KR20140026284A - Compound for dye - Google Patents

Abstract

Provided are a compound indicated as formula (A-I), a coloring hardening resin composition including the compound, a color filter formed using the resin composition and a display including the color filter. In formula (A-I), X refers to an oxygen atom, a nitrogen atom or a sulfur atom. ′Y′^(m-) refers to any m-valent anion. R^41-R^46 independently refer to a hydrogen atom and an alkyl group having 1-20 carbons capable of being replaced with an amino group or a halogen atom. R^47-R^54 independently refer to a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1-8 carbons. R^55 refers to a hydrogen atom, an alkyl group having 1-20 carbons, or an aryl group capable of being replaced.

Description

Color compound {COMPOUND FOR DYE}

The present invention relates to compounds useful as pigments.

Dye is used as a coloring agent of the color filter contained in a liquid crystal display device, a solid-state image sensor, etc. As the dye, for example, a compound represented by the formula (A-III-1) is described in WO2012 / 053201.

The compound known in the art has not been sufficiently satisfactory in heat resistance, and thus, the colored curable resin composition containing the compound has not been sufficiently satisfactory in terms of heat resistance.

The present invention includes the following inventions.

[1] The compound represented by formula (A-1).

[In Formula (A-1), X represents an oxygen atom, a nitrogen atom, or a sulfur atom. [Vi] ^m- represents an arbitrary m-valent anion. R ⁴¹ to R ⁴⁶ each independently represent a hydrogen atom, an amino group, or a group having 1 to 20 carbon atoms and 2 to 20 carbon atoms that may be substituted with a halogen atom and an oxygen atom inserted between the carbon atoms constituting the alkyl group Or an aryl group which may be substituted. R ⁴¹ and R ⁴² may be bonded to form a ring together with the nitrogen atom to which they are bonded, R ⁴³ and R ⁴⁴ may be bonded to form a ring together with the nitrogen atom to which they are bonded, and R ⁴⁵ and R ⁴⁶ may be You may bond and form a ring with the nitrogen atom to which they couple | bond. R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms, and an oxygen atom is inserted between the carbon atoms constituting the alkyl group. Although the group is present, R ⁴⁸ and R ⁵² may be bonded to each other to form —O—, —NH—, —S—, or —SO ₂ —. R ⁵⁵ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group which may be substituted.

Moreover, a plurality of molecules in one molecule

When is included, these may have the same structure and may differ from each other.

m represents any natural number]

[2] In formula (A-I), X represents an oxygen atom, a nitrogen atom, or a sulfur atom, [k] ^m- represents an arbitrary m-valent anion, and R ⁴¹ to R ⁴⁶ each independently represent a hydrogen atom. , A group having 1 to 20 carbon atoms which may be substituted with an amino group or a halogen atom, an alkyl group having 2 to 20 carbon atoms and an oxygen atom inserted between the carbon atoms constituting the alkyl group, or an aryl group which may be substituted, and R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, but R ⁴⁸ and R ⁵² are bonded to each other to form -O-, -NH-, -S Or -SO ₂ -may be formed, and R ⁵⁵ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group which may be substituted.

[3] The compound as described in [1] or [2], wherein [v] ^m- is an anion containing boron in formula (A-1).

[4] The compound as described in [1] or [2], wherein in formula (A-1), [k] ^m- is an anion containing aluminum.

[5] The compound as described in [1] or [2], wherein in the formula (A-1), [k] ^m- is an anion containing fluorine.

[6] In formula (A-1), [1] or [1] wherein ^m- is an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as an essential element; or The compound as described in [2].

[7] The compound as described in [6], wherein in formula (A-1), [k] ^m- is an anion of a heteropoly acid or isopoly acid containing tungsten as an essential element.

[7] In formula (A-1), [k] ^m- is an anion of tungstophosphoric acid, an anion of tungstosilicic acid, or an anion of tungsten isopoly acid. Described compounds.

[Iii] A colored curable resin composition comprising the compound according to any one of [1] to [v].

[10] A coating film formed by using the colored curable resin composition according to [i].

[11] A color filter formed by using the colored curable resin composition according to [i].

[12] A display device comprising the color filter of [11].

When the colored curable resin composition containing the compound of this invention is used, the color filter excellent in heat resistance can be provided.

The compound of this invention is a compound [Hereinafter, it is called a compound (A-1)] represented by Formula (A-1). The compounds of the present invention also include tautomers thereof and salts thereof.

In Formula (A-1), X represents an oxygen atom, a nitrogen atom, or a sulfur atom. In view of ease of synthesis, the sulfur atom is preferable.

As the alkyl group having 1 to 20 carbon atoms represented by R ⁴¹ to R ^46, there may be mentioned, for example to a group represented by the following formula. In the following formulae, * represents a bonding arm with a nitrogen atom. Among these, a C1-C8 alkyl group is preferable, a C1-C6 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.

Examples of R ⁴¹ to a group having 1 to 20 alkyl group or a halogen atom represented by R ^46, there may be mentioned, for example to a group represented by the following formula. In the following formulae, * represents a bonding arm with a nitrogen atom.

As group which has a C2-C20 alkyl group represented by R <^41> -R <^46> , and the oxygen atom is inserted between the carbon atoms which comprise the said alkyl group, group represented by a following formula is mentioned, for example. In the following formulae, * represents a bonding arm with a nitrogen atom. Especially, the group which has a C2-C10 alkyl group and the oxygen atom inserted between the carbon atoms which comprise the said alkyl group is preferable, The group which has a C2-C6 alkyl group and the oxygen atom is inserted between the carbon atoms which comprise the said alkyl group More preferred.

In the substituted aryl group represented by R ⁴¹ to R ^46, examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and iodine atom; Haloalkyl groups having 1 to 6 carbon atoms such as a chloromethyl group and a trifluoromethyl group; Alkoxy groups having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; A hydroxyl group; Sulfamoyl group; C1-C6 alkylsulfonyl groups, such as a methylsulfonyl group, etc. are mentioned.

As a specific example of the aryl group which may be substituted, group represented by a following formula is mentioned, for example. In the following formulae, * represents a bonding arm with a nitrogen atom.

As a ring which R <^41> and R <^42> couple | bonds and forms with the nitrogen atom which they bond, a pyrrolidine ring, a morpholine ring, a piperidine ring, a piperazine ring, etc. are mentioned.

As a ring which R <^43> and R <^44> couple | bonds and forms with the nitrogen atom to which they couple | bond, a pyrrolidine ring, a morpholine ring, a piperidine ring, a piperazine ring, etc. are mentioned.

As a ring which R <^45> and R <^46> couple | bonds and forms with the nitrogen atom to which they couple | bond, a pyrrolidine ring, a morpholine ring, a piperidine ring, a piperazine ring, etc. are mentioned.

Since R <^41> -R <^46> is easy to synthesize | combine, it is preferable that they are each independently a C1-C20 alkyl group or the aryl group which may be substituted, and each independently is a C1-C8 alkyl group or an aryl group represented by a following formula. More preferred. In the following formulae, * represents a bonding arm with a nitrogen atom.

As a group which has a C1-C8 alkyl group represented by R <^47> -R <^54> , and a C2-C8 alkyl group, and the oxygen atom is inserted between the carbon atoms which comprise the said alkyl group, group represented by a following formula is mentioned, for example. . In the following formulae, * represents a bonding arm with a carbon atom.

Since R ⁴⁷ to R ⁵⁴ are easily synthesized, each independently preferably represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably each independently represents a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom. Do.

As a C1-C20 alkyl group represented by R <^55> , group represented by a following formula is mentioned, for example. In the following formulae, * represents a bonding arm with a carbon atom.

In the aryl group which may be substituted by R <^55> , As a substituent, Halogen atoms, such as a fluorine atom, a chlorine atom, and an iodine atom; Haloalkyl groups having 1 to 6 carbon atoms such as a chloromethyl group and a trifluoromethyl group; Alkoxy groups having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; A hydroxyl group; Sulfamoyl group; C1-C6 alkylsulfonyl groups, such as a methylsulfonyl group, etc. are mentioned.

As a specific example of the aryl group which may be substituted, group represented by a following formula is mentioned, for example. In the following formulae, * represents a bonding arm with a carbon atom.

R ⁵⁵ is easily synthesized, preferably an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted, more preferably an alkyl group having 1 to 8 carbon atoms or an aryl group represented by the following formula, and even more preferably: Is an aryl group represented by the following formula. In the following formulae, * represents a bonding arm with a carbon atom.

As a cation part of Formula (A-1), cation 1 thru | or cation 11 etc. which are represented by Formula (A-1) shown in following Table 1 are mentioned.

Especially, as a cation part of Formula (A-1), cation 1 thru | or cation 6 or cation 11-12 are preferable, and cation 1, cation 2 or cation 12 is especially preferable.

In addition, R ⁴⁸ and R ⁵² are combined to -O-, -NH-, -S- or -SO ₂ each other - be mentioned Specific examples of the cationic portion of the formula (A-Ⅰ) in the case in which the examples, to the have.

[Ｙ] ^{m- may} include various known anions, but preferred anions from the viewpoint of heat resistance are anions containing boron, anions containing aluminum, anions containing fluorine, and tungsten, molybdenum, silicon and phosphorus. And anion containing at least one element selected from the group consisting of and oxygen as essential elements.

As an anion containing boron and an anion containing aluminum, the anion shown by following formula (4) is mentioned, for example.

In Formula (4), W <^1> , W <^2> respectively independently represents group which releases two protons from the compound which has two monovalent proton donor substituents. M represents boron or aluminum]

In the group which releases two protons from a compound having two monovalent proton donor substituents, examples of the monovalent proton donor substituent include a hydroxy group, a carboxyl group and the like. Examples of the compound having two monovalent proton donor substituents include catechol which may have a substituent, 2,3-dihydroxynaphthalene which may have a substituent, 2,2'-biphenol which may have a substituent, and a substituent. 3-hydroxy-2-naphthoic acid which may have, 2-hydroxy-1-naphthoic acid which may have a substituent, 1-hydroxy-2-naphthoic acid which may have a substituent, binaphthol which may have a substituent, It is preferable that they are salicylic acid which may have a substituent, benzyl acid which may have a substituent, or mandelic acid which may have a substituent.

As salicylic acid which may have the said substituent, For example, salicylic acid, 3-methyl salicylic acid, 3-tert- butyl salicylic acid, 3-amino salicylic acid, 3-chlorosalicylic acid, 4-bromosalicylic acid, 3-methoxy salicylic acid, 3 Nitrosalicylic acid, 4-trifluoromethylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3,5-dibromosalicylic acid, 3,5-dichlorosalicylic acid, 3,5,6-trichlorosalicylic acid, 3 -Hydroxysalicylic acid (2,3-dihydroxybenzoic acid), 4-hydroxysalicylic acid (2,4-dihydroxybenzoic acid), 5-hydroxysalicylic acid (2,5-dihydroxybenzoic acid), 6-hydroxy Roxy salicylic acid (2, 6- dihydroxy benzoic acid) etc. are mentioned.

As benzyl acid which may have the said substituent, for example

And the like.

As mandelic acid which may have said substituent, for example

And the like.

As an anion represented by Formula (4), an anion (BC-1)-an anion (BC-2 ') etc. are mentioned, for example.

Among these, anions represented by the formula (4) include anion (BC-1), anion (BC-2), anion (BC-3), anion (BC2-5), anion (BC2-6) and anion (BCC-). 272) are preferable, anion (BC-1) and anion (BC-25) are more preferable, and anion (BC-1) is still more preferable. If it is such an anion, the compound (A-1) of this invention tends to be excellent in the solubility with respect to the organic solvent.

As an anion containing fluorine, the group represented by following formula (6), formula (7), formula (i), and formula (i) is mentioned, for example.

[Formula (6)] W ³ and W ⁴ each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or W ³ and W ⁴ are bonded to form a fluorinated alkanediyl group having 1 to 4 carbon atoms. box]

In formula (7), W ⁵ to W ⁷ each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms.

[Wherein, Y ¹ represents a fluorinated alkanediyl group having 1 to 4 carbon atoms]

[Wherein, Y ² represents a fluorinated alkyl group having 1 to 4 carbon atoms]

The formula (6) and (7) include a fluorinated alkyl group having 1 to 4 carbon atoms represents, respectively W ³ to W ⁷ is an alkyl group preferably a perfluoroalkyl and in, for example _{-CF 3, -CF 2 CF 3,} - CF ₂ CF ₂ CF ₃ , -CF (CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF (CF ₃ ) ₂ , -C (CF ₃ ) ₃ , and the like.

The formula (6) Examples of alkanediyl group in W ³ and W ⁴ are coupled having 2 to 4 carbon atoms formed by the fluorinated Al to perfluoro roal alkanediyl group is preferred, for example, _{-CF 2 CF 2 -, -CF 2} CF ₂ CF _2- , -CF ₂ CF ₂ CF ₂ CF ₂ -and the like.

In said Formula (i), as a C1-C4 fluorinated alkanediyl group represented by Y <^1> , a perfluoro alkanediyl group is preferable. As the perfluoro roal alkanediyl group, for example _{-CF 2 -, -CF 2 CF 2} -, -CF 2 CF 2 CF 2 -, -C (CF 3) 2 -, -CF 2 CF 2 CF 2 CF 2 - Etc. can be mentioned.

As the fluorinated alkyl group having 1 to 4 carbon atoms represented by Y ² in the formula (9) is preferably a perfluoroalkyl group. As a perfluoroalkyl group, for example, -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF (CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF ( CF ₃ ) ₂ , -C (CF ₃ ) ₃ , and the like.

As an anion (henceforth "anion (6)") represented by said Formula (6), the following anions (6-1)-(6-6) are mentioned, for example.

As an anion (henceforth "anion (7)") represented by said Formula (7), the following anion (7-1) is mentioned, for example.

As an anion (henceforth "anion") represented by said formula (i), the following anions (VII-1)-(IV-4) are mentioned, for example.

As an anion (henceforth "anion") represented by said formula (i), the following anions (VII-1)-(IV-4) are mentioned, for example.

By containing at least one anion selected from the group consisting of anion (6), anion (7), anion (i) and anion (hereinafter referred to as "anion (6) to (iii)"), The solubility to the organic solvent of the compound (A-1) of this invention can be improved. Among these, anion (6) is preferable and anion (6-1-1) is more preferable.

[Ｙ] An anion of one or more elements selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus represented by ^m- and an anion containing oxygen as an essential element and an anion of heteropoly acid or isopoly acid containing tungsten as an essential element In particular, anions of tungstophosphoric acid, tungstosilicate and tungsten isopoly acid are preferred.

As an anion of a heteropoly acid or an isopoly acid containing such tungsten as an essential element, for example, Keggin-type tungstophosphate ion α- [PW ₁₂ O ₄₀ ] ^3- , Dawson-type tungstophosphate ion α -[P ₂ W ₁₈ O ₆₂ ] ^6- , β- [P ₂ W ₁₈ O ₆₂ ] ^6- , Kegin type tungstosilicate ion α- [SiW ₁₂ O ₄₀ ] ^4- , β- [SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O ₄₀ ] ^4- , even more other examples [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ 0 ₁₁₀ ] ^14- , α- [SiW ₉ O ₃₄ ] ^10- , γ- [SiW ₁₀ O ₃₆ ] ^8- , α- [SiW ₁₁ 0 ₃₉ ] ^8- , β- [ SiW ₁₁ 0 ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^{2 -} and the like.

Also preferred are anions composed of oxygen and one or more elements selected from the group consisting of silicon and phosphorus.

Examples of anions consisting of at least one element and oxygen, selected from the group consisting of such silicon and phosphorus, SiO ₃ ^{2 -} may be mentioned ^-, PO ₄ ^3.

In particular, since synthesis and post-treatment are easy, heteropolyacid anions such as keginous tungstophosphate ions, Dawson-type tungstophosphate ions, and kegin-type tungstosilicate ions, and isopolyacid anions such as [W ₁₀ O ₃₂ ] ^4- desirable.

Examples of the compound (A-1) include any one of the cations 1 to 11, anions (BC-1) to (BC-2), anions (6-1) to (6-6), and anions (7-). 1) a combination with any one of anions (VII-1) to (IV-4) and anions (VII-1) to (iv-4), and any three cations of the above cations 1 to 11 A combination of anionic α- [PW ₁₂ O ₄₀ ] ^3- with any six cations of cations 1 to 11 and anionic α- [P ₂ W ₁₈ O ₆₂ ] ^6- with any of cations 1 to 11 And combinations of four cations with anions α- [SiW ₁₂ O ₄₀ ] ^4- and [W ₁₀ O ₃₂ ] ^4- .

Compound (A-I) can be manufactured by mixing the compound represented by Formula (A-II) (henceforth "compound (A-II)"), and the alkali metal salt of anion [VII] ^m- in a solvent. . Examples of the alkali metals include lithium, sodium, and potassium.

As the solvent, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, ethyl acetate, toluene, methanol, ethanol, isopropanol, acetone, tetrahydrofuran, di Oxane, water and chloroform.

Among these, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, methanol, ethanol, isopropanol and water are preferable. If it is such a solvent, there exists a tendency for the solubility of the alkali metal salt of a compound (AII) and an anion [ ^m ] ^m- to become high.

When the solvent is water, an acid such as acetic acid or hydrochloric acid may be added into the reaction system.

Mixing of the compound (A-II) and the alkali metal salt of the anion ^m- may be performed by dissolving both in the above-mentioned solvent, or may be performed without dissolving. By using the solvent in which both are dissolved, and making it melt | dissolve, the compound (AI) of this invention can be obtained with a high yield.

The mixing temperature of the compound (A-II) and the alkali metal salt of the anion [VII] ^m- is preferably 0 ° C to 150 ° C, more preferably 10 ° C to 120 ° C, even more preferably 20 ° C to 100 ° C. . The mixing time is preferably 1 hour to 72 hours, more preferably 2 hours to 24 hours, even more preferably 3 hours to 12 hours.

In the case of using a solvent compatible with water, the compound of the present invention (A-I) is obtained by mixing the solvent, stirring further for 1 to 3 hours as necessary, and then obtaining a precipitate by filtration. ) Can be obtained. As needed, you may wash | clean the obtained compound (A-I) with ion-exchange water.

In the case of using a solvent which is not compatible with water, the reaction mixture and ion-exchanged water are mixed, and further stirred for 1 hour to 3 hours as necessary, and after that, the organic layer is obtained by liquid separation. The solution containing -I) can be obtained. If necessary, the solution may be washed with ion-exchanged water. The compound (A-I) of this invention can be obtained by removing a solvent from the solution containing the compound (A-I) of this invention.

Furthermore, the compound (A-I) of the present invention may be dissolved in a solvent such as acetonitrile, ethyl acetate, toluene, methanol, ethanol, isopropanol, acetone, chloroform and purified by recrystallization.

A compound (AII) can be manufactured by making the compound represented by a formula (XI) and the compound represented by a formula (CII), for example react. This reaction may be carried out in the presence of an organic solvent or may be carried out without a solvent.

[In Formula (XI) and Formula (C-I), R ⁴¹ to R ⁵⁵ each represent the same meaning as described above.]

A compound (A-II) can also be manufactured by making the compound represented by a formula (XII) and the compound represented by a formula (C-II) react. This reaction may be carried out in the presence of an organic solvent or may be carried out without a solvent.

[In Formulas (XII) and (CII), R ⁴¹ to R ⁵⁵ each represent the same meaning as described above.

The amount of the compound represented by the formula (C-I) is preferably 0.5 mol or more and 8 mol or less, more preferably 1 mol or more and 3 mol or less, based on 1 mol of the compound represented by the formula (XI-I).

The amount of the compound represented by the formula (C-II) is preferably 0.5 mol or more and 8 mol or less, and more preferably 1 mol or more and 3 mol or less with respect to 1 mol of the compound represented by the formula (XII).

30 to 180 degreeC is preferable and 80 to 130 degreeC of reaction temperature is more preferable. The reaction time is preferably 1 hour to 12 hours, more preferably 3 hours to 8 hours.

Also in any reaction, it is preferable to carry out in an organic solvent from a viewpoint of a yield. As an organic solvent, Hydrocarbon solvents, such as toluene and xylene; Halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; Alcohol solvents such as methanol, ethanol, isopropanol and butanol; Nitrated hydrocarbon solvents such as nitrobenzene; Ketone solvents such as methyl isobutyl ketone; Amide solvents, such as 1-methyl- 2-pyrrolidone, etc. are mentioned. The amount of the organic solvent used is preferably 1 part by mass or more and 20 parts by mass or less, and more preferably 2 parts by mass or more and 10 parts by mass with respect to 1 part by mass of the compound represented by the formula (XI) or formula (XI-II). It is as follows.

It is preferable to perform the said reaction in presence of a condensation agent from a viewpoint of a yield. Phosphoric acid, polyphosphoric acid, phosphorus oxychloride, sulfuric acid, thionyl chloride, etc. are mentioned as a condensing agent.

The amount of the condensing agent used is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.2 parts by mass or more and 5 parts by mass to 1 part by mass of the compound represented by the formula (XI-I) or formula (XI-II). It is as follows.

The method of obtaining the compound (A-II) which is a target compound from a reaction mixture is not specifically limited, Various well-known methods can be employ | adopted. For example, the method of mixing a reaction mixture with alcohol (for example, methanol, etc.) and filtering the precipitated crystal | crystallization is mentioned. The reaction mixture is preferably added to alcohol. The temperature at the time of adding a reaction mixture becomes like this. Preferably it is -100 degreeC or more and 50 degrees C or less, More preferably, it is -80 degreeC or more and 0 degrees C or less. Moreover, after mixing, it is preferable to stir at the same temperature for 0.5 to 2 hours. The crystals obtained by filtration are preferably washed with water or the like and then dried. Or you may refine | purify further by well-known methods, such as recrystallization as needed.

As a manufacturing method of a compound (XI-I) and (XI-II), various well-known methods, for example, the method described in West Germany patent application P3928243.0 are mentioned.

As a manufacturing method of a compound (C-I) and (C-II), various well-known methods, for example, the method described in patent document 1 are mentioned.

The alkali metal salt of the anion represented by Formula (4) may use a commercially available thing, for example, by the method described in JP4097704-B or JP4341251-B and Journal of The Electrochemical Society, Vol. 148, Vol. 1, 2001. It can manufacture.

A commercially available alkali metal salt of the anion represented by the compounds (6), (7), (iii) and (iii) may be used, and can be produced, for example, by the method described in WO2008 / 075672 or JP2010-280586-A. have.

Alkali metal salts of anions containing at least one element selected from the group consisting of tungsten, silicon and phosphorus and oxygen as essential atoms can be produced by known conventional methods, but commercial products may be used as they are. As such a compound, the corresponding heteropoly acid salt, isopoly acid salt, silicate, phosphate, etc. are mentioned, for example. As these various salts, monovalent metal salts such as sodium, lithium and potassium are preferred because they are excellent in water solubility and therefore easy to synthesize and post-treat.

It is preferable that the colored curable resin composition of this invention contains the dye which uses the compound of this invention as an active ingredient as a coloring agent (henceforth "coloring agent (A)), and also contains resin further. It is further more preferable that the colored curable resin composition of this invention contains a polymeric compound (C), a polymerization initiator (D), and a solvent (E) further.

It is preferable that the colored curable resin composition of this invention contains a surface leveling agent [F] further.

It is preferable that the colored curable resin composition of this invention further contains a polymerization initiator (D1).

In this specification, the compound illustrated as each component can be used individually or in combination of multiple types unless there is particular notice.

<Coloring agent (A)>

The coloring agent (A) may be used solely as a dye containing the compound of the present invention as an active ingredient, but for further coloring, that is, to adjust the spectral characteristics, the other dye (A1), pigment (P) or These mixtures may be included.

Examples of the dye (A1) include dyes such as oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes. For example, the color index (The Society of Dyers) and Colors) and the known dyes described in the dyeing notes (Shiksensha). Moreover, according to chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, naphthoquinone dye, quinone imine dye, methine dye, azomethine dye, squarylium dye, acridine dye , Styryl dyes, coumarin dyes, quinoline dyes and nitro dyes. Among these, an organic solvent soluble dye can be used preferably.

Specifically, C.I. Solvent Yellow 4 (hereinafter, the description of C.I.Solvent Yellow is omitted, only numbers are listed), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;

C.I. Solvent red 45, 49, 125, 130, 218;

C.I. Solvent orange 2, 7, 11, 15, 26, 56;

C.I. Solvent blue 4, 5, 37, 67, 70, 90;

C.I. Solvent Green 1, 4, 5, 7, 34, 35, etc. C.I. Solvent dyes,

C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 112, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

C.I. Acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;

C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

C.I. Acid violet 6B, 7, 9, 17, 19, 30, 102;

C.I. Acid blue 1, 7, 9, 15, 18, 22, 29, 42, 59, 60, 62, 70, 72, 74, 82, 83, 86, 87, 90, 92, 93, 100, 102, 103, 104, 113, 117, 120, 126, 130, 131, 142, 147, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335;

C.I. C.I. such as acid green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109 and the like. Acid dyes,

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 136, 138, 141;

C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

C.I. Direct Blue 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, Direct dyes,

C.I. Dispulse Yellow 54, 76 and the like C.I. Disperse dye,

C.I. Basic red 1, 10;

C.I. Basic blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;

C.I. C.I. of Basic Green 1 et al. Basic Dye,

C.I. Reactive Yellow 2, 76, 116;

C.I. Reactive Orange 16;

C.I. C.I. of Reactive Red 36 et al. Reactive dyes,

C.I. Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C.I. Modern Red 1, 2, 4, 9, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32, 33, 36, 37, 38, 39, 41, 43 , 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

C.I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

C.I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

C.I. Modern Blue 1, 2, 3, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61 , 74, 77, 83, 84;

C.I. Modern Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53 and the like. Modern dyes,

C.I. C.I. Bat dye

And the like.

Among these, blue dye, violet dye, and red dye are preferable.

These dyes may be used independently and may use 2 or more types together.

Moreover, xanthene dye is preferable as classification by a chemical structure. As xanthene dye, a well-known substance can be used. For example, the compound represented by Formula (1) is preferable.

[In formula (1), R <^1> and R <^2> respectively independently represents the phenyl group which may have a substituent.

R ³ and R ⁴ each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom included in the saturated hydrocarbon group may be substituted with a halogen atom, and -CH ₂ -contained in the saturated hydrocarbon group is -O. -, -CO- or -NR ¹¹ -may be substituted.

R ¹ and R ³ may be bonded to each other to form a ring containing a nitrogen atom as one with the nitrogen atom to which they are bonded, and R ² and R ⁴ may be bonded to each other to become one with the nitrogen atom to which they are bonded to a nitrogen atom You may form the ring containing.

R ⁵ is _{-OH, -SO 3 H, -SO 3} - of _{^{Z +, -CO 2 R 8,}} -SO 3 R 8 or _{^{-SO 2 NR 9 R 10 - Z}} +, -CO 2 H, -CO 2 Indicates.

R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

m represents the integer of 0-4. When m is an integer of 2 or more, some R <^5> may be the same or different.

R <^8> represents a C1-C20 monovalent saturated hydrocarbon group, and the hydrogen atom contained in the said saturated hydrocarbon group may be substituted by the halogen atom.

Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ .

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ and R ¹⁰ are bonded to each other to form a nitrogen atom and contain 3 to 10 atoms of nitrogen. A heterocycle may be formed.

Each R ¹¹ independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms]

As a C1-C20 monovalent saturated hydrocarbon group which shows R <^8> , R <^9> , R <^10> and R <^11> , a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, C1-C20 linear alkyl groups, such as a nonyl group, a decyl group, a dodecyl group, a hexadecyl group, and an icosyl group; Branched alkyl groups having 3 to 20 carbon atoms such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; C3-C20 alicyclic saturated hydrocarbon groups, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group, are mentioned.

Examples of -CO ₂ R ^8, for example, and the like can be mentioned methoxy group, an ethoxy group, a propoxy group, a tert- butoxy group, a hexyloxy group and an oxycarbonyl group Aiko chamber.

Examples of -SO ₃ R ^8, and examples thereof include a methoxy group, etc. Four treatment groups, ethoxy procedure Four group, propoxy procedure Four group, tert- butoxy procedure Four group, hexyloxy group and PO procedure Aiko -1,3 procedure Four groups.

As —SO ₂ NR ⁹ R ¹⁰ , for example, a sulfamoyl group;

N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulf Pamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1, 2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- ( 3-methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexyl sulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamo Diary, N-heptyl sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octyl sulfamoyl group, N- (2-ethylhexyl) N-1 substituted sulfamoyl groups, such as a sulfamoyl group, N- (1,5-dimethyl) hexyl sulfamoyl group, and N- (1,1,2,2- tetramethylbutyl) sulfamoyl group;

N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfamoyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl group, etc. N-2 substituted sulfamoyl group, etc. are mentioned.

R ⁹ and R ¹⁰ may be bonded to each other to form a nitrogen-containing heterocycle of 3 to 10 atoms by becoming one with the nitrogen atom. As said heterocycle, the following are mentioned, for example.

As a C1-C10 monovalent saturated hydrocarbon group which shows R <^3> and R <^4> , a C1-C10 thing is mentioned in the above. R ³ and a hydrogen atom contained groups having 1 to 10 carbon atoms of the monovalent saturated hydrocarbon group representing the R ⁴ is optionally substituted with a halogen atom, -CH ₂ contained to said saturated hydrocarbon - is -O-, -CO-, or -NR ¹¹ -may be substituted.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.

As a saturated hydrocarbon group substituted by the halogen atom, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, a chlorobutyl group, etc. are mentioned, for example.

As a C1-C6 alkyl group which shows R <^6> and R <^7> , for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl Group, isopentyl group, neopentyl group and the like.

As a C7-10 aralkyl group which shows R <^11> , a benzyl group, a phenylethyl group, a phenylbutyl group, etc. are mentioned, for example.

Z ⁺ is ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ¹¹ ) ₄ .

As said ⁺ N (R <^11> ) _4, it is preferable that two or more of four R <^11> is a C5-C20 monovalent saturated hydrocarbon group. Moreover, 20-80 pieces are preferable and, as for the sum total carbon number of four R <^11> , 20-60 pieces are more preferable.

The phenyl group which represents R <^1> and R <^2> may have a substituent. Examples of the substituent include a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ and -SO ₂ NR ⁹ R ¹⁰ . Among these substituents, -R ⁸ is preferable, and a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is more preferable. Examples of Z ⁺ -SO ₃ ^{- -} -SO ₃ in this case is N ⁺ (R ¹¹⁾ ₄ are preferred.

As -OR <^8> , a methoxy group, an ethoxy group, a propoxy group, butoxy group, a pentyloxy group, hexyloxy group, heptyloxy group, an octyloxy group, 2-ethylhexyloxy group, an icosyloxy group etc. are mentioned, for example. Can be.

Examples of -SR ⁸ include methylsulfanyl group, ethylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, decylsulfanyl group, and icosylsulfanyl group.

Examples of -SO ₂ R ^8, and examples thereof include a methyl sulfonyl group, ethyl sulfonyl, butyl sulfonyl group, sulfonyl group, hexyl, octyl sulfonyl group, sulfonyl group Aiko chamber.

As R ³ and R ^{4, an} unsubstituted monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is preferable, a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms is more preferable, and a methyl group and an ethyl group are even more preferable.

R ¹ and R ³ may be bonded to each other to form a ring containing a nitrogen atom as one with the nitrogen atom to which they are bonded, and R ² and R ⁴ may be bonded to each other to become one with the nitrogen atom to which they are bonded to a nitrogen atom You may form the ring containing. As a ring containing the said nitrogen atom, the following are mentioned, for example.

Examples of R ⁵ -SO ₃ H, -SO ₃ ^- Z ⁺ is preferable, and -SO ₂ NR ⁹ R ^10.

As R <^6> and R <^7> , a hydrogen atom, a methyl group, and an ethyl group are preferable, and a hydrogen atom is more preferable.

The integer of 0-2 is preferable, and, as for m, it is more preferable that it is 0 or 1.

As compound (1), the compound represented by Formula (2) is preferable.

[In formula (2), R <^21> , R <^22> , R <^23> and R <^24> represent a C1-C4 alkyl group each independently.

p and q represent the integer of 0-5 independently of each other. When p is 2 or more, a plurality of R ²³ may be the same or different, and when q is 2 or more, a plurality of R ²⁴ may be the same or different.]

Examples of the alkyl group having 1 to 4 carbon atoms for R ²¹ , R ²² , R ²³ and R ²⁴ include methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and the like. Can be.

It is preferable that R ²¹ and R ²² are each independently a methyl group and an ethyl group. R ²³ and R ²⁴ are preferably methyl.

The integer of 0-2 is preferable, and, as for m and n, it is more preferable that it is 0 or 1.

As compound (1), the compound represented by Formula (3) is preferable.

[In formula (3), R <^31> and R <^32> respectively independently represents a C1-C4 alkyl group.

R ³³ and R ³⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms]

The same thing as the above is mentioned as a C1-C4 alkyl group which shows R <^31> , R <^32> , R <^33> and R <^34> . It is preferable that R ³¹ and R ³² are each independently a methyl group or an ethyl group. It is preferable that R ³³ and R ³⁴ each independently represent a hydrogen atom or a methyl group.

As compound (1), the compound represented, for example by Formula (1-1)-Formula (1-7) is mentioned, respectively. Among these, the compound represented by Formula (1-1) is preferable at the point which is excellent in the solubility with respect to the organic solvent.

As a manufacturing method of a compound (1), it is Formula (1a).

Represented by the compound, the compound represented by the formula (1) and the compound represented by the formula (1c)

[In formula (1 ') and formula (1c), R <^1> -R <^4> represents the same meaning as the above respectively.]

The method of making it react with or without an organic solvent is mentioned. In view of yield, it is preferred to react without solvent. 30 to 180 degreeC is preferable and 80 to 130 degreeC of reaction temperature is more preferable. The reaction time is preferably 1 hour to 12 hours, more preferably 3 hours to 8 hours.

As said organic solvent, Hydrocarbon solvent, such as toluene and xylene; Halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; Alcohol solvents such as methanol, ethanol and butanol; Nitrated hydrocarbon solvents such as nitrobenzene; Ketone solvents such as methyl isobutyl ketone; Amide solvents, such as 1-methyl- 2-pyrrolidone, etc. are mentioned.

The amount of the compound represented by the formula (1) and the compound represented by the formula (1c) is preferably 1 mol or more and 8 mol or less, more preferably 1 mol or more 5 to 1 mol of the compound represented by the formula (1a). It is below moles. The reaction may be carried out step by step, or may be reacted simultaneously.

Since manufacture of compound (1) is easy, it is preferable that the compound represented by Formula (1) and the compound represented by Formula (1c) are the same compound.

The method of obtaining the compound (1) which is a target compound from a reaction mixture is not specifically limited, Various well-known methods can be employ | adopted. For example, the reaction mixture can be mixed with an acid (eg acetic acid, etc.) and the precipitated crystals can be obtained by filtration. It is preferable that the said acid prepares the aqueous solution of acid previously, and then adds a reaction mixture to the said aqueous solution. The temperature at the time of adding a reaction mixture becomes like this. Preferably it is 10 degreeC or more and 50 degrees C or less. Moreover, after that, it is preferable to stir at the same temperature for 0.5 to 2 hours. The crystals obtained by filtration are preferably washed with water or the like and then dried. Or you may refine | purify further by well-known methods, such as recrystallization as needed.

It does not specifically limit as pigment (P), A well-known pigment can be used, For example, the pigment classified by the pigment in the color index (The Society of Dyers and Colourists) is mentioned.

As the pigment, for example, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 , 147, 148, 150, 153, 154, 166, 173, 194 and 214;

C.I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and the like orange pigments;

C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, ;

C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60;

C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;

C.I. Green pigments such as Pigment Green 7, 36, and 58;

C.I. Brown pigments such as Pigment Brown 23 and 25;

C.I. Pigment black 1, pigment black 7, and the like.

Pigment (P) is preferably a phthalocyanine pigment and a dioxazine pigment, more preferably C.I. Pigment blue 15: 6 and pigment violet 23 are one or more selected from the group consisting of. By including said pigment, optimization of a transmission spectrum is easy and the light resistance and chemical-resistance of a color filter become favorable.

Pigments may be rosin-treated, surface-treated using a pigment derivative having an acidic or basic group introduced therein, graft treatment on the surface of the pigment with a high molecular compound, atomization by sulfuric acid atomization, or the like, or removing impurities. In order to do this, a washing treatment with an organic solvent, water, or the like, a removal treatment by an ion exchange method of ionic impurities, or the like may be performed. It is preferable that the particle diameter of a pigment is respectively uniform.

The pigment contains a pigment dispersant and is subjected to dispersion treatment, whereby a pigment dispersion liquid in which the pigment dispersant is uniformly dispersed in a solution can be obtained. A pigment may be disperse | distributing individually, respectively, and may mix and disperse multiple types.

Examples of the pigment dispersant include pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used alone or in combination of two or more thereof. As a pigment dispersant, brand names KP [made by Shin-Etsu Chemical Co., Ltd.], Floren [made by Kyoeisha Chemical Co., Ltd.], Solsperth [made by Geneca Co., Ltd.], EFKA (made by BASF Corporation), Ajisper [Ajinomoto Fine Co., Ltd.] Techno Co., Ltd.], Disperbyk (made by BIC Chem), etc. are mentioned.

When using a pigment dispersant, its usage-amount is preferably 100 mass parts or less with respect to 100 mass parts of pigments, More preferably, it is 5 mass parts or more and 50 mass parts or less. When the usage-amount of a pigment dispersant exists in said range, there exists a tendency for the pigment dispersion liquid of a uniform dispersion state to be obtained.

The content rate of the compound (A-1) is preferably 1% by mass or more and 100% by mass or less, and more preferably 10% by mass or more and 100% by mass or less with respect to the total amount of the coloring agent (A).

When it contains dye (A1), its content rate is 0.5 mass% or more and 80 mass% or less with respect to the total amount of a coloring agent (A), More preferably, they are 40 mass% or more and 90 mass% or less. When it contains a pigment (P), its content rate is 35 mass% or more and 99 mass% or less with respect to the total amount of a coloring agent (A), More preferably, it is 1 mass% or more and 70 mass% or less, More preferably, It is 1 mass% or more and 50 mass% or less.

The content rate of the coloring agent (A) is preferably 5% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, even more preferably 5% by mass or more and 50% by mass or less, based on the total amount of solids. to be. If the content rate of a coloring agent (A) exists in the said range, desired spectroscopy and color density can be obtained.

In this specification, "total amount of solid content" means the total amount of the component remove | excluding the solvent (E) from the colored curable resin composition of this invention. The total amount of solids and the content of each component thereof can be measured by known analytical means, such as liquid chromatography or gas chromatography, for example.

<Resin>

It is preferable that resin is alkali-soluble resin. Alkali-soluble resin (hereinafter, referred to as "resin") is a copolymer containing a structural unit derived from at least one monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. to be.

As such resin, following resin [K1]-[K6] etc. are mentioned.

Resin [1] At least one monomer (a) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter referred to as "(a)"), cyclic ether structure having 2 to 4 carbon atoms and ethylenic Copolymers of monomers having an unsaturated bond (hereinafter referred to as "(iii)");

The resin (a) and (b) and the air of the monomer (c) copolymerizable with (a), but different from (a) and (v) (hereinafter referred to as "(c)"). coalescence;

Copolymers of the resins (a) and (c);

Resin [4] Resin which (v) was made to react with the copolymer of (a) and (c);

Resin [A5] (a) was made to react the copolymer of (b) and (c);

Resin [6] Resin which (a) was made to react with the copolymer of (b) and (c), and the carboxylic anhydride was made to react.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinyl benzoic acid;

Maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetra Unsaturated dicarboxylic acids such as hydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene , 5-carboxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-methylbicyclo Bicyclo unsaturated compounds containing a carboxyl group such as [2.2.1] hepto-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hepto-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, Unsaturated dicarboxylic anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride;

Unsaturated mono [(meth) acryloyloxyalkyl] of divalent or higher polyhydric carboxylic acid such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Esters;

and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule such as α- (hydroxymethyl) acrylic acid.

Among them, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity or the solubility of the obtained resin in the aqueous alkali solution.

(iii) represents, for example, an ethylenically unsaturated bond with a cyclic ether structure having 2 to 4 carbon atoms (e.g., at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) Eggplant refers to a polymerizable compound.

(VIII) The monomer which has a C2-C4 cyclic ether and a (meth) acryloyloxy group is preferable.

Moreover, in this specification, "(meth) acrylic acid" represents 1 or more types chosen from the group which consists of acrylic acid and methacrylic acid. Notation, such as "(meth) acryloyl" and "(meth) acrylate", has the same meaning.

As (iii), for example, a monomer (X1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter referred to as "(X1)") and a monomer (X2) having an oxetanyl group and an ethylenically unsaturated bond [hereinafter, "(B2)", the monomer (3) (henceforth "(3)") etc. which have a tetrahydrofuryl group and ethylenically unsaturated bond are mentioned.

As (b1), for example, a monomer having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (X1-1) (hereinafter referred to as "(X1-1)"), and an alicyclic unsaturated hydrocarbon is epoxy Monomer (X12) (hereinafter, referred to as "(X1-2)") having a structured structure is mentioned.

As (191-1) glycidyl (meth) acrylate, (beta) -methylglycidyl (meth) acrylate, (beta) -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, and o-vinyl benzylglycol Cylyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α- Methyl-p-vinylbenzylglycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl ) Styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2 , 3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) styrene, and the like. have.

Examples of (B1-2) include vinylcyclohexene monooxide and 1,2-epoxy-4-vinylcyclohexane [eg, ceoxide 2000; Daicel Corporation], 3, 4- epoxycyclohexylmethyl (meth) acrylate [for example, cyclomer A400; Daicel Corporation], 3, 4- epoxycyclohexylmethyl (meth) acrylate [for example, cyclomer M100; Daicel Corporation], the compound represented by Formula (II), the compound represented by Formula (III), etc. are mentioned.

[In formula (II) and formula (III), R ^<a> and R <^b> represent a hydrogen atom or a C1-C4 alkyl group, and the hydrogen atom contained in the said alkyl group may be substituted by the hydroxy group.

X ^a and X ^b represent a single bond, -R ^c- , * -R ^c -O-, * -R ^c -S- or * -R ^c -NH-.

R ^c represents an alkanediyl group having 1 to 6 carbon atoms.

* Represents the arm with O]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group and the like.

As an alkyl group in which a hydrogen atom was substituted by hydroxy, it is a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy The -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. are mentioned.

R ^a and R ^{b are} preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group having 1 to 6 carbon atoms include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group and pentane-1,5-diyl group And hexane-1,6-diyl group.

X ^a and X ^{b are} preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O- and * -CH ₂ CH ₂ -O-, and more preferably a single bond and * -CH ₂ CH ₂ -O- (* represents a bonding arm with O).

As a compound represented by Formula (II), the compound etc. which are represented by either of Formula (II-1)-Formula (II-15) are mentioned. Among these, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-X) or formulas (II-1 11) to formula (II-15). ) Is preferable, and the compound represented by formula (II-1), formula (II-7), formula (II-1) or formula (II-15) is more preferable.

As a compound represented by Formula (III), the compound etc. which are represented by either of Formula (III-1)-Formula (III-15) are mentioned. Among these, formula (III-1), formula (III-3), formula (III-5), formula (III-7), formula (III-V), or formulas (III-1 11) to formula (III-15) ) Is preferable, and the compound represented by formula (III-1), formula (III-7), formula (III-X), or formula (III-15) is more preferable.

The compound represented by Formula (II) and the compound represented by Formula (III) may be used independently, respectively, and may use together the compound represented by Formula (II) and the compound represented by Formula (III). When using these together, the content rate of the compound represented by Formula (II) and the compound represented by Formula (III) is preferably from 5:95 to 95: 5, more preferably from 10:90 to 90:10 on a molar basis. And even more preferably 20:80 to 80:20.

As (b2), the monomer which has an oxetanyl group and a (meth) acryloyloxy group is more preferable. As (b2), 3-methyl-3-methacryloyloxy methyl oxetane, 3-methyl-3- acryloyloxy methyl oxetane, 3-ethyl-3-methacryloyloxy methyl oxetane, 3- Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacrylo Iloxy ethyl oxetane, 3-ethyl-3- acryloyloxy ethyl oxetane, etc. are mentioned.

As (b3), the monomer which has a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of (iii) include tetrahydrofurfuryl acrylate (for example, biscot V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

(b) It is preferable that it is (b1) from the point which can further improve reliability, such as heat resistance and chemical-resistance of the color filter obtained. Furthermore, (b 1-2) is more preferable at the point which is excellent in the storage stability of colored curable resin composition.

As (c), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- butyl (meth) acrylate, 2 Ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2 -Methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate (in the art, it is commonly known as "dicyclopentanyl (meth) acrylate" Also referred to as "tricyclodecyl (meth) acrylate", tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (in the art, the common name is "dicyclopentenyl ( Methacrylate)), dicycle Lofentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, aryl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, (Meth) acrylic acid esters such as naphthyl (meth) acrylate and benzyl (meth) acrylate;

Hydroxyl group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid;

Bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxybi Cyclo [2.2.1] hepto-2-ene, 5-hydroxymethylbicyclo [2.2.1] hepto-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hepto-2 -Ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, 5,6-dihydroxybicyclo [2.2.1 ] Hepto-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hepto-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] Hepto-2-ene, 5,6-dimethoxybicyclo [2.2.1] hepto-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5 -Methylbicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2. 1] hepto-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5- Cyclohexyloxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5,6-bis (tert-butoxycarbonyl Bicyclo unsaturated compounds, such as) bicyclo [2.2.1] hepto-2-ene and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene;

N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl- Dicarbonylimide derivatives such as 6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N- (9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among them, from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyltoluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, N-phenylmaleimide, Preference is given to N-cyclohexylmaleimide, N-benzylmaleimide and bicyclo [2.2.1] hepto-2-ene.

In resin [K1], the ratio of the structural unit derived from each is in all the structural units which comprise resin [K1],

structural unit derived from (a); 2 to 60 mol%

structural units derived from (iii); 40 to 98 mol%

Is preferably,

structural unit derived from (a); 10 to 50 mol%

structural units derived from (iii); 50 to 90 mol%

More preferably.

When the ratio of the structural unit of resin [X1] exists in the said range, there exists a tendency for the storage stability of colored curable resin composition, the developability at the time of forming a coloring pattern, and the solvent resistance of the color filter obtained to be excellent.

Resin [1] is, for example, the method described in the document "Experimental method of polymer synthesis" [Okasu Takayuki, published by Chemical Co., Ltd., First Edition, First Edition, issued March 1, 1972] and the documents described above. It may be prepared with reference to the cited literature.

Specifically, the method of heating and keeping warm while putting predetermined amount of (a) and (iv), a polymerization initiator, a solvent, etc. in a reaction container, and replacing oxygen with nitrogen, for example, stirring in a deoxidation atmosphere is mentioned. have. Moreover, the polymerization initiator, solvent, etc. which are used here are not specifically limited, What is normally used in the said field | area can be used. As a polymerization initiator, For example, an azo compound [2,2'- azobisisobutyronitrile, 2,2'- azobis (2, 4- dimethylvaleronitrile), etc.] and an organic peroxide (benzoyl peroxide etc.) Examples of the solvent may be those obtained by dissolving respective monomers, and examples of the solvent (E) described below as the solvent (E) of the colored curable resin composition of the present invention may be mentioned.

Moreover, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what extracted as solid (powder) by methods, such as reprecipitation. In particular, since the solution after reaction can be used for preparation of the colored curable resin composition of this invention as it is by using the solvent contained in the colored curable resin composition of this invention as a solvent at the time of this superposition | polymerization, of the colored curable resin composition of this invention The manufacturing process can be simplified.

In resin [K2], the ratio of the structural unit derived from each is in the all the structural units which comprise resin [K2],

structural unit derived from (a); 2 to 45 mol%

structural units derived from (iii); 2 to 95 mol%

structural unit derived from (c); 1 to 65 mol%

Is preferably,

structural unit derived from (a); 5 to 40 mol%

structural units derived from (iii); 5 to 80 mol%

structural unit derived from (c); 5 to 60 mol%

More preferably.

When the ratio of the structural unit of resin is in the said range, the storage stability of a colored curable resin composition, developability at the time of forming a colored pattern, and the solvent resistance, heat resistance, and mechanical strength of the color filter obtained tend to become excellent. There is this.

Resin [K2] can be manufactured similarly to the method described as a manufacturing method of resin [K1], for example.

In resin [K3], the ratio of the structural unit derived from each is in the all the structural units which comprise resin [K3],

structural unit derived from (a); 2 to 60 mol%

structural unit derived from (c); 40 to 98 mol%

Is preferably,

structural unit derived from (a); 10 to 50 mol%

structural unit derived from (c); 50 to 90 mol%

More preferably.

Resin [K3] can be manufactured similarly to the method described as a manufacturing method of resin [K1], for example.

Resin [4] can be manufactured by obtaining the copolymer of (a) and (c), and adding the C2-C4 cyclic ether which (b) has to the carboxylic acid and / or carboxylic anhydride which (a) has Can be.

First, the copolymer of (a) and (c) is manufactured similarly to the method described as a manufacturing method of resin [K1]. In this case, it is preferable that the ratio of the structural unit derived from each is the same ratio as what was heard with resin [K3].

Next, the C2-C4 cyclic ether which (b) has is made to react with a part of carboxylic acid and / or carboxylic anhydride derived from (a) in the said copolymer.

Subsequent to the production of the copolymers of (a) and (c), the atmosphere in the flask was replaced with nitrogen from air, and (i) a reaction catalyst of carboxylic acid or carboxylic anhydride with a cyclic ether [for example, Tris (dimethylaminomethyl) phenol and the like] and a polymerization inhibitor (for example, hydroquinone and the like) and the like are placed in a flask and reacted at 60 to 130 ° C. for 1 to 10 hours to produce a resin [4]. Can be.

The use amount of (iii) is preferably 5 to 80 moles, more preferably 10 to 75 moles, relative to 100 moles of (a). By setting it as this range, there exists a tendency for the balance of the storage stability of colored curable resin composition, the developability at the time of forming a pattern, and the solvent resistance, heat resistance, mechanical strength, and the sensitivity of the pattern obtained to become favorable. Since the reactivity of a cyclic ether is high and it is hard to remain unreacted (iv), as (v) used for resin [4], (b1) is preferable and (b1-1) is still more preferable.

As for the usage-amount of the said reaction catalyst, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (iii) and (c). As for the usage-amount of the said polymerization inhibitor, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (iv) and (c).

Reaction conditions, such as a compounding method, reaction temperature, and time, can be suitably adjusted in consideration of the amount of heat generated by a manufacturing facility, polymerization, etc. In addition, the mixing method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the production equipment, polymerization, and the like in the same manner as the polymerization conditions.

Resin [K5] is carried out similarly to the manufacturing method of resin [K1] mentioned above as a 1st step, and obtains the copolymer of (i) and (c). In the same manner as described above, the obtained copolymer may be used as it is, the concentrated or diluted solution may be used, or the extracted copolymer may be used as a solid (powder) by a method such as reprecipitation.

The ratio of the structural unit derived from (iii) and (c) is respectively with respect to the total number of moles of all the structural units which comprise the said copolymer.

structural units derived from (iii); 5 to 95 mol%

structural unit derived from (c); 5 to 95 mol%

Is preferably,

structural units derived from (iii); 10 to 90 mol%

structural unit derived from (c); 10 to 90 mol%

More preferably.

Furthermore, the carboxylic acid or carboxylic anhydride which (a) has reacts with the cyclic ether derived from (i) which the copolymer of (i) and (c) has on the same conditions as the manufacturing method of resin [4]. By doing so, resin [K5] can be obtained.

As for the usage-amount of (a) made to react with said copolymer, 5-80 mol is preferable with respect to 100 mol of (iv). Since the reactivity of a cyclic ether is high and it is hard to remain unreacted, (b) is preferable as (b) used for resin [k5], and (b1-1) is still more preferable.

Resin [6] is resin which made carboxylic anhydride further react with resin [5]. A carboxylic anhydride is made to react with the hydroxyl group which arises by reaction of a cyclic ether and carboxylic acid or carboxylic anhydride.

As the carboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetra Hydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride, and the like. As for the usage-amount of carboxylic anhydride, 0.5-1 mol is preferable with respect to 1 mol of use of (a).

Specific examples of the resin include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxycyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate / (meth Resins such as) acrylic acid copolymer; Glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxy cicyclo [5.2 .1.0 ^2.6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate / (meth) acrylic acid / Resins such as vinyltoluene copolymer and 3-methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; Resins such as benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer [3] ]; Glycidyl (meth) to a resin in which glycidyl (meth) acrylate is added to a benzyl (meth) acrylate / (meth) acrylic acid copolymer, and tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer Resin, such as resin which added the acrylate and resin which added glycidyl (meth) acrylate to the tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; Of resin which made (meth) acrylic acid react with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, and tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resins such as resins in which (meth) acrylic acid is reacted with a copolymer; Resins, such as resin which made tetrahydrophthalic anhydride react with resin which (meth) acrylic acid reacted with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, etc. are mentioned. .

Resin (VIII) is preferably 1 type selected from the group which consists of resin [K1], resin [K2], and resin [K3], More preferably, it is selected from the group which consists of resin [K2] and resin [K3]. It is one kind. If it is such resin, colored curable resin composition is excellent in developability. Resin [B2] is still more preferable from a viewpoint of adhesiveness of a coloring pattern and a board | substrate.

The weight average molecular weight of polystyrene conversion of resin (B) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000. When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is also high, and the solubility in the developer of the unexposed part is good, so that the resolution of the coloring pattern tends to be improved.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of resin (B) becomes like this. Preferably it is 1.1-6, More preferably, it is 1.2-4.

The acid value of the resin is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, even more preferably 70 to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained by, for example, titration using an aqueous potassium hydroxide solution.

The content of the resin is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, still more preferably 17 to 55% by mass relative to the total amount of solids. When content of resin exists in the said range, a coloring pattern can be formed and there exists a tendency for the resolution and residual film rate of a coloring pattern to improve.

<Polymeric Compound (C)>

The polymerizable compound (C) is a compound which can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D). Examples thereof include a compound having a polymerizable ethylenically unsaturated bond, and the like. It is a (meth) acrylic acid ester compound.

As a polymeric compound which has one ethylenically unsaturated bond, nonylphenyl carbitol acrylate, 2-hydroxy-3- phenoxy propyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl, for example Acrylate, N-vinylpyrrolidone, etc., and (a), (iv), and (c) mentioned above are mentioned.

As a polymeric compound which has two ethylenically unsaturated bonds, for example, 1, 6- hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene Glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

Among these, it is preferable that a polymeric compound (C) is a polymeric compound which has three or more ethylenically unsaturated bonds. As such a polymeric compound, a trimethylol propane tri (meth) acrylate, a pentaerythritol tri (meth) acrylate, a pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, for example , Dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (Meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol Modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate Nitrate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like; among these, dipentaerythritol penta (meth) acrylate and dipenta Erythritol hexa (meth) acrylate is preferable.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 to 1,500 or less.

It is preferable that content of a polymeric compound (C) is 7-65 mass% with respect to the total amount of solid content, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%.

In addition, the content ratio [resin: polymerizable compound (C)] of the resin and the polymerizable compound (C) is preferably 20:80 to 80:20, more preferably on a mass basis. 35:65 to 80:20.

When content of a polymeric compound (C) exists in the said range, it exists in the tendency for the residual film ratio at the time of coloring pattern formation, and the chemical-resistance of a color filter to improve.

<Polymerization Initiator (D)>

The polymerization initiator (D) is not particularly limited so long as it is a compound capable of generating an active radical, an acid, or the like by the action of light or heat and can initiate polymerization, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include O-acyl oxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, acylphosphine oxide compounds and the like.

The O-acyl oxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * represents a coupling arm.

As said O-acyl oxime compound, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl, for example) ) Octan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3 , 3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] -3-cyclopentylpropane-1-one-2-imine, and the like. You may use commercially available products, such as monocure OXE01, OXE02 (above, BASF Corporation), and N-1919 (ADEKA Corporation). Among these, the O-acyl oxime compound is N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane At least one selected from the group consisting of -1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine is preferred, And N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine is more preferable.

The said alkylphenone compound is a compound which has a partial structure represented by a formula (d2) or a partial structure represented by a formula (d3), for example. In these partial structures, the benzene ring may have a substituent.

As a compound which has a partial structure represented by a formula (d2), for example, 2-methyl- 2-morpholino- 1- (4-methylsulfanylphenyl) propane- 1-one, 2-dimethylamino-1- ( 4-morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane -1-one etc. are mentioned. You may use commercial items, such as Ilgacure 369, 907, 379 (above, BASF Corporation make).

As a compound which has a partial structure represented by a formula (d3), for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2 Oligomers of -hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, (alpha), (alpha)-diethoxy acetophenone, benzyl dimethyl ketal, etc. are mentioned.

From the viewpoint of sensitivity, a compound having a partial structure represented by formula (d2) is preferable as the alkylphenone compound.

The said biimidazole compound is a compound represented by a formula (d5), for example.

[In formula (d5), R <^13> -R <^18> represents the C6-C10 aryl group which may have a substituent.]

As a C6-C10 aryl group, a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, etc. are mentioned, for example, Preferably it is a phenyl group.

As a substituent, a halogen atom, a C1-C4 alkoxy group, etc. are mentioned, for example. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example, Preferably it is a chlorine atom. As a C1-C4 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, butoxy group etc. are mentioned, for example, Preferably it is a methoxy group.

As a biimidazole compound, it is 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2,3-dichloro, for example). Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JPH06-75372-A, JPH06-75373-A, etc.), 2,2'-bis (2-chloro Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, eg, JPS48-38403-B, JPS62-174204-A, etc.), phenyl group at 4,4', 5,5'-position And imidazole compounds substituted with a carboalkoxy group (for example, see JPH07-10913-A). Among these, compounds represented by the following formula and mixtures thereof are preferable.

As said triazine compound, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl)-, for example. 6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2 -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-tri Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

2,4,6-trimethylbenzoyl diphenylphosphine oxide etc. are mentioned as said acylphosphine oxide compound.

Furthermore, as a polymerization initiator (D), Benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone, and campquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound and the like.

It is preferable to use these in combination with the polymerization initiator adjuvant (D1) [especially amines] mentioned later.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one member selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyl oxime compounds and biimidazole compounds, more preferably. Preferably it is a polymerization initiator containing an O-acyl oxime compound.

Content of a polymerization initiator (D) becomes like this. Preferably it is 0.1-40 mass parts with respect to 100 mass parts of total amounts of resin (K) and a polymeric compound (C), More preferably, it is 1-30 mass parts.

<Polymerization start preparation (D1)>

The polymerization initiator (D1) is a compound or sensitizer used to promote the polymerization of the polymerizable compound in which polymerization is initiated by the polymerization initiator. When it contains a polymerization initiator (D1), it is normally used in combination with a polymerization initiator (D).

Examples of the polymerization initiator (D1) include an amine compound, an alkoxy anthracene compound, a thioxanthone compound, a carboxylic acid compound, and the like.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, 2-dimethylaminoethyl benzoic acid and 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone [commonly known as Michler's ketone], 4,4'-bis (diethylamino) benzophenone, 4,4 '-Bis (ethylmethylamino) benzophenone and the like can be cited. Among these, 4,4'-bis (diethylamino) benzophenone is preferable. You may use commercial items, such as EAB-F (made by Hodogaya Chemical Co., Ltd.).

Examples of the alkoxy anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibu Methoxy anthracene, 2-ethyl-9, 10-dibutoxy anthracene, etc. are mentioned.

As said thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy city Oxanthone etc. are mentioned.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid and chlorophenyl Sulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxy acetic acid, naphthylthioacetic acid, N-naphthyl glycine, naphthoxy acetic acid, and the like.

When using such a polymerization initiator (D1), its content becomes like this. Preferably it is 0.1-30 mass parts with respect to 100 mass parts of total amounts of resin (K) and a polymeric compound (C), More preferably, it is 1-20. It is a mass part. When the amount of the polymerization initiator (D1) is within this range, the coloring pattern can be formed with higher sensitivity, and the productivity of the color filter tends to improve.

<Solvent (E)>

Although solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (solvent containing -COO- in a molecule and not containing -O-), an ether solvent (solvent containing -O- in a molecule and not containing -COO-), ether ester Solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and no -COO-), alcoholic solvents (containing OH in the molecule,- Solvents not containing O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.

As the ester solvent, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyric acid Butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetic acid, ethyl acetoacetic acid, cyclohexanol acetate, gamma -butyrolactone, and the like.

As the ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1 , 4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phentol, methyl anisole, etc. Can be mentioned.

As an ether ester solvent, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate butyl, ethoxy acetate methyl, ethoxy acetate ethyl, 3-methoxy propionate methyl, 3-methoxy propionate ethyl, 3-ethoxy propionate methyl, Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methyl Methyl propionate, 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl Ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol mono There may be mentioned ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate and the like.

As the ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentane Warm, cyclohexanone, isophorone and the like.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.

Benzene, toluene, xylene, mesitylene etc. are mentioned as an aromatic hydrocarbon solvent.

Examples of the amide solvents include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

These solvents may be used independently or may use 2 or more types together.

Among these, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxy propionate ethyl, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, N-methylpyrrolidone and the like are preferred. , Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 3-ethoxy Ethyl propionate, N-methylpyrrolidone and the like are more preferable.

Content of a solvent (E) becomes like this. Preferably it is 70-95 mass% with respect to the total amount of colored curable resin composition, More preferably, it is 75-92 mass%. In other words, solid content of colored curable resin composition becomes like this. Preferably it is 5-30 mass%, More preferably, it is 8-25 mass%. When content of a solvent (E) exists in the said range, since the flatness at the time of application | coating becomes good and a color filter will not run short, there exists a tendency for display characteristics to become favorable.

<Surface Leveler (F)>

Examples of the surface leveling agent (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymeric group in a side chain.

As silicone type surfactant, surfactant etc. which have a siloxane bond in a molecule | numerator are mentioned. Specifically, Torre silicon DC3PA, toray silicon SH7PA, toray silicon DC11PA, toray silicon SH21PA, toray silicon SH28PA, toray silicon SH29PA, toray silicon SH30PA, toray silicon SH8400 , KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 [Momental Performance Materials Japan Corporation ]] Etc. are mentioned.

As said fluorine-type surfactant, surfactant etc. which have a fluoro carbon chain in a molecule | numerator are mentioned. Specifically, Floroid (registered trademark) FC430, Floride FC431 (manufactured by Sumitomo 3M Co., Ltd.), Mega Pack (registered trademark) F142D, Mega Pack F171, Mega Pack F172, Mega Pack F173, Mega Pack F177, Mega Pack F183, Megapack F554, Megapack R30, Megapack RS-718-K [manufactured by DIC Corporation], FTOP® EF301, Ftop EF303, Ftop EF351, Ftop EF352 [Mitsubishi Material Electronic Chemicals ], Saffron (registered trademark) S381, Saffron S382, Saffron SC101, Saffron SC105 (made by Asahi Glass Co., Ltd.), E5844 (made by Daikin Fine Chemical Research Institute, Inc.), etc. are mentioned. have.

As silicone type surfactant which has the said fluorine atom, surfactant etc. which have a siloxane bond and a fluorocarbon chain in a molecule | numerator are mentioned. Specifically, Mega Pack (R) R08, Mega Pack BL20, Mega Pack F475, Mega Pack F477, Mega Pack F443 (manufactured by DIC Corporation), and the like.

When it contains a surface leveling agent (F), it is content with respect to the total amount of colored curable resin composition, Preferably it is 0.001 mass% or more and 0.2 mass% or less, More preferably, it is 0.002 mass% or more and 0.1 mass% or less, More preferably, they are 0.005 mass% or more and 0.07 mass% or less. If the content of the surface leveling agent (F) is within the above range, the flatness of the color filter can be further improved.

<Other ingredients>

The colored curable resin composition of this invention may contain additives known in the art, such as a filler, another high molecular compound, an adhesion promoter, antioxidant, an optical stabilizer, a chain transfer agent, as needed.

<The manufacturing method of colored curable resin composition>

The colored curable resin composition of this invention can be used, for example, a coloring agent (A), resin (B), a polymeric compound (C), a polymerization initiator (D), and a solvent (E), and the surface leveling agent which can be used as needed. It can prepare by mixing (F), a polymerization start adjuvant (D1), and other components.

The pigment in the case of containing a pigment (P) is previously mixed with a part or all of the solvent (E), and it disperse | distributes using a beads mill etc. until the average particle diameter of a pigment becomes about 0.2 micrometer or less. It is preferable. At this time, you may mix | blend a part or all of the said pigment dispersant and resin as needed. The target colored curable resin composition can be prepared by mixing in the pigment dispersion liquid obtained in this way and making the remaining component into a predetermined density | concentration.

It is preferable to dissolve compound (1) in one part or all part of solvent (E) in advance, and to prepare a solution. It is preferable to filter the said solution with the filter of about 0.01-1 micrometer of pore diameters.

It is preferable to filter the colored curable resin composition after mixing with the filter of about 0.01-10 micrometers of pore diameters.

<Manufacturing Method of Color Filter>

As a method of manufacturing a colored patterned coating film from the colored curable resin composition of this invention, the photolithographic method, the inkjet method, the printing method, etc. are mentioned. Among these, the photolithographic method is preferable. The photolithographic method is a method of apply | coating the said colored curable resin composition to a board | substrate, drying to form a coloring composition layer, exposing the said coloring composition layer by photomask insertion, and developing. In the photolithographic method, the colored coating film which is the hardened | cured material of the said coloring composition layer can be formed by not using a photomask and / or developing at the time of exposure. The coloring patterning coating film and coloring coating film which were formed in this way are the color filter of this invention.

Although the film thickness of the produced color filter is not specifically limited, According to the objective, a use, etc., it can adjust suitably, For example, it is 0.1-30 micrometers, Preferably it is 0.1-20 micrometers, More preferably, it is 0.5-6 micrometers.

Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass coated with silica on the surface, resin plates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, and aluminum on the substrate. And silver, and the thing which formed the silver / copper / palladium alloy thin film etc. can be used. Another color filter layer, a resin layer, a transistor, a circuit, etc. may be formed on such a board | substrate.

Formation of each color pixel by the photolithographic method can be performed by a known or conventional apparatus or conditions. For example, it can produce as follows.

First, a coloring curable resin composition is apply | coated on a board | substrate, volatile components, such as a solvent, are removed and dried by heat-drying (prebake) and / or vacuum drying, and a smooth coloring composition layer is obtained.

As a coating method, the spin coat method, the slit coat method, the slit & spin coat method, etc. are mentioned.

30-120 degreeC is preferable and, as for the temperature in the case of heat-drying, 50-110 degreeC is more preferable. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

When drying under reduced pressure, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.

Although the film thickness of a coloring composition layer is not specifically limited, What is necessary is just to select suitably according to the film thickness of the target color filter.

Subsequently, the coloring composition layer is exposed by sandwiching a photomask in order to form a desired colored patterned coating film. Although the pattern on the said photomask is not specifically limited, The pattern according to the intended use can be used.

As a light source used for exposure, the light source which produces the light of the wavelength of 250-450 nm is preferable. For example, light below 350 nm can be cut using a filter that cuts this wavelength range, or a band pass filter can be used that extracts light around 436 nm, near 408 nm, and around 365 nm. May be selectively extracted. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp etc. are mentioned as a light source.

An exposure apparatus such as a mask aligner and a stepper is used to irradiate the parallel light beam uniformly on the entire exposure surface or to perform a precise position combination between the photomask and the substrate on which the colored composition layer is formed. It is desirable to.

The coloring patterning coating film is formed on a board | substrate by developing the coloring composition layer after exposure contacting with a developing solution. By development, the unexposed part of a coloring composition layer melt | dissolves in a developing solution and is removed. As a developing solution, aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide, is preferable, for example. The concentration in the aqueous solution of such an alkaline compound is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Furthermore, the developing solution may contain surfactant.

The developing method may be any of a paddle method, a dipping method and a spray method. Further, the substrate may be tilted at any angle during development.

It is preferable to wash with water after image development.

Furthermore, it is preferable to postbake the obtained colored patterned coating film. 150-250 degreeC is preferable and, as for post-baking temperature, 160-235 degreeC is more preferable. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

Since the compound of this invention has a high light absorbency, especially the high brightness color filter can be manufactured with the colored curable resin composition using the same. The said color filter is useful as a color filter used for a display apparatus (for example, a liquid crystal display device, organic electroluminescent apparatus, an electronic paper, etc.) and a solid-state image sensor.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the examples,% and parts representing the content to the amount of use are based on mass unless otherwise specified.

In the following, the structure of the compound was confirmed by mass spectrometry (LC; Form Agilent 1200, MASS; Form Agilent LC / MSD).

Example 1

The following reaction was performed in nitrogen atmosphere.

After adding 36.3 parts of potassium thiocyanate and 160.0 parts of acetone to the flask provided with a cooling tube and a stirring apparatus, it stirred for 30 minutes at room temperature. Subsequently, 50.0 parts of benzoic acid chloride (made by Tokyo Kasei Co., Ltd.) was dripped over 10 minutes. After completion of dropping, the mixture was further stirred at room temperature for 2 hours. Next, after cooling the reaction mixture, 45.7 parts of N-ethyl-o-toluidine (made by Tokyo Kasei Co., Ltd.) was dripped. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, after cooling the reaction mixture, 34.2 parts of an aqueous 30% sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, 35.3 parts of chloroacetic acid were dripped under room temperature. After completion of dropping, the mixture was stirred for 7 hours under reflux. Subsequently, after cooling the reaction mixture to room temperature, the reaction solution was poured into 120.0 parts of tap water, and then 200 parts of toluene were added and stirred for 30 minutes. Subsequently, stirring was stopped and allowed to stand for 30 minutes, followed by separation into an organic layer and a water layer. After discarding the water layer by separation operation, the organic layer was washed with 200 parts of 1 N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was removed by evaporation of the solvent by an evaporator to obtain a pale yellow liquid. The pale yellow liquid obtained was purified by column chromatography. The purified pale yellow liquid was dried at 60 degreeC under reduced pressure, and 52.0 parts of compounds which are represented by a formula (XI-I-1) were obtained. Yield 50%

The following reaction was performed in nitrogen atmosphere.

9.3 parts of the compound represented by formula (VII-I-1), 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Kasei Co., Ltd.) in a flask equipped with a cooling tube and a stirring device, and toluene After adding 20.0 parts, 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100 ° C for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline solution, then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped and allowed to stand for 30 minutes, followed by separation into an organic layer and a water layer. After discarding the water layer by a separating operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The solvent was evaporated and removed by the evaporator of the obtained organic layer, and the blue-purple solid was obtained. Furthermore, a blue-purple solid was dried at 60 degreeC under reduced pressure, and 19.8 parts of compounds which are represented by a formula (A-II-1) were obtained. Yield 100%

Identification of the compound represented by formula (A-II-1)

(Mass spectrometry) ionization mode = ESI +: m / z = 601.3 [M-Cl] ⁺

                          Exact Mass: 636.3

The following reaction was performed in nitrogen atmosphere.

10.0 parts of compounds represented by formula (A-II-1), bis (trifluoromethanesulfonyl) imide lithium [manufactured by Tokyo Kasei Co., Ltd.] 4.5 parts and N, in a flask equipped with a cooling tube and a stirring device; After adding 100.0 parts of N-dimethylformamide, it stirred at 50-60 degreeC for 3 hours. Subsequently, after cooling the reaction mixture to room temperature, it is dripped at 2000.0 parts of tap waters, stirring for 1 hour, and a dark blue suspension is obtained. Filtration of the obtained suspension gave a turquoise solid. Furthermore, the turquoise solid was dried at 60 degreeC under reduced pressure, and 11.3 parts of compounds which are represented by a formula (AI-1) were obtained. Yield 82%

0.35 g of the compound represented by the formula (A-I-1) is dissolved in chloroform to make a volume of 250 cm 3, of which 2 cm 3 is diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound indicated an absorbance of 2.9 (arbitrary unit) at λmax = 628 nm.

Synthesis Example 1

An appropriate amount of nitrogen was flowed into a flask equipped with a reflux cooler, a dropping funnel, and a stirrer to obtain a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was added thereto, and the mixture was heated to 85 ° C while stirring. Subsequently, in the flask, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decane-9- A solution in which 171 parts of a mixture of monoacrylates (content ratio is 50:50 in a molar ratio) (trade name "E-DCPA", manufactured by Daicel Co., Ltd.) was dissolved in 40 parts of propylene glycol monomethyl ether acetate was added dropwise using a pump. Was dripped over about 5 hours. In addition, the flask which melt | dissolved the solution which melt | dissolved 26 parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetates, was used for about 5 hours, using a separate dropping pump. It dripped in the inside. After completion of the dropwise addition of the polymerization initiator, the mixture was kept at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer [resin (X-1)] having a solid content of 43.5%. The weight average molecular weight of obtained resin (XI-1) was 8000, the molecular weight distribution was 1.98, and the acid value of conversion of solid content was 53 mg-KOH / g.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of polystyrene conversion of resin was performed on condition of the following by GPC method.

Equipment: HLC-8120GPC [manufactured by Tosso Corporation]

Column: TSK-GELG2000HXL

Column temperature: 40 ℃

Solvent: THF

Flow rate: 1.0 mL / min

Test liquid solid concentration: 0.001 to 0.01 mass%

Injection volume: 50 μL

Detector: RI

Calibration standard: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500

The ratio (Mw / Mn) of the weight average molecular weight and number average molecular weight of polystyrene conversion obtained above was made into molecular weight distribution.

Synthesis Example 2

250.4 parts of propylene glycol monomethyl ether acetate was taken into a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the mixture was stirred with nitrogen, and heated to 120 ° C. Next, a monomer mixture consisting of 37.4 parts of methacrylic acid, 61.3 parts of benzyl methacrylate, 18.5 parts of glycidyl methacrylate, and 19.2 parts of monomethacrylate (Hitachi Kasei Co., Ltd. FA-513M) having a tricyclodecane skeleton. 6.13 parts of t-butyl hydroperoxide [Perbutyl O made by Nippon Oil Industries, Ltd.] was added. This was dropped into the flask over 2 hours from the dropping funnel, and further aged at 120 ° C. for 2 hours to carry out aging. Subsequently, the flask was replaced with air to be replaced, and 0.9 parts of trisdimethylaminomethylphenol (DMP-30) and 0.145 parts of hydroquinone were added to 10.6 parts of acrylic acid during the aging, and the reaction was continued at 120 ° C. for 6 hours. A solution of a copolymer [resin (X-2)] of 38.4 mass% and an acid value of 122 mg-KOH / g was obtained. The weight average molecular weight (Mw) of obtained resin (B-2) was 10700, and molecular weight distribution was 2.18. The weight average molecular weight and molecular weight distribution were measured by the same method as resin (XI-1).

Synthesis Example 3

To 2.00 parts of sodium hydroxide [manufactured by Wako Pure Chemical Industries, Ltd.], 50 parts of methanol was added and dissolved. Further, 15.41 parts of 2,6-dihydroxybenzoic acid (manufactured by Tokyo Kasei Co., Ltd.) and 3.09 parts of boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) were added, and the mixture was stirred at 65 ° C for 8.5 hours. After cooling the mixture to room temperature, the precipitate was obtained by suction filtration and washed with 237 parts of ion-exchanged water to obtain 10.90 parts of the compound represented by the formula (BCC-Na).

Example 2

The following reaction was performed in nitrogen atmosphere.

10.0 parts of the compound represented by the formula (A-II-1), 5.3 parts of the compound represented by the formula (BC-1-NA) and 100.0 parts of N, N-dimethylformamide were charged into a flask equipped with a cooling tube and a stirring device. It stirred at 50-60 degreeC for 3 hours. Subsequently, after cooling the reaction mixture to room temperature, it is dripped at 2000.0 parts of tap waters, stirring for 1 hour, and a dark blue suspension is obtained. Filtration of the obtained suspension gave a turquoise solid. Furthermore, the turquoise solid was dried at 60 degreeC under reduced pressure, and 12.0 parts of compounds which are represented by a formula (A-I-3) were obtained. Yield 83%

0.35 g of the compound represented by the formula (A-I-3) is dissolved in chloroform to make a volume of 250 cm 3, of which 2 cm 3 is diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound indicated an absorbance of 2.6 (arbitrary unit) at λmax = 628 nm.

Example 3

The following reaction was performed in nitrogen atmosphere.

10.0 parts of the compound represented by the formula (A-II-1), 14.1 parts of tungstosilicate hydrate (manufactured by SIGMA-ALDRICH) and 100.0 parts of N, N-dimethylformamide were charged into a flask equipped with a cooling tube and a stirring device. It stirred at 50-60 degreeC for 3 hours. Subsequently, after cooling the reaction mixture to room temperature, it is dripped at 2000.0 parts of tap waters, stirring for 1 hour, and a dark blue suspension is obtained. Filtration of the obtained suspension gave a turquoise solid. Furthermore, the turquoise solid was dried at 60 degreeC under reduced pressure, and 17.3 parts of compounds which are represented by Formula (A-I-4) were obtained. Yield 83%

0.35 g of the compound represented by the formula (A-I-4) was dissolved in chloroform to make a volume of 250 cm 3, of which 2 cm 3 was diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound indicated an absorbance of 1.5 (arbitrary units) at λ max = 638 nm.

Example 4

The following reaction was performed in nitrogen atmosphere.

After adding 32.2 parts of potassium thiocyanate and 160.0 parts of acetone to the flask provided with a cooling tube and a stirring apparatus, it stirred for 30 minutes at room temperature. Next, 50.0 parts of 2-fluorobenzoic acid chloride (made by Tokyo Kasei Co., Ltd.) was dripped over 10 minutes. After completion of dropping, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture, 40.5 parts of N-ethyl-o-toluidine (made by Tokyo Kasei Co., Ltd.) was dripped. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, after cooling the reaction mixture, 34.2 parts of an aqueous 30% sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, 31.3 parts of chloroacetic acid were added dropwise under room temperature. After completion of dropping, the mixture was stirred for 7 hours under reflux. Subsequently, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, and then 200 parts of toluene were added and stirred for 30 minutes. Subsequently, stirring was stopped and allowed to stand for 30 minutes, followed by separation into an organic layer and a water layer. After discarding the water layer by a separating operation, the organic layer was washed with 200 parts of 1 N hydrochloric acid, followed by 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was removed by evaporation of the solvent by an evaporator to obtain a pale yellow liquid. The pale yellow liquid obtained was purified by column chromatography. The purified pale yellow liquid was dried at 60 degreeC under reduced pressure, and 49.9 parts of compounds which are represented by a formula (VII-I-7) were obtained. Yield 51%

The following reaction was performed in nitrogen atmosphere. 9.9 parts of compounds represented by formula (VII-I-7), 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Kasei Co., Ltd.) in a flask equipped with a cooling tube and a stirring device, and toluene After adding 20.0 parts, 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100 ° C for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline solution, then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped and allowed to stand for 30 minutes, followed by separation into an organic layer and a water layer. After discarding the water layer by a separating operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The solvent was evaporated and removed by the evaporator of the obtained organic layer, and the blue-purple solid was obtained. The resulting blue violet solid was purified by column chromatography. The purified blue-purple solid was dried at 60 degreeC under reduced pressure, and 17.2 parts of compounds which are represented by Formula (A-II-7) were obtained. Yield 85%

Identification of the compound represented by formula (A-II-7)

(Mass spectrometry) ionization mode = ESI +: m / z = 619.3 [M-Cl] ⁺

                          Exact Mass: 654.3

The following reaction was performed in nitrogen atmosphere. 10.0 parts of compounds represented by Formula (A-II-7), bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Kasei Co., Ltd.) in a flask equipped with a cooling tube and a stirring device, and N, After adding 30.0 parts of N-dimethylformamide, it stirred at 40 degreeC for 3 hours. Subsequently, after cooling the reaction mixture to room temperature, it is dripped at 500.0 parts of tap waters, stirring for 1 hour, and a dark blue suspension is obtained. Filtration of the obtained suspension gave a turquoise solid. Furthermore, the turquoise solid was dried at 60 degreeC under reduced pressure, and 11.9 parts of compounds which are represented by Formula (A-I-7) were obtained. Yield 86%

0.35 g of the compound represented by the formula (A-I-7) was dissolved in chloroform to make a volume of 250 cm 3, of which 2 cm 3 was diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound indicated an absorbance of 3.1 (arbitrary units) at λ max = 630 nm.

Example 5

The following reaction was performed in nitrogen atmosphere.

23.3 parts of potassium thiocyanate and 160.0 parts of acetone were added to a flask equipped with a cooling tube and a stirring device, followed by stirring for 30 minutes at room temperature. Next, 50.0 parts of 2-bromobenzoic acid chloride (made by Tokyo Kasei Co., Ltd.) were dripped over 10 minutes. After completion of dropping, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture, 29.3 parts of N-ethyl-o-toluidine (manufactured by Tokyo Kasei Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, after cooling the reaction mixture, 34.2 parts of an aqueous 30% sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, 22.6 parts of chloroacetic acid were added dropwise at room temperature. After completion of dropping, the mixture was stirred for 7 hours under reflux. Subsequently, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, and then 200 parts of toluene were added and stirred for 30 minutes. Subsequently, stirring was stopped and allowed to stand for 30 minutes, followed by separation into an organic layer and a water layer. After discarding the water layer by a separating operation, the organic layer was washed with 200 parts of 1 N hydrochloric acid, followed by 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was removed by evaporation of the solvent by an evaporator to obtain a pale yellow liquid. The pale yellow liquid obtained was purified by column chromatography. The purified pale yellow liquid was dried at 60 degreeC under reduced pressure, and 41.6 parts of compounds which are represented by a formula (VII-II-V) were obtained. Yield 45%

The following reaction was performed in nitrogen atmosphere. 12.9 parts of compounds represented by formula (VII-II), 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Kasei Co., Ltd.) in a flask equipped with a cooling tube and a stirring device, and toluene After adding 20.0 parts, 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100 ° C for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline solution, then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped and allowed to stand for 30 minutes, followed by separation into an organic layer and a water layer. After discarding the water layer by a separating operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The solvent was evaporated and removed by the evaporator of the obtained organic layer, and the blue-purple solid was obtained. The resulting blue violet solid was purified by column chromatography. The purified blue-purple solid was dried at 60 degreeC under reduced pressure, and 17.6 parts of compounds which are represented by a formula (A-II-IX) were obtained. Yield 80%

Identification of the compound represented by formula (A-II-X)

(Mass spectrometry) ionization mode = ESI +: m / z = 679.3 [M-Cl] ⁺

                          Exact Mass: 714.2

The following reaction was performed in nitrogen atmosphere.

10.0 parts of compounds represented by formula (A-II-X), bis (trifluoromethanesulfonyl) imide lithium [manufactured by Tokyo Kasei Co., Ltd.] 5.2 parts and N, in a flask equipped with a cooling tube and a stirring device; After adding 30.0 parts of N-dimethylformamide, it stirred at 40 degreeC for 3 hours. Subsequently, after cooling the reaction mixture to room temperature, it is dripped at 500.0 parts of tap waters, stirring for 1 hour, and a dark blue suspension is obtained. Filtration of the obtained suspension gave a turquoise solid. Furthermore, the turquoise solid was dried at 60 degreeC under reduced pressure, and 12.9 parts of compounds which are represented by a formula (A-II-X) were obtained. Yield 96%

0.35 g of the compound represented by the formula (A-I-X) is dissolved in chloroform to make a volume of 250 cm 3, of which 2 cm 3 is diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound indicated an absorbance of 2.6 (arbitrary unit) at λ max = 632 nm.

Example 6

The following reaction was performed in nitrogen atmosphere.

After adding 33.0 parts of potassium thiocyanate and 160.0 parts of acetone to the flask provided with a cooling tube and a stirring apparatus, it stirred for 30 minutes at room temperature. Next, 50.0 parts of 2-methyl-benzoic acid chloride (made by Tokyo Kasei Co., Ltd.) were dripped over 10 minutes. After completion of dropping, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture, 41.6 parts of N-ethyl-o-toluidine (manufactured by Tokyo Kasei Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, after cooling the reaction mixture, 34.2 parts of an aqueous 30% sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, 32.1 parts of chloroacetic acid were added dropwise under room temperature. After completion of dropping, the mixture was stirred for 7 hours under reflux. Subsequently, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, and then 200 parts of toluene were added and stirred for 30 minutes. Subsequently, stirring was stopped and allowed to stand for 30 minutes, followed by separation into an organic layer and a water layer. After discarding the water layer by a separating operation, the organic layer was washed with 200 parts of 1 N hydrochloric acid, followed by 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was removed by evaporation of the solvent by an evaporator to obtain a pale yellow liquid. The pale yellow liquid obtained was purified by column chromatography. The purified pale yellow liquid was dried at 60 degreeC under reduced pressure, and 40.5 parts of compounds which are represented by a formula (VII-IX) were obtained. Yield 41%

The following reaction was performed in nitrogen atmosphere. 9.7 parts of compounds represented by a formula (VII-II), 4,4'-bis (diethylamino) benzophenone (made by Tokyo Kasei Co., Ltd.) in a flask equipped with a cooling tube and a stirring device, and toluene After adding 20.0 parts, 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100 ° C for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline solution, then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped and allowed to stand for 30 minutes, followed by separation into an organic layer and a water layer. After discarding the water layer by a separating operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The solvent was evaporated and removed by the evaporator of the obtained organic layer, and the blue-purple solid was obtained. The resulting blue violet solid was purified by column chromatography. The purified blue-purple solid was dried at 60 degreeC under reduced pressure, and 15.1 parts of compounds which are represented by a formula (A-II-IX) were obtained. Yield 75%

Identification of the compound represented by formula (A-II-X)

(Mass spectrometry) ionization mode = ESI +: m / z = 615.4 [M-Cl] ⁺

                          Exact Mass: 650.3

The following reaction was performed in nitrogen atmosphere. 10.0 parts of compounds represented by formula (A-II-X), bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Kasei Co., Ltd.) in a flask equipped with a cooling tube and a stirring device, and N, After adding 30.0 parts of N-dimethylformamide, it stirred at 40 degreeC for 3 hours. Subsequently, after cooling the reaction mixture to room temperature, it is dripped at 500.0 parts of tap waters, stirring for 1 hour, and a dark blue suspension is obtained. Filtration of the obtained suspension gave a turquoise solid. Furthermore, the turquoise solid was dried at 60 degreeC under reduced pressure, and 13.2 parts of compounds which are represented by a formula (A-II-X) were obtained. Yield 96%

0.35 g of the compound represented by the formula (A-I-X) is dissolved in chloroform to make a volume of 250 cm 3, of which 2 cm 3 is diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound indicated an absorbance of 2.7 (arbitrary units) at lambda max = 627 nm.

Example 7

The following reaction was performed in nitrogen atmosphere.

After adding 24.5 parts of potassium thiocyanate and 160.0 parts of acetone to the flask provided with a cooling tube and a stirring apparatus, it stirred for 30 minutes at room temperature. Next, 50.0 parts of 2-trifluoromethylbenzoic acid chloride (made by Tokyo Kasei Co., Ltd.) were dripped over 10 minutes. After completion of dropping, the mixture was further stirred at room temperature for 2 hours. Next, after cooling the reaction mixture, 30.8 parts of N-ethyl-o-toluidine (manufactured by Tokyo Kasei Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, after cooling the reaction mixture, 34.2 parts of an aqueous 30% sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, 23.8 parts of chloroacetic acid were added dropwise under room temperature. After completion of dropping, the mixture was stirred for 7 hours under reflux. Subsequently, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, and then 200 parts of toluene were added and stirred for 30 minutes. Subsequently, stirring was stopped and allowed to stand for 30 minutes, followed by separation into an organic layer and a water layer. After discarding the water layer by a separating operation, the organic layer was washed with 200 parts of 1 N hydrochloric acid, followed by 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was removed by evaporation of the solvent by an evaporator to obtain a pale yellow liquid. The pale yellow liquid obtained was purified by column chromatography. The purified pale yellow liquid was dried at 60 degreeC under reduced pressure, and 31.1 parts of compounds which are represented by a formula (XI-I-10) were obtained. Yield 36%

The following reaction was performed in nitrogen atmosphere. 11.4 parts of compounds represented by a formula (VII-I-10), 4,4'-bis (diethylamino) benzophenone (made by Tokyo Kasei Co., Ltd.) to a flask equipped with a cooling tube and a stirring device, and toluene After adding 20.0 parts, 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100 ° C for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline solution, then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped and allowed to stand for 30 minutes, followed by separation into an organic layer and a water layer. After discarding the water layer by a separating operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The solvent was evaporated and removed by the evaporator of the obtained organic layer, and the blue-purple solid was obtained. The resulting blue violet solid was purified by column chromatography. The purified blue-purple solid was dried at 60 degreeC under reduced pressure, and 15.2 parts of compounds which are represented by a formula (A-II-10) were obtained. Yield 70%

Identification of Compound Represented by Formula (A-II-10)

(Mass spectrometry) ionization mode = ESI +: m / z = 669.3 [M-Cl] ⁺

                          Exact Mass: 704.3

The following reaction was performed in nitrogen atmosphere. 10.0 parts of compounds represented by Formula (A-II-10), bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Kasei Co., Ltd.) 4.1 parts and N, in a flask equipped with a cooling tube and a stirring device; After adding 30.0 parts of N-dimethylformamide, it stirred at 40 degreeC for 3 hours. Subsequently, after cooling the reaction mixture to room temperature, when it is dripped at 500.0 parts of tap water, stirring for 1 hour, a dark blue suspension is obtained. Filtration of the obtained suspension gave a turquoise solid. Furthermore, the turquoise solid was dried at 60 degreeC under reduced pressure, and 11.4 parts of compounds which are represented by a formula (AI-10) were obtained. Yield 85%

0.35 g of the compound represented by formula (AI-10) is dissolved in chloroform to make a volume of 250 cm 3, of which 2 cm 3 is diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound indicated an absorbance of 1.9 (arbitrary units) at λ max = 631 nm.

Example 8

The following reaction was performed in nitrogen atmosphere.

After adding 33.0 parts of potassium thiocyanate and 160.0 parts of acetone to the flask provided with a cooling tube and a stirring apparatus, it stirred for 30 minutes at room temperature. Next, 50.0 parts of 2-methyl-benzoic acid chloride (made by Tokyo Kasei Co., Ltd.) were dripped over 10 minutes. After completion of dropping, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture, 39.7 parts of dibutylamine (manufactured by Tokyo Kasei Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, after cooling the reaction mixture, 34.2 parts of an aqueous 30% sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, 32.1 parts of chloroacetic acid were added dropwise under room temperature. After completion of dropping, the mixture was stirred for 7 hours under reflux. Subsequently, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, and then 200 parts of toluene were added and stirred for 30 minutes. Subsequently, stirring was stopped and allowed to stand for 30 minutes, followed by separation into an organic layer and a water layer. After discarding the water layer by a separating operation, the organic layer was washed with 200 parts of 1 N hydrochloric acid, followed by 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was removed by evaporation of the solvent by an evaporator to obtain a pale yellow liquid. The pale yellow liquid obtained was purified by column chromatography. The purified pale yellow liquid was dried at 60 degreeC under reduced pressure, and 70.0 parts of compounds which are represented by a formula (XI-I-11) were obtained. Yield 72%

The following reaction was performed in nitrogen atmosphere. 9.6 parts of compounds represented by formula (VII-I-1), 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Kasei Co., Ltd.) in a flask equipped with a cooling tube and a stirring device, and toluene After adding 20.0 parts, 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100 ° C for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline solution, then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped and allowed to stand for 30 minutes, followed by separation into an organic layer and a water layer. After discarding the water layer by a separating operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The solvent was evaporated and removed by the evaporator of the obtained organic layer, and the blue-purple solid was obtained. The resulting blue violet solid was purified by column chromatography. The purified blue-purple solid was dried at 60 degreeC under reduced pressure, and 19.7 parts of compounds which are represented by Formula (A-II-111) were obtained. Yield 98%

Identification of Compound Represented by Formula (A-II-1 11)

(Mass spectrometry) ionization mode = ESI +: m / z = 609.4 [M-Cl] ⁺

                          Exact Mass: 644.4

The following reaction was performed in nitrogen atmosphere. 10.0 parts of compounds represented by formula (A-II-111), bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Kasei Co., Ltd.) 4.4 parts and N, in a flask equipped with a cooling tube and a stirring device. After adding 30.0 parts of N-dimethylformamide, it stirred at 40 degreeC for 3 hours. Subsequently, after cooling the reaction mixture to room temperature, it is dripped at 500.0 parts of tap waters, stirring for 1 hour, and a dark blue suspension is obtained. Filtration of the obtained suspension gave a turquoise solid. Furthermore, the turquoise solid was dried at 60 degreeC under reduced pressure, and 11.7 parts of compounds which are represented by a formula (AII-11) were obtained. Yield 85%

0.35 g of the compound represented by the formula (AI-11) was dissolved in chloroform to make a volume of 250 cm 3, 2 cm 3 of which was diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound indicated an absorbance of 3.0 (arbitrary units) at lambda max = 613 nm.

Example 9

The following reaction was performed in nitrogen atmosphere.

29.2 parts of potassium thiocyanate and 160.0 parts of acetone were thrown into the flask provided with a cooling tube and the stirring apparatus, and it stirred for 30 minutes at room temperature. Next, 50.0 parts of 2-chlorobenzoic acid chloride (made by Tokyo Kasei Co., Ltd.) were dripped over 10 minutes. After completion of dropping, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture, 43.8 parts of bis (2-ethoxyethyl) amine (manufactured by Tokyo Kasei Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, after cooling the reaction mixture, 34.2 parts of an aqueous 30% sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, 28.4 parts of chloroacetic acid were dripped under room temperature. After completion of dropping, the mixture was stirred for 7 hours under reflux. Subsequently, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, and then 200 parts of toluene were added and stirred for 30 minutes. Subsequently, stirring was stopped and allowed to stand for 30 minutes, followed by separation into an organic layer and a water layer. After discarding the water layer by a separating operation, the organic layer was washed with 200 parts of 1 N hydrochloric acid, followed by 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was removed by evaporation of the solvent by an evaporator to obtain a pale yellow liquid. The pale yellow liquid obtained was purified by column chromatography. The purified pale yellow liquid was dried at 60 degreeC under reduced pressure, and 45.0 parts of compounds which are represented by a formula (XI-I-12) were obtained. Yield 44%

The following reaction was performed in nitrogen atmosphere. 10.6 parts of compounds represented by the formula (VII-I-12), 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Kasei Co., Ltd.) in a flask equipped with a cooling tube and a stirring device, and toluene After adding 20.0 parts, 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100 ° C for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline solution, then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped and allowed to stand for 30 minutes, followed by separation into an organic layer and a water layer. After discarding the water layer by a separating operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The solvent was evaporated and removed by the evaporator of the obtained organic layer, and the blue-purple solid was obtained. The resulting blue violet solid was purified by column chromatography. The purified blue-purple solid was dried at 60 degreeC under reduced pressure, and 21.3 parts of compounds which are represented by a formula (A-II-12) were obtained. Yield 99%

Identification of the compound represented by formula (A-II-1 12)

(Mass spectrometry) ionization mode = ESI +: m / z = 661.3 [M-Cl] ⁺

                          Exact Mass: 696.3

The following reaction was performed in nitrogen atmosphere. 10.0 parts of the compound represented by Formula (A-II-12), bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Kasei Co., Ltd.) 4.1 parts and N, in a flask equipped with a cooling tube and a stirring device. After adding 30.0 parts of N-dimethylformamide, it stirred at 40 degreeC for 3 hours. Subsequently, after cooling the reaction mixture to room temperature, it is dripped at 500.0 parts of tap waters, stirring for 1 hour, and a dark blue suspension is obtained. Filtration of the obtained suspension gave a turquoise solid. Furthermore, the turquoise solid was dried at 60 degreeC under reduced pressure, and 11.4 parts of compounds which are represented by a formula (AII-12) were obtained. Yield 85%

0.35 g of the compound represented by the formula (A-I-12) was dissolved in chloroform to make a volume of 250 cm 3, of which 2 cm 3 was diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound indicated an absorbance of 2.5 (arbitrary units) at lambda max = 625 nm.

Example 10

The following reaction was performed in nitrogen atmosphere.

5.0 parts of 2-bromo-4 '-(methylsulfonyl) acetophenone (manufactured by Tokyo Kasei Co., Ltd.) and 50.0 parts of 50% isopropanol aqueous solution were added to a flask equipped with a cooling tube and a stirring device. Stirred to min. Then 2.6 parts of potassium thiocyanate were added over 10 minutes. After the addition was completed, the mixture was further stirred at room temperature for 3 hours. Subsequently, 50.0 parts of tap water was dripped. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. After the precipitated yellow solid was separated by filtration, the obtained yellow solid was purified by column chromatography. The refined yellow solid was dried at 60 degreeC under reduced pressure, and 1.0 part of compounds which are represented by a formula (VII-II-13) were obtained. Yield 22%

The following reaction was performed in nitrogen atmosphere. 5.0 parts of compounds and 50.0 parts of ethanol which were represented by Formula (XII-13) were put into the flask provided with a cooling tube and the stirring apparatus, and it stirred for 30 minutes at room temperature. Subsequently, 2.5 parts of piperidine (made by Tokyo Kasei Co., Ltd.) and 1.2 parts of glacial acetic acid were dripped over 10 minutes, respectively. After completion of the dropwise addition, the mixture was further stirred for 2 hours under reflux. After the reaction solution was allowed to cool to room temperature, 70.0 parts of tap water was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. After the precipitated yellow solid was separated by filtration, the obtained yellow solid was purified by column chromatography. The refined yellow solid was dried at 60 degreeC under reduced pressure, and 3.8 parts of compounds which are represented by a formula (XI-I-13) were obtained. Yield 61%

The following reaction was performed in nitrogen atmosphere.

10.2 parts of the compound represented by the formula (VII-I-13), 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Kasei Co., Ltd.) in a flask equipped with a cooling tube and a stirring device, and toluene After adding 20.0 parts, 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100 ° C for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline solution, then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped and allowed to stand for 30 minutes, followed by separation into an organic layer and a water layer. After discarding the water layer by a separating operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The solvent was evaporated and removed by the evaporator of the obtained organic layer, and the blue-purple solid was obtained. The resulting blue violet solid was purified by column chromatography. The purified blue-purple solid was dried at 60 degreeC under reduced pressure, and 6.8 parts of compounds which are represented by a formula (A-II-13) were obtained. Yield 33%

Identification of the compound represented by formula (AA-13)

(Mass spectrometry) ionization mode = ESI +: m / z = 629.3 [M-Cl] ⁺

                          Exact Mass: 664.3

The following reaction was performed in nitrogen atmosphere. 10.0 parts of compounds represented by formula (A-II-1), bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Kasei Co., Ltd.) 4.7 parts and N, in a flask equipped with a cooling tube and a stirring device. After adding 30.0 parts of N-dimethylformamide, it stirred at 40 degreeC for 3 hours. Subsequently, after cooling the reaction mixture to room temperature, it is dripped at 500.0 parts of tap waters, stirring for 1 hour, and a dark blue suspension is obtained. Filtration of the obtained suspension gave a turquoise solid. Furthermore, the turquoise solid was dried at 60 degreeC under reduced pressure, and 11.4 parts of compounds which are represented by a formula (AI-13) were obtained. Yield 80%

0.35 g of the compound represented by formula (AI-13) was dissolved in chloroform to make a volume of 250 cm 3, and 2 cm 3 of this was diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound indicated an absorbance of 2.5 (arbitrary units) at λ max = 636 nm.

Example 11

The following reaction was performed in nitrogen atmosphere.

5.0 parts of 4-chlorophenacyl bromide (made by Tokyo Kasei Co., Ltd.) and 50.0 parts of 50% isopropanol aqueous solution were thrown into the flask provided with a cooling tube and the stirring apparatus, and it stirred for 30 minutes at room temperature. Subsequently, 3.1 parts of potassium thiocyanate was added over 10 minutes. After the addition was completed, the mixture was further stirred at room temperature for 3 hours. Subsequently, 50.0 parts of tap water was dripped. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. After the precipitated yellow solid was separated by filtration, the obtained yellow solid was purified by column chromatography. The refined yellow solid was dried at 60 degreeC under reduced pressure, and 4.0 parts of compounds which are represented by a formula (VII-II-14) were obtained. Yield 89%

The following reaction was performed in nitrogen atmosphere.

5.0 parts of compounds and 50.0 parts of ethanol which were represented by Formula (XII-146) were thrown into the flask provided with a cooling tube and the stirring apparatus, and it stirred at room temperature for 30 minutes. Subsequently, 3.0 parts of piperidine (made by Tokyo Kasei Co., Ltd.) and 1.4 parts of glacial acetic acid were dripped over 10 minutes, respectively. After completion of the dropwise addition, the mixture was further stirred for 2 hours under reflux. After the reaction solution was allowed to cool to room temperature, 70.0 parts of tap water was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. After the precipitated yellow solid was separated by filtration, the obtained yellow solid was purified by column chromatography. The refined yellow solid was dried at 60 degreeC under reduced pressure, and 3.7 parts of compounds which are represented by a formula (XI-I-14) were obtained. Yield 57%

The following reaction was performed in nitrogen atmosphere.

8.8 parts of the compound represented by a formula (VII-IV-1), 4,4'-bis (diethylamino) benzophenone (made by Tokyo Kasei Co., Ltd.) to a flask equipped with a cooling tube and a stirring device, and toluene After adding 20.0 parts, 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100 ° C for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline solution, then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped and allowed to stand for 30 minutes, followed by separation into an organic layer and a water layer. After discarding the water layer by a separating operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The solvent was evaporated and removed by the evaporator of the obtained organic layer, and the blue-purple solid was obtained. The resulting blue violet solid was purified by column chromatography. The purified blue-purple solid was dried at 60 degreeC under reduced pressure, and 5.3 parts of compounds which are represented by a formula (A-II-14) were obtained. Yield 26%

Identification of Compound Represented by Formula (A-II-1)

(Mass spectrometry) ionization mode = ESI +: m / z = 585.3 [M-Cl] ⁺

                          Exact Mass: 620.3

The following reaction was performed in nitrogen atmosphere.

10.0 parts of the compound represented by Formula (A-II-12.4), potassium tris (trifluoromethanesulfonyl) methide (manufactured by Central Glass Co., Ltd.) in a flask equipped with a cooling tube and a stirring device, and N After adding 30.0 parts of, N-dimethylformamide, the mixture was stirred at 40 ° C for 3 hours. Subsequently, after cooling the reaction mixture to room temperature, it is dripped at 500.0 parts of tap waters, stirring for 1 hour, and a dark blue suspension is obtained. Filtration of the obtained suspension gave a turquoise solid. Furthermore, the turquoise solid was dried at 60 degreeC under reduced pressure, and 13.6 parts of compounds which are represented by Formula (A-I-14) were obtained. Yield 85%

0.35 g of the compound represented by the formula (A-I-14) was dissolved in chloroform to make a volume of 250 cm 3, of which 2 cm 3 was diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound indicated an absorbance of 2.7 (arbitrary units) at λmax = 623 nm.

Example 12

The following reaction was performed in nitrogen atmosphere.

After adding 33.0 parts of potassium thiocyanate and 160.0 parts of acetone to the flask provided with a cooling tube and a stirring apparatus, it stirred for 30 minutes at room temperature. Subsequently, 50.0 parts of benzoic acid chloride (made by Tokyo Kasei Co., Ltd.) was dripped over 10 minutes. After completion of dropping, the mixture was further stirred at room temperature for 2 hours. Next, after cooling the reaction mixture, 41.6 parts of N-isopropyl aniline (manufactured by Tokyo Kasei Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, after cooling the reaction mixture, 34.2 parts of an aqueous 30% sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, 32.1 parts of chloroacetic acid were added dropwise under room temperature. After completion of dropping, the mixture was stirred for 7 hours under reflux. Subsequently, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, and then 200 parts of toluene were added and stirred for 30 minutes. Subsequently, stirring was stopped and allowed to stand for 30 minutes, followed by separation into an organic layer and a water layer. After discarding the water layer by a separating operation, the organic layer was washed with 200 parts of 1 N hydrochloric acid, followed by 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was removed by evaporation of the solvent by an evaporator to obtain a pale yellow liquid. The pale yellow liquid obtained was purified by column chromatography. The purified pale yellow liquid was dried at 60 degreeC under reduced pressure, and 44.8 parts of compounds which are represented by a formula (XI-I-15) were obtained. Yield 47%

The following reaction was performed in nitrogen atmosphere.

9.3 parts of the compound represented by the formula (VII-I-15), 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Kasei Co., Ltd.) in a flask equipped with a cooling tube and a stirring device, and toluene After adding 20.0 parts, 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100 ° C for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline solution, then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped and allowed to stand for 30 minutes, followed by separation into an organic layer and a water layer. After discarding the water layer by a separating operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The solvent was evaporated and removed by the evaporator of the obtained organic layer, and the blue-purple solid was obtained. The resulting blue violet solid was purified by column chromatography. The purified blue-purple solid was dried at 60 degreeC under reduced pressure, and 20.5 parts of compounds which are represented by a formula (A-II-15) were obtained. Yield 100%

Identification of the compound represented by formula (A-II-1)

(Mass spectrometry) ionization mode = ESI +: m / z = 601.3 [M-Cl] ⁺

                          Exact Mass: 636.3

The following reaction was performed in nitrogen atmosphere.

10.0 parts of compounds represented by formula (A-II-1), bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Kasei Co., Ltd.) in a flask equipped with a cooling tube and a stirring device, 5.9 parts, and N, After adding 30.0 parts of N-dimethylformamide, it stirred at 40 degreeC for 3 hours. Subsequently, after cooling the reaction mixture to room temperature, it is dripped at 500.0 parts of tap waters, stirring for 1 hour, and a dark blue suspension is obtained. Filtration of the obtained suspension gave a turquoise solid. Furthermore, the turquoise solid was dried at 60 degreeC under reduced pressure, and 11.7 parts of compounds which are represented by Formula (A-I-15) were obtained. Yield 85%

0.35 g of the compound represented by formula (AI-15) was dissolved in chloroform to make a volume of 250 cm 3, of which 2 cm 3 was diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound indicated an absorbance of 2.8 (arbitrary unit) at λmax = 626 nm.

Example 13

A solution of N, N-dimethylformamide (100 ml) of 4,4'-dichlorobenzophenone (manufactured by Tokyo Kasei Co., Ltd.) (10 g, 90 mmol) was cooled in an ice bath and sodium hydroxide (60%, 4.3 g, 90 mmol) was added and after a while stirring, Compound 2 (6.5 g, 30 mmol) was added portionwise. After stirring at room temperature for 5 hours, water was added, dichloromethane extraction was performed, and the residue was purified by silica gel column chromatography to obtain a compound (3.1 g, yield 24%) represented by formula (GP2).

The following reaction was performed in nitrogen atmosphere.

To a flask equipped with a cooling tube and a stirring device, 7.6 parts of the compound represented by the formula (VII-I-7), 10.0 parts of the compound represented by the formula (PP2) and 20.0 parts of toluene were added thereto, followed by addition of 11.4 parts of phosphorus oxychloride. It stirred at 95-100 degreeC for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline solution, then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped and allowed to stand for 30 minutes, followed by separation into an organic layer and a water layer. After discarding the water layer by a separating operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The solvent was evaporated and removed by the evaporator of the obtained organic layer, and the blue-purple solid was obtained. The resulting blue violet solid was purified by column chromatography. The purified blue-purple solid was dried at 60 degreeC under reduced pressure, and 17.8 parts of compounds which are represented by a formula (AII-166) were obtained. Yield 100%

Identification of Compound Represented by Formula (A-II-1)

(Mass spectrometry) ionization mode = ESI +: m / z = 715.3 [M-Cl] ⁺

                          Exact Mass: 750.3

The following reaction was performed in nitrogen atmosphere.

10.0 parts of the compound represented by a formula (A-II-1-6), bis (trifluoromethanesulfonyl) imide lithium (made by Tokyo Kasei Co., Ltd.) 5.0 parts, and N, in the flask provided with a cooling tube and the stirring apparatus; After adding 30.0 parts of N-dimethylformamide, it stirred at 40 degreeC for 3 hours. Subsequently, after cooling the reaction mixture to room temperature, it is dripped at 500.0 parts of tap waters, stirring for 1 hour, and a dark blue suspension is obtained. Filtration of the obtained suspension gave a turquoise solid. Furthermore, the turquoise solid was dried at 60 degreeC under reduced pressure, and 11.9 parts of compounds which are represented by a formula (A-I-6) were obtained. Yield 90%

0.35 g of the compound represented by the formula (A-I-6) was dissolved in chloroform to make a volume of 250 cm 3, of which 2 cm 3 was diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound indicated an absorbance of 2.9 (arbitrary unit) at λmax = 622 nm.

Example 14

The following reaction was performed in nitrogen atmosphere.

After adding 28.9 parts of potassium thiocyanate and 160.0 parts of acetone to the flask provided with a cooling tube and a stirring apparatus, it stirred for 30 minutes at room temperature. Subsequently, 50.0 parts of 2, 6- difluoro benzoic acid chloride (made by Tokyo Kasei Co., Ltd.) was dripped over 10 minutes. After completion of dropping, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture, 36.4 parts of N-ethyl-o-toluidine (manufactured by Tokyo Kasei Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, after cooling the reaction mixture, 34.2 parts of an aqueous 30% sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, 28.1 parts of chloroacetic acid were dripped under room temperature. After completion of dropping, the mixture was stirred for 7 hours under reflux. Subsequently, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, and then 200 parts of toluene were added and stirred for 30 minutes. Subsequently, stirring was stopped and allowed to stand for 30 minutes, followed by separation into an organic layer and a water layer. After discarding the water layer by a separating operation, the organic layer was washed with 200 parts of 1 N hydrochloric acid, followed by 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was removed by evaporation of the solvent by an evaporator to obtain a pale yellow liquid. The pale yellow liquid obtained was purified by column chromatography. The purified pale yellow liquid was dried at 60 degreeC under reduced pressure, and 25.2 parts of compounds which are represented by a formula (XI-I-17) were obtained. Yield 27%

The following reaction was performed in nitrogen atmosphere.

Into a flask equipped with a cooling tube and a stirring device, 8.1 parts of the compound represented by the formula (VII-I-17), 10.0 parts of the compound represented by the formula (PP2) and 20.0 parts of toluene were added thereto, followed by addition of 11.4 parts of phosphorus oxychloride. It stirred at 95-100 degreeC for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline solution, then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped and allowed to stand for 30 minutes, followed by separation into an organic layer and a water layer. After discarding the water layer by a separating operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The solvent was evaporated and removed by the evaporator of the obtained organic layer, and the blue-purple solid was obtained. The resulting blue violet solid was purified by column chromatography. The purified blue-purple solid was dried at 60 degreeC under reduced pressure, and 18.3 parts of compounds which are represented by a formula (A-II-17) were obtained. Yield 100%

Identification of the compound represented by formula (AA-17)

(Mass spectrometry) ionization mode = ESI +: m / z = 733.3 [M-Cl] ⁺

                          Exact Mass: 768.3

The following reaction was performed in nitrogen atmosphere.

10.0 parts of compounds represented by formula (A-II-17.1), bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Kasei Co., Ltd.) 4.9 parts, and N, in a flask equipped with a cooling tube and a stirring device. After adding 30.0 parts of N-dimethylformamide, it stirred at 40 degreeC for 3 hours. Subsequently, after cooling the reaction mixture to room temperature, it is dripped at 500.0 parts of tap waters, stirring for 1 hour, and a dark blue suspension is obtained. Filtration of the obtained suspension gave a turquoise solid. Furthermore, the turquoise solid was dried at 60 degreeC under reduced pressure, and 11.5 parts of compounds which are represented by a formula (AI-17) were obtained. Yield 87%

0.35 g of the compound represented by formula (AI-17) was dissolved in chloroform to make a volume of 250 cm 3, 2 cm 3 of which was diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound indicated an absorbance of 2.6 (arbitrary unit) at lambda max = 626 nm.

Example 15

The following reaction was performed in nitrogen atmosphere.

10.0 parts of compounds represented by Formula (A-II-7), potassium bis (fluorosulfonyl) imide [manufactured by Mitsubishi Material Electron Co., Ltd.] to a flask equipped with a cooling tube and a stirring device, and N After adding 30.0 parts of, N-dimethylformamide, the mixture was stirred at 40 ° C for 3 hours. Subsequently, after cooling the reaction mixture to room temperature, it is dripped at 500.0 parts of tap waters, stirring for 1 hour, and a dark blue suspension is obtained. Filtration of the obtained suspension gave a turquoise solid. Furthermore, the turquoise solid was dried at 60 degreeC under reduced pressure, and 10.8 parts of compounds which are represented by a formula (A-I-1) were obtained. Yield 89%

0.35 g of the compound represented by the formula (AI-13) was dissolved in chloroform to make a volume of 250 cm 3, of which 2 cm 3 was diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound indicated an absorbance of 2.8 (arbitrary units) at λ max = 631 nm.

Example 16

The following reaction was performed in nitrogen atmosphere.

10.0 parts of the compound represented by Formula (A-II-7) and cyclohexafluoropropane-1,3-bis (sulfonyl) imide potassium salt in a flask equipped with a cooling tube and a stirring device [Mitsubishi Material Electronization ( 6.6 parts and 30.0 parts of N, N-dimethylformamide were added, and it stirred at 40 degreeC for 3 hours. Subsequently, after cooling the reaction mixture to room temperature, it is dripped at 500.0 parts of tap waters, stirring for 1 hour, and a dark blue suspension is obtained. Filtration of the obtained suspension gave a turquoise solid. Furthermore, a turquoise solid was dried at 60 degreeC under reduced pressure, and 13.0 parts of compounds which are represented by a formula (A-I-1) were obtained. Yield 93%

0.35 g of the compound represented by the formula (AI-13) was dissolved in chloroform to make a volume of 250 cm 3, of which 2 cm 3 was diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound indicated an absorbance of 2.6 (arbitrary unit) at λ max = 631 nm.

Example 17

The following reaction was performed in nitrogen atmosphere.

10.0 parts of compounds represented by the formula (A-II-7) and bis (nonnafluorobutanesulfonyl) imide potassium salt in a flask equipped with a cooling tube and a stirring device [manufactured by Mitsubishi Material Electrochemical Co., Ltd.] 12.3 Part and 30.0 parts of N, N-dimethylformamide were added, followed by stirring at 40 ° C for 3 hours. Subsequently, after cooling the reaction mixture to room temperature, it is dripped at 500.0 parts of tap waters, stirring for 1 hour, and a dark blue suspension is obtained. Filtration of the obtained suspension gave a turquoise solid. Furthermore, the turquoise solid was dried at 60 degreeC under reduced pressure, and 15.4 parts of compounds which are represented by a formula (AI-20) were obtained. Yield 84%

0.35 g of the compound represented by the formula (AI-20) was dissolved in chloroform to make a volume of 250 cm 3, of which 2 cm 3 was diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound indicated absorbance 2.1 (arbitrary unit) at λ max = 630 nm.

Example 18

The following reaction was performed in nitrogen atmosphere.

10.0 parts of the compound represented by Formula (A-II-7), 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonic acid dipotassium salt in a flask equipped with a cooling tube and a stirring device [Mitsubishi Material Electrochemical Co., Ltd. product] 3.9 parts and 30.0 parts of N, N-dimethylformamide were added, and it stirred at 40 degreeC for 3 hours. Subsequently, after cooling the reaction mixture to room temperature, it is dripped at 500.0 parts of tap waters, stirring for 1 hour, and a dark blue suspension is obtained. Filtration of the obtained suspension gave a turquoise solid. Furthermore, the turquoise solid was dried at 60 degreeC under reduced pressure, and 10.7 parts of compounds represented by a formula (AII-21) were obtained. Yield 91%

0.35 g of the compound represented by formula (AI-21) was dissolved in chloroform to make a volume of 250 cm 3, of which 2 cm 3 was diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound indicated an absorbance of 3.0 (arbitrary units) at λ max = 638 nm.

[Preparation of Colored Curable Resin Composition]

Example 19

Coloring agent (A): 26 parts of dye represented by a formula (A-I-1);

Alkali-soluble resin (i): 53 parts of resin (i-1) [in terms of solid content];

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.] 16 parts;

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Igurecure® OXE-01; Manufactured by BASF Corporation; 0-acyl oxime compound] 4 parts;

Solvent (E): 120 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 480 parts of 4-hydroxy-4-methyl-2-pentanone; And

Surface leveling agent (F): polyether modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.15 part

Was mixed to obtain a colored curable resin composition.

Comparative Example 1

Coloring agent (A): 26 parts of dye represented by a formula (A-III-1);

Alkali-soluble resin (i): 53 parts of resin (i-1) [in terms of solid content];

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.] 16 parts;

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Igurecure® OXE-01; Manufactured by BASF Corporation; 0-acyl oxime compound] 4 parts;

Solvent (E): 120 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 480 parts of 4-hydroxy-4-methyl-2-pentanone; And

Surface leveling agent (F): polyether modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.15 part

Was mixed to obtain a colored curable resin composition.

[Production of color filter]

The colored curable resin composition was applied by a spin coat method on a 2-inch square glass substrate (# 1737; manufactured by Corning), and prebaked at 100 ° C. for 3 minutes to form a colored composition layer. After cooling, the exposure machine [TME-150RSK; Topcon Co., Ltd.] was used to irradiate light at an exposure amount (365 nm standard) of 150 mJ / cm 2 under an air atmosphere. Moreover, no photomask was used. The color filter (film thickness of 2.8 micrometers) was produced by performing the post-baking the coloring composition layer after exposure at 180 degreeC in oven for 20 minutes.

[Heat resistance evaluation]

The coating film of colored curable resin composition was heated at 230 degreeC for 20 minutes, and the color difference ((DELTA) Eab *) before and behind heating of the coating film was measured using the colorimeter (OSP-SP-200; product made by OLYMPUS). The color difference (ΔEab *) was 4.1 as a result of the above heat resistance evaluation of the coating film obtained in Example 1.

As a result of evaluating the above heat resistance of the coating film obtained in Comparative Example 1, the color difference (ΔEab *) was 12.1.

Moreover, the color difference ΔEab * indicates that the smaller its value, the higher the heat resistance material.

Example 20

The coating film of the coloring composition was produced in the same manner as in Example 19, except that the coloring agent (A-I-1) of Example 19 was changed to the coloring agent (A-I-3), and the heat resistance evaluation was performed. The color difference (ΔEab *) of the coating film of the coloring composition was 3.0.

Example 21

Except having changed the coloring agent (A-I-1) of Example 19 into the coloring agent (A-IV), it carried out similarly to Example 19, and produced the coating film of a coloring composition, and as a result of performing heat resistance evaluation, a coloring composition. The color difference (ΔEab *) of the coating film was 6.0.

Example 22

Except having changed the coloring agent (A-1) of Example 19 into the coloring agent (A-7), it carried out similarly to Example 19, and produced the coating film of a coloring composition, and as a result of performing heat resistance evaluation, a coloring composition. The color difference (ΔEab *) of the coating film was 2.7.

Example 23

Except having changed the coloring agent (A-I-1) of Example 19 into the coloring agent (A-I-B), it carried out similarly to Example 19, and produced the coating film of a coloring composition, and as a result of performing heat resistance evaluation, a coloring composition. The color difference (ΔEab *) of the coating film was 3.8.

Example 24

Except having changed the coloring agent (A-I-1) of Example 19 into the coloring agent (A-I-B), it carried out similarly to Example 19, and produced the coating film of a coloring composition, and as a result of performing heat resistance evaluation, a coloring composition. The color difference (ΔEab *) of the coating film was 2.8.

Example 25

Except having changed the coloring agent (A-I-1) of Example 19 into the coloring agent (A-I-10), it carried out similarly to Example 19, and produced the coating film of a coloring composition, and as a result of performing heat resistance evaluation, a coloring composition. The color difference (ΔEab *) of the coating film was 6.8.

Example 26

Except having changed the coloring agent (A-1) of Example 19 into the coloring agent (A-1), it carried out similarly to Example 19, and produced the coating film of a coloring composition, and as a result of performing heat resistance evaluation, a coloring composition. The color difference (ΔEab *) of the coating film was 3.9.

Example 27

Except having changed the coloring agent (A-I-1) of Example 19 into the coloring agent (A-I-12), it carried out similarly to Example 19, and produced the coating film of a coloring composition, and as a result of performing heat resistance evaluation, a coloring composition. The color difference (ΔEab *) of the coating film was 4.1.

Example 28

Except having changed the coloring agent (A-1) of Example 19 into the coloring agent (A-13), it carried out similarly to Example 19, and produced the coating film of a coloring composition, and as a result of performing heat resistance evaluation, a coloring composition. The color difference (ΔEab *) of the coating film was 3.2.

Example 29

Except having changed the coloring agent (A-I-1) of Example 19 into the coloring agent (A-I-14), it carried out similarly to Example 19, and produced the coating film of a coloring composition, and as a result of performing heat resistance evaluation, a coloring composition. The color difference (ΔEab *) of the coating film was 5.7.

Example 30

Except having changed the coloring agent (A-I-1) of Example 19 into the coloring agent (A-I-15), it carried out similarly to Example 19, and produced the coating film of a coloring composition, and as a result of performing heat resistance evaluation, a coloring composition. The color difference (ΔEab *) of the coating film was 3.4.

Example 31

Except having changed the coloring agent (A-I-1) of Example 19 into the coloring agent (A-I-6), it carried out similarly to Example 19, and produced the coating film of a coloring composition, and as a result of performing heat resistance evaluation, a coloring composition. The color difference (ΔEab *) of the coating film was 1.9.

Example 32

Except having changed the coloring agent (A-I-1) of Example 19 into the coloring agent (A-I-7), it carried out similarly to Example 19, and produced the coating film of a coloring composition, and as a result of performing heat resistance evaluation, a coloring composition. The color difference (ΔEab *) of the coating film was 2.2.

Example 33

Except having changed the coloring agent (A-I-1) of Example 19 into the coloring agent (A-I-1), it carried out similarly to Example 19, and produced the coating film of a coloring composition, and as a result of performing heat resistance evaluation, a coloring composition. The color difference (ΔEab *) of the coating film was 2.9.

Example 34

Except having changed the coloring agent (A-I-1) of Example 19 into the coloring agent (A-I-1), it carried out similarly to Example 19, and produced the coating film of a coloring composition, and as a result of performing heat resistance evaluation, a coloring composition. The color difference (ΔEab *) of the coating film was 3.5.

Example 35

Except having changed the coloring agent (A-II) of Example 19 into the coloring agent (A-II), it carried out similarly to Example 19, and produced the coating film of a coloring composition, and as a result of performing heat resistance evaluation, a coloring composition. The color difference (ΔEab *) of the coating film was 3.8.

Example 36

Except having changed the coloring agent (A-I-1) of Example 19 into the coloring agent (A-II-21), it carried out similarly to Example 19, and produced the coating film of a coloring composition, and as a result of performing heat resistance evaluation, a coloring composition. The color difference (ΔEab *) of the coating film was 4.9.

When the colored curable resin composition containing the compound of this invention is used, the color filter excellent in heat resistance can be provided. The said color filter is useful as a color filter which can be used for a display apparatus (for example, a liquid crystal display device, an organic electroluminescent apparatus, an electronic paper, etc.) and a solid-state image sensor.

Claims (12)

The compound represented by a formula (A-1).

[In formula (A-1), X represents an oxygen atom, a nitrogen atom, or a sulfur atom. [Vi] ^m- represents an arbitrary m-valent anion. R ⁴¹ to R ⁴⁶ each independently represent a hydrogen atom, an amino group, or a group having 1 to 20 carbon atoms and 2 to 20 carbon atoms that may be substituted with a halogen atom and an oxygen atom inserted between the carbon atoms constituting the alkyl group Or an aryl group which may be substituted. R ⁴¹ and R ⁴² may be bonded to form a ring together with the nitrogen atom to which they are bonded, R ⁴³ and R ⁴⁴ may be bonded to form a ring together with the nitrogen atom to which they are bonded, and R ⁴⁵ and R ⁴⁶ may be You may bond and form a ring with the nitrogen atom to which they couple | bond. R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl atom having 1 to 8 carbon atoms or an alkyl group having 2 to 8 carbon atoms, and an oxygen atom is inserted between the carbon atoms constituting the alkyl group. Although the group is represented, R ⁴⁸ and R ⁵² may be bonded to each other to form —O—, —NH—, —S—, or —SO ₂ —. R ⁵⁵ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group which may be substituted.
Moreover, a plurality of molecules in one molecule

When is included, these may have the same structure and may differ from each other.
m represents any natural number] The method of claim 1,
In the formula (A-1), X represents an oxygen atom, a nitrogen atom or a sulfur atom, [k] ^m- represents an arbitrary m-valent anion, and R ⁴¹ to R ⁴⁶ each independently represent a hydrogen atom or an amino group. Or a group having 1 to 20 carbon atoms which may be substituted with a halogen atom, a group having 2 to 20 carbon atoms and an oxygen atom inserted between the carbon atoms constituting the alkyl group, or an aryl group which may be substituted, and R ⁴⁷ to R ⁵⁴ each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, but R ⁴⁸ and R ⁵² are bonded to each other to form -O-, -NH-, -S- or -SO ₂ -may be formed, and R ⁵⁵ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group which may be substituted. 3. The method according to claim 1 or 2,
[V] ^m- in the formula (A-1) is an anion containing boron. 3. The method according to claim 1 or 2,
[V] ^m- in the formula (A-I) is an anion containing aluminum. 3. The method according to claim 1 or 2,
^M- in the formula (A-1) is an anion containing fluorine. 3. The method according to claim 1 or 2,
^M- in the formula (AI) is an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as an essential element. The method according to claim 6,
^M- in the formula (A-1) is an anion of a heteropoly acid or isopoly acid containing tungsten as an essential element. The method of claim 7, wherein
^M- in the formula (A-1) is an anion of tungstophosphoric acid, an anion of tungstosilicic acid, or an anion of tungsten isopoly acid. The colored curable resin composition containing the compound of any one of Claims 1-8. The coating film formed using the colored curable resin composition of Claim 9. The color filter formed using the colored curable resin composition of Claim 9. A display device comprising the color filter of claim 11.