine atom include a surfactant having a decane bond and a fluorocarbon chain. Specific examples are: Megafac (registered trademark) R08, Megafac BL20, Megafac F475, 156704.doc -47- 201213310

Megafac F477, Megafac F443 (manufactured by DIC Corporation), etc. β These surfactants may be used singly or in combination of two or more. The content of the surfactant (G) is preferably 〇1% by mass or more and 0.2% by mass or less based on the coloring composition. More preferably 〇〇〇1 to 〇1% by mass. When the content of the surfactant (G) is in the above range, the flatness of the film obtained by applying the coloring composition tends to be good. In the case where the coloring composition of the present invention contains only the dye of the present invention and the solvent (e), it can be prepared by mixing the dye of the present invention with the solvent (E) to form a solution. After mixing, the components were insoluble by filtration using a filter. The pore diameter of m is (3) is 3 Å or less, more preferably 0.1 to 2 μιη. In the case where the coloring composition of the present invention comprises a component other than the dye and the solvent of the present invention, it is preferred to produce a coloring composition comprising only the dye and solvent of the present invention by the above method. The mixture is prepared by mixing a component other than the dye of the present invention. When mixing, further adding a solvent (Ε) other than the dye of the present invention may be divided into dissolved or dispersed in a solvent; the human mt J is added after mixing, and the solvent for dissolving the above various components is used. (8) 'The solvent may be the same as the solvent 1 is compatible. It is preferred to remove the insoluble component by filtration using a device after mixing. As the pore diameter of the filter, the colorant (4) Contains the remaining

In the case of U) _ or less, preferably 5 〜 μ μ 〇, in the case of a coloring agent (A in the case where A does not contain a pigment, it is 3 or less, preferably Ο». As the use of the present invention荖 έ έ έ ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' A method of forming a coloring layer by removing/drying a volatile component such as a solvent on a substrate or another resin layer (for example, another coloring composition layer formed on a substrate in advance), and exposing the colored layer through a photomask There is no need to use an inkjet machine by photolithography, etc. Depending on the use of -30 μm, the film thickness of the coating film in this case is not particularly limited, and materials, uses, etc. are appropriately adjusted. Preferably, it is 1 to 20 μm, and more preferably 1 to 6 μη. Examples of the coating method of the coloring composition include extrusion coating, direct gravure coating, and reverse gravure coating. Cloth method, (10) coating method, die coating method, etc. Crush coater, bar coater, spin coater 'slit & spin coater, slit coater (sometimes also known as slit squeeze type, curtain type coater, The coating machine is applied by a coating machine such as a non-rotating coater. For the removal or drying of the solvent, for example, dryness, drying, decompression, and the like may be mentioned. The specific m degree is preferably ^iG~i2〇ec, Preferably, it is 25 to 1 〇〇. (: The drying time is preferably 10 seconds to 6 minutes, more preferably 3 seconds to 3 minutes, when it is dried under reduced pressure, preferably Under the pressure of 5〇15〇~, in the temperature range of 20~25°C. "Coating film after drying, through the reticle used to form the target pattern, the pattern shape on the reticle is exposed at this time. It is not particularly limited, and a pattern shape corresponding to the intended use can be used. As the light source for exposure, a light source that generates light having a wavelength of 25 〇 to 45 〇 nm is preferable, and specific examples thereof include a mercury lamp and a light-emitting diode. Metal dentate 156704.doc -49· 201213310 Lamps, dentate lamps, etc., can also be used to etch the filters of the cut-off special band Line cut

Alternatively, or selectively extracting and extracting using a bandpass filter that extracts specific subtraction from I, bamboo, and Pinot. In order to be able to illuminate the entire exposure surface with parallel rays or to precisely position the reticle with the substrate, it is preferred to use a mask aligner, stepper or the like. After the exposure, development can be carried out by contacting a developing solution with a specific portion, for example, without exposing the first portion, thereby obtaining a pattern. The developing solution may, for example, be an aqueous solution of a basic compound (potassium hydroxide, sodium carbonate tetramethylphosphoric acid or the like) which may contain a surfactant. Any one of the fog laws. Into. Preferably, the development method after development may be a mixing method, a dipping method, or a spraying, and the substrate may be washed at an arbitrary angle by any angle. Further, it is also possible to carry out a post-baking treatment as a post-baking treatment, preferably, for example, 150 to 23 (TC, a range of 10 to 240 minutes. According to the present invention, it can be provided by dissolving in an organic solvent. A dye excellent in storage stability in a solution. The coloring composition containing the dye of the present invention can be suitably used for forming a color filter or a colored pattern, and can obtain a small amount of foreign matter and color density, brightness, contrast, sensitivity, A coloring pattern and a color filter excellent in resolution, heat resistance, etc. Further, the color filter or the colored pattern may be used as a part of components such as an optical film, an array substrate, and a color filter substrate. At least one of the groups of the optical film, the array substrate, and the color filter substrate can be used in a liquid crystal display device, and the organic EL (Electroluminescence) device is used in a liquid crystal display device. In the display device, such as a solid-state imaging device. EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples. The "%" and "parts" in the comparative examples are % by mass and parts by mass as long as they are not specifically labeled. Example 1 1 part of indole aniline-4-sulfonic acid (compound represented by formula (a_2)) After adding water 200, the pjj was adjusted to 7 to 8 by using a 3〇% aqueous sodium hydroxide solution under ice cooling. The following operation was carried out under ice cooling. Add sodium nitrite 1] L1 part and stir for 30 minutes. 35% hydrochloric acid After adding 39 parts of a small amount to a brown solution and stirring for 2 hours, an aqueous solution in which an amine sulfonate is dissolved in 1 part of water is added to the reaction solution to be stirred, thereby obtaining a diazo content. Suspension of salt.

The following operation was carried out under ice cooling. I56704.doc After the above-mentioned % phase water material was changed to 51-201213310 to make it a colorless solution, the pH was adjusted to 8 to 9 with a 30% sodium hydroxide aqueous solution. The suspension containing the diazonium salt was added dropwise over 2 hours. After the completion of the dropwise addition, the mixture was stirred for 2 hours, whereby a yellow suspension was obtained. The yellow solid obtained by filtration was dried under reduced pressure at 6 ° C to obtain 21.4 parts (yield: 87%) of the compound of formula (d-3).

0.3 g of the compound (d-3) was dissolved in N,N-dimethylformamide to a volume of 250 cm, and 2 cm3 of the solution was diluted with water to have a volume of 100 cm3 (concentration: 0.028). g/L), the absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). The compound showed an absorbance of 2.9 (arbitrary unit) at λπ^χ = 433 nm. In a flask equipped with a cooling tube and a stirring device, 5.0 parts of compound (d_3), 35 parts of acetonitrile and 16 parts of N,N-didecylguanamine were added while maintaining 20 at the stirring. (: The following, - the surface is added with sulfite gas 2 ride. After the end of the dropwise addition, 'heat up to 40t' and maintain at the same temperature for 2 hours to carry out the reaction, and then cool to 2 (TC. - surface disturbing mixing - After the cooled reaction solution was poured into 150 parts of ice water, the mixture was stirred for 3 minutes. The yellow crystals separated by filtration were thoroughly washed with tap water and dried under reduced pressure for 2 hours under thieves. The tube of the tube and the stirring device was charged with 2.0 parts of 1-amino-2-propanol and 2 parts of N-methylpyrrolidone, and the surface was maintained at 20t or less under the surface of (4). 156704.doc -52·201213310 Yellow crystals. After the yellow crystals are charged, the temperature of the solution is raised to room temperature, and then the reaction solution is subjected to (4) for 3 G minutes. 40 parts of the indocol is added to the reaction solution t and stirred, and then acetic acid is added. The mixture solution of 29 parts and ion-exchanged water fan fraction was added to the surface-mixed surface to precipitate crystals. The crystals separated by the separation of the sputum were thoroughly washed with ion-exchanged water and reduced at 60 c. Press drying 'to obtain the formula (m_3) 3.9 parts of the compound represented by (yield 69%). °

f compound (111-3) 0.35 g was dissolved in ethyl lactate to make a volume of 25 〇 cm 3 ' and 2 em 3 was diluted with ion-exchanged water to make the volume _ cm 3 (dimension: 0.028 g / L) The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2·3 (arbitrary unit) at ληι&χ=43ι nm. The following reaction was carried out under a nitrogen atmosphere. After 15 parts of hydrazine-methylpyrrolidone was added to 49 parts of the compound (ΠΙ_3), the reaction solution was prepared by stirring for 3 minutes. The reaction solution was stirred while stirring at room temperature, and 6.8 parts of hydrazine was added dropwise. After the completion of the dropwise addition, the mixture was further stirred for 8 hours. Add 7 parts of hexamethylene gas. After the completion of the dropwise addition, the mixture was further stirred for 8 hours. After the reaction solution was poured into 3 parts of water, 80 parts of ethyl acetate was added and stirred for 3 minutes. After separating the organic phase using a separatory funnel, further use 5 parts of water, 3000 parts of ITO, sodium carbonate solution, 1 part of 1% acetic acid aqueous solution, and 1 part of ion exchange water into 156704. Doc -53- 201213310 The organic phase of the organic washing system is subjected to a solvent column to obtain a mixture of the compound represented by the formula (1-6) and the compound represented by the formula (IV), that is, the dye (1) 2.0 parts. The yield was 85%.

, the dye (a) 0.35 g is dissolved in ethyl lactate to make a volume of 25 〇cm and 2 cm 3 of it is diluted with ion-exchanged water to make a volume of 100 cm (concentration 〇 〇 28 g / L), The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2·2 (arbitrary unit) at Xmax = 431 nm. &lt;Measurement of content ratio in mixture&gt; The content ratio of the compound represented by the formula (1_6) in the dye (I) and the compound represented by the formula (I) can be corrected by using a liquid chromatograph (HpLC) The curve method was used for the measurement. The calibration curve method refers to a method of determining an unknown concentration from the concentration-absorbance relationship of a standard solution series of a known concentration when determining the concentration of a substance in a solution. HPLC device Prominence (manufactured by Shimadzu Corporation) Liquid feeding unit: LC-20AT two automatic sampler: SIL-20A - Taiwan column oven: CTO-20A - Taiwan 156704.doc • 54· 201213310 UV detector: SPD-20A— Online degasser: DGU-20A - Taiwan tube Wakosil II 3C18HG (3 μιη, 3 mm / xl50 mm) Mobile phase A: 0·1% ΤΒΑΒ / water: acetonitrile (9:1) Β liquid: 0 · 1°/〇ΤΒΑΒ/water: acetonitrile (1··9) Gradient (sputum) 初始 initial concentration 25% 25%-&gt;(30 minutes)-&gt; 100% (for 20 minutes) Detection wavelength 254 nm tube Column temperature 40 ° C Flow rate 0.5 mL / min Injection amount 5 pL TBAB : tetrabutylammonium bromide The compound represented by the formula (1-6) and the compound represented by the formula (1-7) are dissolved in acetonitrile, respectively. A solution of the concentration described in Table 22 was prepared. With respect to this solution, liquid chromatography analysis was carried out under the above conditions, and the elution time and peak area were measured. The results are shown in Table 22. [Table 22] Compound concentration (g/L) Lysis time (minutes) Peak area Compound represented by formula (1-6) 0.222 39.8 1562509 0.296 39.6 2139881 0.432 39.6 3144362 0.555 39.6 4040232 Formula (1-7) Compound 0.236 37.7 1793650 0.314 37.5 2404909 0.400 37.4 2973931 0.555 37.2 4263412 156704.doc -55- 201213310 Based on the concentration of the solution and the measured peak area, the calibration curve was obtained by the following formula. Calibration curve of compound represented by formula (1-6): (peak area) = 72 2 χ (concentration) Calibration curve of compound represented by formula (1-7): (peak area) = 76 〇 gas concentration) (1) 13.9 mg was dissolved in acetonitrile to a volume of 5 〇 (concentrated j^O.278 g/L). Liquid chromatography analysis was carried out under the above conditions, and the elution time and peak area were measured. When the elution time was 35 9 minutes, the compound of the formula (4) was dissolved, and the peak area was 944,436. When the elution time is ==, the compound represented by the formula (IV) is eluted. The peak area is ...% σ milk <-) The content ratio of each compound, and the result is the compound represented by formula (1-6) / formula (Ι·7 44.7/55.3. mouth ^ example 2 ^ using - formula (4) Mixing 101 parts of the compound of the compound of U to prepare the dye (2). Dissolve the wood (-) 12·9 mg in acetonitrile to prepare a solution of 5〇3 (concentration··〇.258 ff/ The volume of T彳 is 50 em. Time and peak area. In the dissolution: the compound represented by the fineness in the same manner as in Example 1, the peak surface enthalpy is 37.6 minutes, and the formula (4) is eluted; the time of dissolution is 964928 ° The dissolution time is 39.8 矣 using the above-mentioned calibration =:: compound, the peak area is 1. ίί Μ Β , ' each compound in the wood (2), '·. Fruit 疋 (1-6) Still 3 1 to 49.9/50. b ^ Compound represented by formula (ί-7) = I56704.doc -56-201213310 Example 3 Using the formula of the compound i4i represented by the formula (4) Mix 60 parts of the compound to prepare the dye (3). Dissolve the dye (Sanchuan. 5 mg in B guess) and prepare a cold liquid with a volume of 5 〇3 The degree of dissolution was 0.230 g/L. The dissolution time and the peak area were measured in the same manner as in Example 。. When the elution time was 37.6 minutes, the precipitate was precipitated (Ι·7). ## Peak area was 512173. The compound represented by the formula (4) is eluted at a dissolution time of Μ $min, and its area is (10) (4). The content ratio of each compound in the dye (III) is determined by using the above calibration curve, and the result is a formula (Ι·6). The compound represented by the formula / formula (4) is represented by 70.3/49.9. Example 4 Using Makan Research, 18 parts of the compound represented by the formula (4) and 2G parts of the compound represented by the formula (4) are mixed to prepare a dye (four : Six dyes (8) 1 〇. 9 mg were dissolved in acetonitrile to prepare a volume of 5 〇 coffee 3: liquid U degree. 0.218 g / L. The dissolution time and sound area were measured in the same manner as in Example J. When the analysis time was 37. 6 minutes, the compound represented by (ι_7) showed a peak area of 173668. When the elution time was (four) minutes, the compound represented by (4) was eluted, and the peak area was ι 336 〇 73. The calibration curve is used to determine the content ratio of each compound in the dye (4), and the result is the formula 7 The compound represented by the formula / formula (IV) = 89 9 / ι〇ι. Example 5 &lt;Preparation of coloring composition&gt; In the sample tube, 5 parts of the dye (I) and propylene glycol monomethyl bond acetic acid Vinegar 156704.doc •57·201213310 95 parts were mixed, plugged and shaken at 40 ° C for 10 minutes using an ultrasonic oscillator. After standing at room temperature for 30 minutes, filter with a membrane with a pore size of 0.45 μm The filter (HLC-DISK 13: manufactured by Kanto Chemical Co., Ltd.) was filtered to obtain a coloring composition. It was visually confirmed that there was no insoluble matter on the filter at the time of filtration. Synthesis Example 1 The following compound (ΙΙΙ-2) was synthesized by the method described in Patent Document 1. 0.35 g of the compound (111-2) was dissolved in ethyl lactate to a volume of 250 cm3, and 2 cm3 of the compound (111-2) was diluted with ion-exchanged water to have a volume of 100 cm3 (concentration: 0.028 g/L), and spectroscopic use was used. The absorption spectrum was measured with a photometer (quartz cell, optical path length: 1 cm). The compound showed an absorbance of 2.2 (arbitrary unit) at Xmax = 425 nm.

Examples 6 to 8 and Comparative Examples 1 to 3 The dyes described in Table 23 were mixed with a solvent to obtain a coloring composition in the same manner as in Example 5. [Table 23] Dyes (parts) Solvent (parts) Example 5 Dye (I) 5 PGMEA 95 Example 6 Dye (2) 5 PGMEA 95 Example 7 Dye (3) 5 PGMEA 95 Example 8 Dye (4) 5 PGMEA 95 156704.doc -58- 201213310 Dyes (parts) Solvent (parts) Comparative Example 1 CI Solvent Yellow 162 5 PGMEA 95 Comparative Example 2 Oil Soluble Yellow 1151 0.5 PGMEA 99.5 Comparative Example 3 Compound (III-2) 3 PGMEA 97 In Table 23, PGMEA represents propylene glycol monomethyl ether acetate. &lt;Evaluation of storage stability&gt; The sample tube in which the colored composition was sealed was stored in an incubator (manufactured by Sanyo Electric Co., Ltd.: MIR-553) at 5 °C. With respect to the colored composition after storage, the presence or absence of the precipitate was visually confirmed. After storage for 10 days, the insoluble matter was found to be X; insoluble matter was not found in the colored composition after 10 days of storage, but the insoluble matter was found in the colored composition after 20 days of storage as Δ; No insoluble matter was found in the colored composition after 20 days of storage, but the insoluble matter was found in the colored composition after storage for 30 days as 〇; no insoluble matter was found in the colored composition after 30 days of storage. The situation is recorded as ◎. The results are shown in Table 24. [Table 24]

Storage stability Example 5 ◎ Example 6 ◎ Example 7 ◎ Example 8 Δ Comparative Example 1 X Comparative Example 2 X Comparative Example 3 X Example 9 [Preparation of coloring composition] (A) Coloring agent: Dye ( a) 0.30 parts by mass of (B) resin: methacrylic acid / benzyl methacrylate copolymer (mol ratio is 156704.doc • 59· 201213310 30/70 'average molecular weight is 1〇7〇〇, acid value is 7 〇mgKOH/g) (HN-123; manufactured by Tiangang Chemical Industry Co., Ltd.) 33 8〇/〇 propylene glycol monomethyl ether acetate vinegar solution 1.67 parts by mass: 1.48 parts by mass (D) Polymerization initiator: N_benzonitrile Phenylthioalkylphenyl)octane-1-one-2-imine (Irgacure®xe〇1 (manufactured by BASF Japan)) 0.22 parts by mass of (G) surfactant: polyether modified eucalyptus oil (T 〇 ray sincone SH8400; Dow Corning Toray Co., Ltd.) 1 〇 / 〇 propylene glycol monoethyl ether acetate solution 10. 10 parts by mass (E) solvent propylene glycol monomethyl ether acetate g 6.23 parts by mass mixed A coloring composition is obtained. &lt;Evaluation of storage stability&gt; The sample tube in which the color composition was sealed was placed in a thermostat (manufactured by Sanyo Electric Co., Ltd.: MIR-553), and stored at 5 ° C for 30 days. [Production of color filter] The preserved coloring composition was applied to glass (#1737; Corning) by a spin coating method and baked at 100X: for 3 minutes to volatilize volatile components. After the glass coated with the colored composition was cooled to room temperature, light exposure was performed at 150 mJ/cm 2 (365 nm basis) in an atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.). . Then, it was baked in an oven at 220 ° C for 2 hours to prepare a color extinction film (film thickness 2.2 μιη) ° [foreign matter evaluation] 156704.doc • 60· 201213310 For the color filter month obtained, a surface shape measuring microscope was used. 7510; manufactured by Keyence) Observe at a magnification of 250 times and check the number of black spots or white spots in the field of view. When the number of the foreign matter is 2 or more, it is judged that the amount of foreign matter derived from the dye is small and the amount of foreign matter is more than 20, and it is referred to as X. The results are shown in Table 25. Example 10 A coloring composition was obtained in the same manner as in Example 9 except that the dye (I) was changed to the dye (II). In the same manner as in the embodiment 9, the price of the stableness is saved. The results are shown in Table 25. [Table 25] Impurity Example 9 〇 Example 10 〇 From the results of Tables 24 and 25, it was confirmed that the coloring composition containing the dye of the present invention and an organic solvent can suppress the generation of precipitates and has excellent storage stability. Industrial Applicability The dye of the present invention is excellent in storage stability in a solution obtained by dissolving in an organic solvent. The colored composition of the dye of the present invention can be suitably used for forming a color filter or a colored pattern, and can obtain a colored pattern excellent in color density, brightness, contrast, sensitivity, resolution, and heat, and the like. Color filter. Further, the color filters or colored patterns may be used as part of components such as an optical film, an array substrate, and a color filter substrate. Further, at least one of the groups selected from the group consisting of the optical film, the array substrate, and the color filter substrate 156704.doc-61 · 201213310 is used in a display device such as a liquid crystal display device or an organic EL device. ; in solid state imaging devices and other machines. 156704.doc -62-

Claims (1)

201213310 VII. Patent application scope: 1. A dye comprising at least two compounds represented by formula (1): B2-N=N-A2-S-N-Z2—0—?.___11 § Λ 9 Ancient 0 c— L - C - 〇 - 21 ~ N - S - A1 - N = N - B1 (j O [弋 (I) wherein Z, Z and L each independently represent a carbon number which may have a substituent of 1 to 16 a divalent aliphatic hydrocarbon group, the _CH2 contained in the aliphatic hydrocarbon group may be substituted by -CO- or 〇_; R and R each independently represent a hydrogen atom, and may have a substituent having a carbon number of 1 to 16 a monovalent saturated hydrocarbon group or a mercapto group having a carbon number of 2 to 18 which may have a substituent; and A and A2 each independently represent a divalent aromatic nicotine group having a carbon number of a substituent; Each of the monovalent aromatic hydrocarbon groups having a carbon number of 6 to &lt; or a carbon number which may have a substituent is 3 to 4 4 valent heterocyclic groups, which are contained in the heterocyclic group, respectively · CH2• can also (3) _ replace Bu 2 · such as the dye of the requester, in which the base represented by the formula (9) is independently expressed by the heart: (II) The carbon number which may have a substituent is [in the formula (II), R4 represents a hydrogen atom or a monovalent saturated hydrocarbon group of also 1 to 16; and R represents a valence of a carbon number which may have a substituent of from 1 to 16 Saturated hydrocarbon 156704.doc 201213310 base]. 3. The dye according to claim 1, wherein at least two of the compounds represented by the formula (I) are one or more compounds represented by the formula (Ι-A) and two or more formulas (summer B') a mixture obtained by reacting a compound, 0 0 -X2 α·Β,) [In the formula (Ι-Α) and the formula (Ι-B·), Ri, Αι, Β!, Z1, and the same meaning as above; X1 and X2 are independently represented Nansu atom]. 4. A coloring composition comprising a dye and a solvent as claimed. The colored composition of claim 4, which further comprises at least an anthracene selected from the group consisting of a resin, a polymerizable compound, and a polymerization initiator. A 6. A color calender sheet is formed. It is a coloring composition as claimed in claim 4, and a display device comprising a color filter as claimed in claim 6 156704.doc 201213310 IV. Designated representative figure (1) The representative representative figure of the case is: (None) (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: OR2 Ο O R1 Ο β2-Ν=Ν-A2-SN-Z2— O—C—L1—C—O—Z1-N—S—A1-N=N-B1 II O II o 156704.doc -2-