KR102105617B1 - Compound for dye - Google Patents

Abstract

식 (Ａ―Ⅰ)에서, X는 산소 원자, 질소 원자 또는 유황 원자를 가리킨다. [Ｙ]^m-은 임의의 m가의 음이온을 나타낸다. R⁴¹ 내지 R⁴⁶은 각각 독립적으로 수소 원자, 아미노기로 또는 할로겐 원자로 치환되어 있어도 되는 탄소수 1 내지 20개의 알킬기를 나타낸다. R⁴⁷ 내지 R⁵⁴는 각각 독립적으로 수소 원자, 할로겐 원자, 니트로기, 하이드록실기, 또는 탄소수 1 내지 8개의 알킬기를 나타낸다. R⁵⁵는 수소 원자, 탄소수 1 내지 20개의 알킬기, 또는 치환되어 있어도 되는 아릴기를 나타낸다. A compound represented by formula (A-I), a colored curable resin composition containing the compound, a color filter formed using the resin composition, and a display device comprising the color filter.

In formula (A-I), X represents an oxygen atom, a nitrogen atom, or a sulfur atom. [Iii] ^m- represents an arbitrary m-valent anion. R ⁴¹ to R ⁴⁶ each independently represents a hydrogen atom, an amino group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom. 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. R ⁵⁵ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group which may be substituted.

Description

Compound for coloring matter {COMPOUND FOR DYE}

The present invention relates to compounds useful as pigments.

Dyestuffs are used as colorants for color filters included in liquid crystal displays, solid-state imaging devices, and the like. As a dye, the compound represented by Formula (A-III-1) is described in WO2012 / 053201, for example.

The above-mentioned compound, which has been conventionally known, was not capable of satisfactorily satisfying heat resistance. Therefore, the colored curable resin composition containing the compound was not sufficiently satisfactory from the viewpoint of heat resistance.

The present invention includes the following inventions.

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

[In formula (A-I), X represents an oxygen atom, a nitrogen atom, or a sulfur atom. [Iii] ^m- represents an arbitrary m-valent anion. Each of R ⁴¹ to R ⁴⁶ is independently a hydrogen atom, an amino group, or an alkyl group having 1 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms, which may be substituted with a halogen atom, and oxygen atoms are inserted between carbon atoms constituting the alkyl group. Or an aryl group which may be substituted. R ⁴¹ and R ⁴² may combine to form a ring with the nitrogen atom to which they are attached, R ⁴³ and R ⁴⁴ may combine to form a ring with the nitrogen atom to which they are attached, and R ⁴⁵ and R ⁴⁶ may be They may combine to form a ring together with the nitrogen atom to which they are attached. R ⁴⁷ to R ⁵⁴ are each independently a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, or an alkyl atom having 2 to 8 carbon atoms, and an oxygen atom is inserted between the carbon atoms constituting the alkyl group Although a group is present, R ⁴⁸ and R ⁵² may combine with 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, multiple within a molecule

When is included, these may be the same structure or different structures.

m represents an arbitrary natural number]

[2] In formula (A-I), X represents an oxygen atom, a nitrogen atom, or a sulfur atom, [i] ^m- represents an arbitrary m-valent anion, and R ⁴¹ to R ⁴⁶ are each independently a hydrogen atom , An alkyl group having 1 to 20 carbon atoms which may be substituted with an amino group or a halogen atom, a group in which an oxygen atom is inserted between carbon atoms constituting the alkyl group having 2 to 20 carbon atoms, or an aryl group which may be substituted, 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 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a compound described in [1], which may be substituted.

[3] The compound according to [1] or [2], in which [Ｙ] ^m- is an anion containing boron in formula (A-I).

[4] The compound according to [1] or [2], wherein [Ｙ] ^m- in formula (A-I) is an anion containing aluminum.

[5] The compound according to [1] or [2], wherein [(] ^m- in formula (A-I) is an anion containing fluorine.

[6] In formula (A-I), [Ｙ] ^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 [1] or [2] ].

[7] The compound according to [6], in which formula [A-I] [i] ^m- is an anion of a heteropoly acid or isopoly acid containing tungsten as an essential element.

[８] In formula (A-I), [에] ^m- is anion of tungstophosphoric acid, anion of tungstosilicic acid, or [7] which is anion of tungsten-based isopoly acid. Compounds described.

[９] A colored curable resin composition comprising the compound according to any one of [1] to [８].

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

[11] A color filter formed using the colored curable resin composition described in [iii].

[11] A display device comprising the color filter according to [11].

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

The compound of the present invention is a compound represented by formula (A-I) (hereinafter referred to as compound (A-I)). The compounds of the present invention also include tautomers thereof and salts thereof.

In formula (A-I), X represents an oxygen atom, a nitrogen atom, or a sulfur atom. In terms of easy synthesis, it is preferably a sulfur atom.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁴¹ to R ⁴⁶ include groups represented by the following formula. In the following formula, * represents a bonding arm with a nitrogen atom. Among these, an alkyl group having 1 to 8 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.

Examples of the amino group represented by R ⁴¹ to R ⁴⁶ or an alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include groups represented by the following formula. In the following formula, * represents a bonding arm with a nitrogen atom.

Examples of the group having an alkyl group having 2 to 20 carbon atoms represented by R ⁴¹ to R ⁴⁶ and having an oxygen atom inserted between the carbon atoms constituting the alkyl group include groups represented by the following formula. In the following formula, * represents a bonding arm with a nitrogen atom. Among these, a group having an alkyl group having 2 to 10 carbon atoms and having an oxygen atom inserted between carbon atoms constituting the alkyl group is preferable, and a group having an alkyl group having 2 to 6 carbon atoms and having an oxygen atom inserted between carbon atoms constituting the alkyl group. It is more preferable.

In the aryl group which may be substituted represented by R ⁴¹ to R ⁴⁶ , the substituent includes halogen atoms such as fluorine atom, chlorine atom and iodine atom; A haloalkyl group 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 methoxy groups and ethoxy groups; Hydroxy group; Sulfamoyl group; And alkylsulfonyl groups having 1 to 6 carbon atoms such as methylsulfonyl group.

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

Examples of the ring formed by combining R ⁴¹ and R ⁴² together with the nitrogen atom to which they are attached include a pyrrolidine ring, a morpholine ring, a piperidine ring, and a piperazine ring.

Examples of the ring formed by R ⁴³ and R ⁴⁴ bonding together with the nitrogen atom to which they are attached include a pyrrolidine ring, a morpholine ring, a piperidine ring, and a piperazine ring.

Examples of the ring formed by R ⁴⁵ and R ⁴⁶ bonding together with the nitrogen atom to which they are attached include a pyrrolidine ring, a morpholine ring, a piperidine ring, and a piperazine ring.

From the viewpoint of easy synthesis, R ⁴¹ to R ⁴⁶ are preferably each independently an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted, and each independently an alkyl group having 1 to 8 carbon atoms or an aryl group represented by the following formula. It is more preferable. In the following formula, * represents a bonding arm with a nitrogen atom.

As a group in which an oxygen atom is inserted between the alkyl groups having 1 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ and the carbon atoms constituting the alkyl group having 2 to 8 carbon atoms, for example, a group represented by the following formula is mentioned. . In the following formula, * represents a bonding arm with a carbon atom.

From the viewpoint of easy synthesis, R ⁴⁷ to R ⁵⁴ are preferably each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably each independently a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom. Do.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁵⁵ include, for example, a group represented by the following formula. In the following formula, * represents a bonding arm with a carbon atom.

In the aryl group which may be substituted represented by R ⁵⁵ , the substituent includes halogen atoms such as fluorine atom, chlorine atom and iodine atom; A haloalkyl group 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 methoxy groups and ethoxy groups; Hydroxy group; Sulfamoyl group; And alkylsulfonyl groups having 1 to 6 carbon atoms such as methylsulfonyl group.

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

R ⁵⁵ from the viewpoint of easy synthesis, 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, even more preferably Is an aryl group represented by the following formula. In the following formula, * represents a bonding arm with a carbon atom.

Examples of the cation portion of the formula (A-I) include cations 1 to 11 represented by the formula (A-1) shown in Table 1 below.

Among these, cation 1 to cation 6 or cation 11 to 12 are preferred as the cation portion of formula (A-I), and cation 1, cation 2 or cation 12 is particularly preferred.

Moreover, the following are mentioned as a specific example of the cation part of Formula (A-I) when R ⁴⁸ and R ⁵² combine with each other and form -O-, -NH-, -S-, or -SO _2-. have.

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

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

In the formula (4), W ¹ and W ² each independently represent a group that releases two protons from a compound having 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, a hydroxy group, a carboxy group, etc. are mentioned as a monovalent proton donor substituent. As a compound having two monovalent proton donor substituents, 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 be present, 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 it is 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 above substituents, for example, salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-aminosalicylic acid, 3-chlorosalicylic acid, 4-bromosalicylic acid, 3-methoxysalicylic 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 And hydroxysalicylic acid (2,6-dihydroxybenzoic acid).

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

And the like.

As mandelic acid which may have the above substituent, for example,

And the like.

Examples of the anion represented by the formula (4) include anion (XC-1) to anion (XC-2X) and the like.

Among these, as anions represented by formula (4), anions (FC-1), anions (FC-2), anions (FC-3), anions (FC-25), anions (FC-2026) and anions (FCC-) 25) is preferable, anions (FC-1) and anions (FC-25) are more preferred, and anions (FC-1) are even more preferred. If it is such an anion, the compound (A-I) of the present invention tends to have excellent solubility in an 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.

[In the formula (6), W ³ and W ⁴ each independently represents a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or W ³ and W ⁴ are combined to form a fluorinated alkanediyl group having 1 to 4 carbon atoms. box]

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

[In formula (VII), Y ¹ represents a fluorinated alkanediyl group having 1 to 4 carbon atoms]

[In the formula (VII), Y ² represents a fluorinated alkyl group having 1 to 4 carbon atoms]

As the fluorinated alkyl groups having 1 to 4 carbon atoms represented by W ³ to W ⁷ in the formulas (6) and (7), perfluoroalkyl groups are preferable, 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 the fluorinated alkanediyl group having 2 to 4 carbon atoms formed by combining W ³ and W ⁴ in the formula (6), a perfluoroalkane diyl group is preferable, for example, -CF ₂ CF _2- , -CF ₂ CF ₂ CF _2- , -CF ₂ CF ₂ CF ₂ CF ₂ -and the like.

As the fluorinated alkanediyl group having 1 to 4 carbon atoms represented by Y ¹ in the formula (iv), a perfluoroalkanediyl 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 - And the like.

As the fluorinated alkyl group having 1 to 4 carbon atoms represented by Y ² in the formula (iv), a perfluoroalkyl group is preferable. As the 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.

Examples of the anion represented by the formula (6) (hereinafter referred to as "anion (6)") include the following anions (6-1) to (6-6).

Examples of the anion represented by the formula (7) (hereinafter referred to as "anion (7)") include, for example, the following anion (7-1).

Examples of the anion represented by the formula (i) (hereinafter referred to as "anion") include the following anions (i-1) to (i-4).

Examples of the anion represented by the formula (iv) (hereinafter referred to as "anion") include the following anions (i-1) to (i-4).

By containing one or more anions selected from the group consisting of anions (6), anions (7), anions (８), and anions (hereinafter referred to as "anions (6) to (９)"), the present The solubility of the compound (A-I) of the invention in an organic solvent can be improved. Among these, anions (6) are preferred, and anions (6-1-1) are more preferred.

[Ｙ] As an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen as an essential element, represented by ^m- , anion of a heteropoly acid or isopoly acid containing tungsten as an essential element In particular, anions of tungstophosphoric acid, tungstosilicic acid and tungsten-based isopoly acid are preferred.

As anions of heteropolyacids or isopolyacids 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- , Keggin type tungstosilicate ion α- [SiW ₁₂ O ₄₀ ] ^4- , β- [SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O ₄₀ ] ^4- , and 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 is an anion consisting of one or more elements and oxygen 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 it is easy to synthesize and post-process, heteropolyacid anions such as keggin-type tungstophosphate ions, Dawson-type tungstophosphate ions, and keggin-type tungstosilicate ions, and isopolyacid anions such as [W ₁₀ O ₃₂ ] ^4- desirable.

As the compound (A-1), any one of the cations 1 to 11 above, anion (ＢC-1) to (ＢC-2８), anion (6-1) to (6-6), anion (7―) 1), anion (８-1) to (８-4), and a combination with any one anion of anions (i-1) to (i-4), any three cations of the cations 1-11 And anion α- [PW ₁₂ O ₄₀ ] ^3- , combination with any 6 cations of the cations 1 to 11 above and anion α- [P ₂ W ₁₈ O ₆₂ ] ^6- , any of the cations 1 to 11 above And combinations of the four cations and anions α- [SiW ₁₂ O ₄₀ ] ^4- and [W ₁₀ O ₃₂ ] ^4- .

Compound (A-I) can be prepared by mixing a compound represented by formula (A-II) (hereinafter referred to as "compound (A-II)") and an alkali metal salt of anion [i] ^m- in a solvent. . Lithium, sodium and potassium are mentioned as an alkali metal.

As the solvent, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, ethyl acetate, toluene, methanol, ethanol, isopropanol, acetone, tetrahydrofuran, di And oxalic acid, 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, the solubility of the compound (A-II) and the alkali metal salt of the anion [Ｙ] ^m- tends to be high.

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

Mixing of the alkali metal salt of the compound (A-II) and the anion [i] ^m- may be carried out by dissolving both in the above solvent or without dissolving it. The compound (A-I) of the present invention can be obtained with a high yield by using a solvent in which both are dissolved and dissolving.

The mixing temperature of the compound (A-II) and the alkali metal salt of the anion [Ｙ] ^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.

When a solvent compatible with water is used, the above-mentioned compound (A-I) is obtained by mixing the above solvent, stirring for 1 hour to 3 hours as necessary, and then obtaining the precipitate by filtration. ). If necessary, the obtained compound (A-I) may be washed with ion-exchanged water.

When a solvent that is not compatible with water is used, the reaction mixture and ion-exchanged water are mixed, and if necessary, stirred for 1 hour to 3 hours, and then the organic layer is obtained by separating the compound of the present invention (A A solution containing -I) can be obtained. If necessary, the solution may be washed with ion-exchanged water. The compound (A-I) of the present invention can be obtained by removing the solvent from a solution containing the compound (A-I) of the present 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 or chloroform, and purified by recrystallization.

Compound (A-II) can be produced, for example, by reacting a compound represented by formula (X-I) with a compound represented by formula (C-I). Such a reaction may be carried out in the presence of an organic solvent or may be carried out without a solvent.

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

Compound (A-II) can also be produced by reacting a compound represented by formula (VII-II) with a compound represented by formula (C-II). Such a reaction may be carried out in the presence of an organic solvent or may be carried out without a solvent.

[In formulas (i-II) and (C-II), R ⁴¹ to R ⁵⁵ each represent the same meaning as above.]

The use 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, with respect to 1 mol of the compound represented by the formula (X-I).

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

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

In any reaction, it is preferable to perform in an organic solvent from a viewpoint of a yield. Examples of the organic solvent include 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; And amide solvents such as 1-methyl-2-pyrrolidone. The amount of the organic solvent used is preferably 1 part by mass or more and 20 parts by mass or less, 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 formula (X-I) or formula (X-II). Is below.

It is preferable to perform the said reaction from a viewpoint of a yield in presence of a condensing agent. Examples of the condensing agent include phosphoric acid, polyphosphoric acid, phosphorus oxychloride, sulfuric acid, and thionyl chloride.

The amount of the condensing agent to be 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 or less with respect to 1 part by mass of the compound represented by formula (X-I) or formula (X-II). Is below.

The method for obtaining the target compound (A-II) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, a method of mixing the reaction mixture with alcohol (for example, methanol, etc.) and filtering the precipitated crystals may be mentioned. It is preferable to add the reaction mixture to alcohol. The temperature when adding the reaction mixture is preferably -100 ° C or higher and 50 ° C or lower, and more preferably -80 ° C or higher and 0 ° C or lower. In addition, after mixing, it is preferable to stir at the same temperature for about 0.5 to 2 hours. It is preferable that the crystals obtained by filtration are washed with water or the like and then dried. Alternatively, if necessary, further purification may be performed by a known method such as recrystallization.

As a method for producing the compounds (i-I) and (i-II), there are various known methods, for example, those described in West Germany patent application P3928243.0.

As a method for producing the compounds (C-I) and (C-II), various known methods, such as those described in Patent Document 1, are exemplified.

As the alkali metal salt of the anion represented by formula (4), a commercially available salt may be used, for example, by the method described in JP4097704-B or JP4341251-B and Journal of The Electrochemical Society, Volume 148, Volume 1, 2001. Can be produced.

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

An alkali metal salt of an anion containing at least one element selected from the group consisting of tungsten, silicon and phosphorus and oxygen as an essential atom can be prepared by a known conventional method, but a commercial product may be used as it is. As such a compound, the corresponding heteropolyacid salt, isopolyacid salt, or silicate, phosphate, etc. are mentioned, for example. As these various salts, monovalent metal salts such as sodium, lithium, and potassium are preferable because of their excellent water solubility and ease of synthesis and post-treatment.

It is preferable that the coloring 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 "a coloring agent (A)"), and further contains a resin. It is more preferable that the colored curable resin composition of the present invention further contains a polymerizable compound (C), a polymerization initiator (D), and a solvent (E).

It is preferable that the colored curable resin composition of the present invention further includes a leveling agent [Ｆ].

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

In this specification, the compound illustrated as each component can be used alone or in combination of a plurality of species, unless otherwise specified.

<Coloring agent (A)>

The colorant (A) may be used alone as a dye containing the compound of the present invention as an active ingredient, but for coloration, that is, to adjust the spectral properties, further other dyes (A1), pigments (P) or You may contain these mixtures.

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 Colourists), and known dyes described in dyeing notes (Shikisensha). In addition, according to the chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, naphthoquinone dye, quinnonimine dye, methine dye, azomethine dye, squarylium dye, acridine dye , Styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Among them, an organic solvent-soluble dye can be preferably used.

Specifically, C.I. Solvent yellow 4 (hereinafter, C.I. solvent yellow is omitted, only numbers are described), 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. C.I. of Solvent Green 1, 4, 5, 7, 34, 35, etc. 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, 111, 112, 113, 114, 116, 119, 123, 128, 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. Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. C.I. Acid Dye,

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 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, 207, 211, 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, 79, 82, etc. C.I. Direct dyes,

C.I. C.I. of Disperse Yellow 54, 76, etc. Disperse dyes,

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. Basic Green 1, etc. C.I. Basic Dye,

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

C.I. Reactive Orange 16;

C.I. C.I., such as Reactive Red 36 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. C.I. of Modern Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, etc. Modern Dye,

C.I. Bat Green 1 et al. C.I. Bat dye

And the like.

Among these, blue dyes, violet dyes and red dyes are preferred.

These dyes may be used alone or in combination of two or more.

Moreover, as a classification by chemical structure, xanthene dye is preferable. Known substances can be used as the xanthene dye. For example, the compound represented by Formula (1) is preferable.

[In formula (1), R ¹ and R ² each independently represent a 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 contained in the saturated hydrocarbon group may be substituted with a halogen atom, and -CH ₂ -contained in the saturated hydrocarbon group is -O It may be substituted with-, -CO- or -NR ^11- .

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

R ⁵ represents -OH, -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ Shows.

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, a plurality of R ⁵ may be the same or different.

R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a 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 combine with each other to become one with a nitrogen atom and contain 3 to 10 atoms (員) of nitrogen. You may form a heterocycle.

R ¹¹ each 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]

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms representing R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, A linear alkyl group having 1 to 20 carbon atoms, such as nonyl group, decyl group, dodecyl group, hexadecyl group, and iconic 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, 2-ethylhexyl group; And alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and tricyclodecyl group.

Examples of -CO ₂ R ⁸ include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, tert-butoxycarbonyl group, hexyloxycarbonyl group, and icosyloxycarbonyl group.

Examples of -SO ₃ R ⁸ include methoxysulfonyl group, ethoxysulfonyl group, propoxysulfonyl group, tert-butoxysulfonyl group, hexyloxysulfonyl group, and icosyloxysulfonyl group.

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-butylsulfide Pamoyl group, N-tert-butyl sulfamoyl group, N-pentyl sulfamoyl 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-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamo Diary, N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) N-1 substituted sulfamoyl groups such as 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, such as N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl group, And N-2 substituted sulfamoyl groups.

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 a nitrogen atom. As said heterocyclic ring, the following are mentioned, for example.

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms and representing R ³ and R ⁴ include those having 1 to 10 carbon atoms. The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms representing R ³ and R ⁴ may be substituted with a halogen atom, and -CH ₂ -contained in the saturated hydrocarbon group is -O-, -CO- or -NR It may be substituted with ^11- .

Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.

Examples of the saturated hydrocarbon group substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, and a chlorobutyl group.

Examples of the alkyl group having 1 to 6 carbon atoms representing R ⁶ and R ⁷ include, for example, a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, sec-butyl group, and tert-butyl Group, isopentyl group, neopentyl group, and the like.

Examples of the aralkyl group having 7 to 10 carbon atoms representing R ¹¹ include, for example, a benzyl group, a phenylethyl group, and a phenylbutyl group.

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

The N ⁺ (R ¹¹⁾ ₄ as the 4 R ¹¹ from two or more is 5 to 20 carbon atoms of the monovalent saturated hydrocarbon group is preferred. Further, the total number of carbon atoms of the four R ¹¹ is preferably 20 to 80, and more preferably 20 to 60.

The phenyl group representing R ¹ and R ² may have a substituent. Examples of the substituent include 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.

Examples of -OR ⁸ include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, and icosyloxy group. You can.

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

Examples of -SO ₂ R ⁸ include methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, decylsulfonyl group, and icosylsulfonyl group.

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 combine with each other to form a ring containing a nitrogen atom by becoming one with the nitrogen atom to which they are bonded, and R ² and R ⁴ may be combined with each other to become one with a nitrogen atom to which they are bonded, and a nitrogen atom You may form a ring containing the. Examples of the ring containing the nitrogen atom include the following ones.

As R ^5, -SO ₃ H, -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ are preferred.

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.

m is preferably an integer from 0 to 2, more preferably 0 or 1.

The compound represented by formula (2) is preferable as the compound (1).

[In the formula (2), R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent an alkyl group having 1 to 4 carbon atoms.

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 representing 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, and tert-butyl group. You can.

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 groups.

m and n are preferably an integer from 0 to 2, more preferably 0 or 1.

The compound represented by formula (3) is preferable as the compound (1).

[In formula (3), R ³¹ and R ³² each independently represent 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]

Examples of the alkyl group having 1 to 4 carbon atoms representing R ³¹ , R ³² , R ³³ and R ³⁴ include the same ones described above. 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 are each independently a hydrogen atom or a methyl group.

As a compound (1), the compound represented by Formula (1-1)-Formula (1-7), for example is mentioned, respectively. Among these, the compound represented by Formula (1-1) is preferable from the viewpoint of excellent solubility in an organic solvent.

As a method for producing compound (1), formula (1a)

Compound represented by, compound represented by formula (1), and compound represented by formula (1c)

[In formulas (1ｂ) and (1c), R ¹ to R ⁴ each have the same meaning as described above.

And a method of reacting with or without an organic solvent. From the viewpoint of yield, it is preferred to react without a solvent. The reaction temperature is preferably 30 ° C to 180 ° C, and more preferably 80 ° C to 130 ° C. The reaction time is preferably 1 hour to 12 hours, and more preferably 3 hours to 8 hours.

Examples of the organic solvent include hydrocarbon solvents 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; And amide solvents such as 1-methyl-2-pyrrolidone.

The use 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 and 5 mol, respectively, relative to 1 mol of the compound represented by the formula (1a). Less than mole. Each may react stepwise or may react simultaneously.

It is preferable that the compound represented by Formula (1) and the compound represented by Formula (1c) are the same compound from the viewpoint of easy production of Compound (1).

The method for obtaining the target compound (1) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, the reaction mixture can be obtained by mixing with an acid (for example, acetic acid, etc.) and filtering the precipitated crystals. It is preferable that the acid is prepared in advance with an aqueous solution of acid, and then the reaction mixture is added to the aqueous solution. The temperature when adding the reaction mixture is preferably 10 ° C or higher and 50 ° C or lower. Moreover, after that, it is preferable to stir at the same temperature for about 0.5 to 2 hours. It is preferable that the crystals obtained by filtration are washed with water or the like and then dried. Alternatively, if necessary, further purification may be performed by a known method such as recrystallization.

The pigment (P) is not particularly limited, and known pigments can be used, and examples thereof include pigments classified as pigments in the color index (published by The Society of Dyers and Colourists).

As a 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 , Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;

C.I. Pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73;

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, 265 ;

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

C.I. And black pigments such as Pigment Black 1 and 7.

The pigment (P) is preferably a phthalocyanine pigment and a dioxazine pigment, more preferably C.I. At least one member selected from the group consisting of Pigment Blue 15: 6 and Pigment Violet 23. The inclusion of the above pigments facilitates the optimization of the transmission spectrum and improves the light resistance and chemical resistance of the color filter.

Pigments are treated with rosin, surface treatment using pigment derivatives with acidic or basic groups introduced as necessary, graft treatment on pigment surfaces with polymer compounds, etc., atomization with sulfuric acid atomization, or removing impurities In order to do so, a washing treatment with an organic solvent, water, or the like, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed. It is preferable that the particle diameters of the pigments are uniform.

The pigment contains a pigment dispersant and subjected to dispersion treatment, whereby a pigment dispersion liquid in a form in which the pigment dispersant is uniformly dispersed in a solution can be obtained. The pigments may be subjected to dispersion treatment alone, or a mixture of a plurality of kinds may be dispersed.

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

When a pigment dispersant is used, its amount is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the pigment. When the amount of the pigment dispersant used is in the above range, a pigment dispersion liquid in a uniform dispersion state tends to be obtained.

The content ratio of the compound (A-I) 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 colorant (A).

When dye (A1) is included, the content thereof is preferably 0.5% by mass or more and 80% by mass or less, more preferably 40% by mass or more and 90% by mass or less, based on the total amount of the colorant (A). When the pigment (P) is included, the content thereof is preferably 35% by mass or more and 99% by mass or less, more preferably 1% by mass or more and 70% by mass or less, more preferably It is 1 mass% or more and 50 mass% or less.

The content rate of the colorant (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 with respect to the total amount of the solid content. to be. When the content rate of the colorant (A) is within the above range, desired spectroscopy or color density can be obtained.

In the present specification, the "total amount of solid content" refers to the total amount of components excluding the solvent (E) in the colored curable resin composition of the present invention. The total amount of solid content and the content of each component therefor can be measured by known analytical means such as liquid chromatography or gas chromatography.

<Resin>

It is preferable that resin (i) is alkali-soluble resin (i). The alkali-soluble resin (Ｂ) (hereinafter referred to as “resin”) is a copolymer comprising a structural unit derived from at least one monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. to be.

Examples of such resins include the following resins [# 1] to [# 6].

Resin [Ｋ1] One or more monomers selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (a) (hereinafter referred to as "(a)"), cyclic ether structures having 2 to 4 carbon atoms and ethylenic properties A copolymer of a monomer (ｂ) having an unsaturated bond (hereinafter referred to as “(ｂ)”);

Resin [Ｋ2] (a) and (ｂ) and a monomer (c) copolymerizable with (a) (however, different from (a) and (및)) (hereinafter referred to as "(c)") coalescence;

Copolymers of resins [VII3] (a) and (c);

Resin [X4] Resin (B) reacted with the copolymer of (a) and (c);

A resin in which (a) is reacted with a copolymer of resin [VII] and (C);

Resin [X6] A resin obtained by reacting (a) with a copolymer of (i) and (c), and further reacting carboxylic anhydride.

Examples of (a) include, for example, 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 Bicyclounsaturated compounds containing carboxyl groups 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 acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride;

Unsaturated mono-((meth) acryloyloxyalkyl) of polyvalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] Esters;

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

Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferred from the viewpoint of copolymerization reactivity or solubility of the resulting resin in an aqueous alkali solution.

(i) represents, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, one or more selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Branch refers to a polymerizable compound.

(iii) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

Moreover, in this specification, "(meth) acrylic acid" refers to one or more selected from the group consisting of acrylic acid and methacrylic acid. Notations such as "(meth) acryloyl" and "(meth) acrylate" have the same meaning.

As (iii), for example, a monomer having an oxiranyl group and an ethylenically unsaturated bond (hereinafter referred to as "(ｂ1)"), a monomer having an oxetanyl group and an ethylenically unsaturated bond (hereinafter referred to as "(2)", "(Ｂ2)", and a monomer (ｂ3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as "(ｂ3)").

As (ｂ1), for example, a monomer having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as "(「 1-1) ") and an alicyclic unsaturated hydrocarbon are epoxy. And a monomer (ｂ1-2) having a chemical structure (hereinafter referred to as “(ｂ1-2)”).

(ｂ1-1) As glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinyl benzyl glycol Cydyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, α-methyl-o-vinylbenzylglycidyl ether, α-methyl-m-vinylbenzylglycidyl 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 And 3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, and 2,4,6-tris (glycidyloxymethyl) styrene. have.

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

[In formulas (II) and (III), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a 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.

* Indicates a bonding 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, and tert-butyl group.

Examples of the alkyl group in which the hydrogen atom is substituted with hydroxy are a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, and 1-hydroxy -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.

Examples of R ^a and R ^b include 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 groups.

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-, more preferably a single bond and * -CH ₂ And CH ₂ -O- (* indicates a bonding arm with O).

Examples of the compound represented by formula (II) include compounds represented by any one of formulas (II-1) to (II-15). Among these, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-Ⅱ), or formula (II-11-1) to formula (II-15) A compound represented by) is preferable, and a compound represented by formula (II-1), formula (II-7), formula (II-VII) or formula (II-15) is more preferable.

Examples of the compound represented by formula (III) include compounds represented by any one of formulas (III-1) to (III-15). Among these, formulas (III-1), formulas (III-3), formulas (III-5), formulas (III-7), formulas (III-III), or formulas (III-11-1) to (III-15) A compound represented by) is preferable, and a compound represented by formula (III-1), formula (III-7), formula (III-VII) or formula (III-15) is more preferable.

The compound represented by formula (II) and the compound represented by formula (III) may be used alone, or a compound represented by formula (II) and a compound represented by formula (III) may be used in combination. When these are used together, the content ratio of the compound represented by formula (II) and the compound represented by formula (III) is on a molar basis, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10 , Even more preferably from 20:80 to 80:20.

As (# 2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. (# 2) As 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3- Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacrylo Iloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, etc. are mentioned.

As (# 3), a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. (ｂ3) specifically, tetrahydrofurfuryl acrylate (for example, biscoat V # 150, Osaka Organic Chemical Industry Co., Ltd. product), tetrahydrofurfuryl methacrylate, etc. are mentioned.

It is preferable that (i) is (i) from the viewpoint of further improving the reliability, such as heat resistance and chemical resistance, of the obtained color filter. Moreover, from the viewpoint of excellent storage stability of the colored curable resin composition, (# 1-2) is more preferable.

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 called "dicyclopentanyl (meth) acrylate" as a common name. Also referred to as "tricyclodecyl (meth) acrylate", tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth) acrylate (in the art, the term "dicyclopentenyl ( Meta) acrylate), 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;

Hydroxy 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, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimidebutyrate, 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, vinyl toluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo [2.2.1] hepto-2-ene are preferred.

In the resin [# 1], the proportion of the structural unit derived from each is among the total structural units constituting the resin [# 1],

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

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

Is preferably,

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

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

It is more preferable.

When the proportion of the structural unit of the resin [# 1] is in the above range, there is a tendency that the storage stability of the colored curable resin composition, developability when forming a colored pattern, and solvent resistance of the resulting color filter tend to be excellent.

Resin [# 1] is described in, for example, the method described in the literature "Experiment of Polymer Synthesis" [Otsu Takayuki, published by the Chemical Industry Co., Ltd., first edition, published on March 1, 1972] and described in the document It can be prepared by referring to the cited literature.

Specifically, a method of heating and keeping warm while stirring in a deoxygenated atmosphere by placing predetermined amounts of (a) and (iii), a polymerization initiator, a solvent, and the like into a reaction vessel and replacing oxygen with nitrogen, for example. have. Moreover, the polymerization initiator and solvent used herein are not particularly limited, and those conventionally used in the art can be used. As the polymerization initiator, for example, an azo compound [2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile, etc.)] or an organic peroxide (such as benzoyl peroxide) Examples thereof include solvents in which respective monomers are dissolved, and examples of the solvent (E) of the colored curable resin composition of the present invention include the solvents described later.

Moreover, the obtained copolymer may use the solution after the reaction as it is, or may use a concentrated or diluted solution, or may be used as a solid (powder) extracted by a method such as reprecipitation. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during its polymerization, the solution after reaction can be used as it is for the preparation of the colored curable resin composition of the present invention, so the colored curable resin composition of the present invention The manufacturing process can be simplified.

In resin [X2], the proportion of the structural unit derived from each is among the total structural units constituting resin [X2],

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

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

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

It is more preferable.

When the proportion of the structural unit of the resin [# 2] is in the above range, the storage stability of the colored curable resin composition, developability when forming a colored pattern, and solvent resistance, heat resistance and mechanical strength of the resulting color filter tend to be excellent. There is this.

Resin [# 2] can be produced in the same manner as described for example as a method for producing resin [# 1].

In resin [X3], the proportion of the structural unit derived from each is among the total structural units constituting resin [X3],

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%

It is more preferable.

Resin [# 3] can be produced in the same manner as described for example as a method for producing resin [# 1].

Resin [# 4] is prepared by obtaining a copolymer of (a) and (c) and adding a cyclic ether having 2 to 4 carbon atoms of (i) to the carboxylic acid and / or carboxylic acid anhydride of (a). You can.

First, the copolymers of (a) and (c) are produced in the same manner as the method described as a method for producing the resin [# 1]. In this case, it is preferable that the ratio of the structural unit derived from each is the same ratio as heard in the resin [# 3].

Subsequently, a part of carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms in (i).

Subsequent to the production of the copolymers of (a) and (c), the atmosphere in the flask is replaced by nitrogen to air, and (iv), a reaction catalyst of carboxylic acid or carboxylic acid anhydride with a cyclic ether [eg, Tris (dimethylaminomethyl) phenol, etc.] and a polymerization inhibitor (for example, hydroquinone, etc.) are placed in a flask and reacted, for example, at 60 to 130 ° C for 1 to 10 hours to produce a resin [# 4]. You can.

The amount of (i) used is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). By setting it as this range, there exists a tendency for the balance of the storage stability of a coloring curable resin composition, the developability at the time of forming a pattern, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern to become favorable. Since the reactivity of the cyclic ether is high and unreacted (VIII) is difficult to remain, (VIII) used for the resin [VIII] is preferably (VIII), and more preferably (VIII-1).

The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (i) and (c). The use amount of the polymerization inhibitor is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (i) and (c).

Reaction conditions, such as a mixing method, reaction temperature, and time, can be appropriately adjusted in consideration of the production facility or the amount of heat generated by polymerization. Moreover, the mixing method and reaction temperature can be appropriately adjusted in consideration of the production facilities and the amount of heat generated by polymerization in the same manner as the polymerization conditions.

As the first step, the resin [IX5] is obtained in the same manner as the method for producing the resin [X1] described above to obtain a copolymer of (X) and (C). As in the above, the obtained copolymer may use the solution after the reaction as it is, or may use a concentrated or diluted solution, or may be used as a solid (powder) extracted by a method such as reprecipitation.

The ratios of the structural units derived from (i) and (c) are respectively based on the total number of moles of all the structural units constituting the copolymer.

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

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

Is preferably,

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

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

It is more preferable.

Further, under the same conditions as the method for producing the resin [X4], the carboxylic ether derived from (X) of the copolymer of (X) and (C) is reacted with the carboxylic acid or carboxylic acid anhydride possessed by (A). By doing this, resin [IX5] can be obtained.

The amount of (a) to be reacted with the copolymer is preferably 5 to 80 moles per 100 moles (i). Since the reactivity of the cyclic ether is high and unreacted (VIII) is difficult to remain, (VIII) used for the resin [VIII] is preferably (VIII), and more preferably (VIII-1).

Resin [Ｋ6] is a resin in which carboxylic acid anhydride is further reacted with resin [Ｋ5]. Carbonic anhydride is reacted with a hydroxy group generated by the reaction of cyclic ether with carboxylic acid or carboxylic anhydride.

As 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 And hydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride. The amount of carboxylic acid anhydride is preferably 0.5 to 1 mole per 1 mole of (a).

As the resin (Ｂ), specifically, 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxycitcyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate / (meth ) Resins such as acrylic acid copolymers [# 1]; Glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxycyclo [5.2 .1.0 ^2.6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxycitcyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate / (meth) acrylic acid / Resins such as vinyl toluene copolymer and 3-methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer [Ｋ2]; 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 [Ｋ3 ]; A resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) to a tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer Resins such as resins to which acrylate is added, resins to which glycidyl (meth) acrylate is added to tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer [# 4]; Tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate copolymer of (meth) acrylic acid reacted with resin, tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resins such as resins in which (meth) acrylic acid is reacted with a copolymer [# 5]; And resins such as resins in which tetrahydrophthalic anhydride is further reacted with a resin in which (meth) acrylic acid is reacted with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate. .

The resin (Ｂ) is preferably one selected from the group consisting of resin [Ｋ1], resin [Ｋ2] and resin [Ｋ3], more preferably selected from the group consisting of resin [Ｋ2] and resin [Ｋ3] It is one. If it is such a resin, the coloring curable resin composition is excellent in developability. From the viewpoint of adhesion between the colored pattern and the substrate, resin [# 2] is even more preferable.

The weight average molecular weight of the resin in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, even more preferably 5,000 to 30,000. When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is high, and the solubility in the developing solution of the unexposed portion is good, so the resolution of the colored pattern tends to be improved.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the resin (i) is preferably 1.1 to 6, and more preferably 1.2 to 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 of potassium hydroxide (mg) required to neutralize 1 g of the resin, and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.

The content of the resin (i) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, even more preferably 17 to 55% by mass relative to the total amount of solids. When the content of the resin is in the above range, a colored pattern can be formed, and the resolution and the residual film rate of the colored pattern tend to improve.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound capable of polymerizing with an active radical and / or acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond, and the like. (Meth) acrylic acid ester compound.

As a polymerizable compound having one ethylenically unsaturated bond, for example, nonylphenylcarbitolacrylate, 2-hydroxy-3-phenoxypropylacrylate, 2-ethylhexylcarbitolacrylate, 2-hydroxyethyl Acrylates, N-vinylpyrrolidone, and the like (a), (iii) and (c) described above.

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

Among these, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. As such a polymerizable compound, for example, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritolhepta (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 Yttrium, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like, among them, dipentaerythritol penta (meth) acrylate and dipenta Erythritol hexa (meth) acrylate is preferred.

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

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and even more preferably 17 to 55% by mass relative to the total amount of solids.

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

When the content of the polymerizable compound (C) is within the above range, the residual film rate at the time of forming the colored pattern and the chemical resistance of the color filter tend to improve.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating active radicals, acids, etc. by the action of light or heat, and capable of initiating polymerization, and a known polymerization initiator can be used.

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

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

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) ) Octan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethan-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3 , 3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethan-1-imine, N-acetoxy-1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropan-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] -3-cyclopentylpropan-1-one-2-imine. You may use commercial items, such as a monocure OXE01, OXE02 (above, BASF company make), N-1919 (made by ADEKA company). Among these, O-acyloxime compounds are N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane At least one member selected from the group consisting of -1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferred. , N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine is more preferred.

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

Examples of the compound having a partial structure represented by formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- ( 4-morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane And -1-one. You may use commercial items, such as Ilgacure 369, 907, 379 (above, BASF Corporation).

Examples of the compound having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2 -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenylketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, and α, α-diethoxyacetophenone and benzyl dimethyl ketal.

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 Formula (d5), for example.

[In the formula (d5), R ¹³ to R ¹⁸ represent an aryl group having 6 to 10 carbon atoms which may have a substituent]

Examples of the aryl group having 6 to 10 carbon atoms include, for example, a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, and a naphthyl group, and preferably 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. Examples of the alkoxy group having 1 to 4 carbon atoms include, for example, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and are preferably methoxy groups.

As the biimidazole compound, for example, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichloro 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, for example, JPS48-38403-B, JPS62-174204-A, etc.), phenyl group at 4,4', 5,5'-position And an imidazole compound substituted with a carboalkoxy group (see, for example, JPH07-10913-A, etc.). Among these, compounds represented by the following formula and mixtures thereof are preferred.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl)- 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.

Moreover, as a polymerization initiator (D), benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, o-benzoyl methyl 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-ethylanthraquinone, and campaquinone; And 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds.

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

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

The content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass, and more preferably 1 to 30 parts by mass, with respect to 100 parts by mass of the total amount of the resin (iii) and the polymerizable compound (C).

<Polymerization start aid (D1)>

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

Examples of the polymerization initiator (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone [common name, Mihiler ketone], 4,4'-bis (diethylamino) benzophenone, 4,4 '-Bis (ethylmethylamino) benzophenone, etc. are mentioned, and among these, 4,4'-bis (diethylamino) benzophenone is preferable. You may use commercial items, such as EAB-F (made by Hodogaya Chemical Industry Co., Ltd.).

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibu And ethoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

As said thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxycity And oxanthone.

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 And sulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

When using such a polymerization initiator (D1), the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin and the polymerizable compound (C). It is the mass part. When the amount of the polymerization initiator (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to improve.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent commonly used in the art may be used. For example, ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether esters Solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule, not containing -COO-), alcohol solvent (containing OH in the molecule,- And solvents that do not contain 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-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyric acid And butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone, and the like.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and 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 methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenitol, methyl anisole, etc. Can be mentioned.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, methyl 3-ethoxypropionic acid, 3-ethoxypropionic acid ethyl, 2-methoxypropionic acid methyl, 2-methoxypropionic acid ethyl, 2-methoxypropionic acid propyl, 2-ethoxypropionic acid methyl, 2-ethoxypropionic acid ethyl, 2-methoxy-2-methyl Methyl propionate, ethyl 2-ethoxy-2-methyl propionate, 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 Monoe There may be mentioned ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate and the like.

As a ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentane And 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 solvent include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

These solvents may be used alone or in combination of two or more.

Among these, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxypropionic acid 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, etc. 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, etc. are more preferred.

The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the total amount of the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 30 mass%, and more preferably 8 to 25 mass%. When the content of the solvent (E) is in the above range, the flatness at the time of application becomes good, and the color density is not insufficient when the color filter is formed, so the display characteristics tend to be improved.

<Surface leveling agent>

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

As a silicone type surfactant, surfactant etc. which have a siloxane bond in a molecule | numerator are mentioned. Specifically, Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 [trade name: manufactured by Torre and Dow Corning Co., Ltd.], KP321, KP322 , KP323, KP324, KP326, KP340, KP341 [manufactured by Shin-Etsu Chemical Co., Ltd.], TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 [Momentive Performance Materials Japan Joint Stock Company And the like.

As said fluorine type surfactant, surfactant etc. which have a fluorocarbon chain in a molecule | numerator are mentioned. Specifically, Floride (registered trademark) FC430, Floride FC431 (Sumitomo 3M Co., Ltd.), Megapack (registered trademark) F142D, Megapack F171, Megapack F172, Megapack F173, Megapack F177, Megapack F183, Megapack F554, Megapack R30, Megapack RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 [Mitsubishi Material Electronic Chemical Etc.), Saffron (registered trademark) S381, Saffron S382, Saffron SC101, Saffron SC105 (Asahi Glass Co., Ltd.), E5844 (Daikin Fine Chemical Research Institute), and the like. have.

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in a molecule. Specifically, Megapack (trademark) R08, Megapack BL20, Megapack F475, Megapack F477, Megapack F443 (made by DIC Corporation), etc. are mentioned.

When a surface leveling agent is contained, the content thereof is preferably 0.001 mass% or more and 0.2 mass% or less, more preferably 0.002 mass% or more and 0.1 mass% or less, based on the total amount of the colored curable resin composition, Even more preferably, it is 0.005 mass% or more and 0.07 mass% or less. When the content of the surface leveling agent is within the above range, the flatness of the color filter can be further improved.

<Other ingredients>

The colored curable resin composition of the present invention may contain additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and the like, if necessary.

<Method for producing a colored curable resin composition>

The colored curable resin composition of the present invention is, for example, a colorant (A), a resin (i), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), a surface leveling agent that can be used as needed It can be prepared by mixing (iv), the polymerization initiation aid (D1) and other components.

In the case of containing the pigment (P), the pigment is mixed with a part or all of the solvent (E) in advance, and dispersed using a beads mill or the like until the average particle diameter of the pigment is about 0.2 µm or less. It is preferred. At this time, a part or all of the said pigment dispersing agent and resin may be mix | blended as needed. The desired colored curable resin composition can be prepared by mixing the pigment dispersion obtained in this way with the remaining components at a predetermined concentration.

It is preferable to prepare the solution by dissolving the compound (1) in part or all of the solvent (E) in advance. It is preferable to filter the solution with a filter having a pore diameter of about 0.01 to 1 μm.

It is preferable to filter the colored curable resin composition after mixing with a filter having a pore diameter of about 0.01 to 10 µm.

<Production Method of Color Filter>

The photolithographic method, the inkjet method, the printing method etc. are mentioned as a method of manufacturing a colored patterned coating film from the colored curable resin composition of this invention. Among these, the photolithography method is preferable. The photolithography method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and a photomask is fitted to expose and develop the colored composition layer. In the photolithography method, a colored coating film which is a cured product of the colored composition layer can be formed by not using and / or developing a photomask during exposure. The colored patterned coating film or colored coating film thus formed is the color filter of the present invention.

The film thickness of the color filter to be produced is not particularly limited, but can be appropriately adjusted depending on the purpose or application, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, even more preferably 0.5 to 6 μm.

As the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass with silica coating on the surface, resin plates such as polycarbonate, methyl polymethacrylate, polyethylene terephthalate, silicon, and aluminum on the substrate , Silver, silver / copper / palladium alloy thin films or the like can be used. A separate color filter layer, resin layer, transistor, circuit, etc. may be formed on such a substrate.

The formation of each color pixel by the photolithographic method can be carried out in a known or conventional apparatus or condition. For example, it can be produced as follows.

First, a colored curable resin composition is applied onto a substrate, and volatile components such as a solvent are removed and dried by heating and drying (prebake) and / or drying under reduced pressure to obtain a smooth colored composition layer.

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

The temperature in the case of performing heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. Moreover, it is preferable that it is 10 to 60 minutes as heating time, and it is more preferable that it is 30 to 30 minutes.

When drying under reduced pressure, it is preferable to carry out under a pressure of 50 to 150 Pa and in a temperature range of 20 to 25 ° C.

The thickness of the colored composition layer is not particularly limited, but may be appropriately selected depending on the thickness of the target color filter.

Subsequently, the colored composition layer is exposed by sandwiching a photomask to form a desired colored patterned coating film. The pattern on the photomask is not particularly limited, but a pattern according to the intended use may be used.

The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or a band pass filter that extracts light near 436 nm, near 408 nm, and around 365 nm from these wavelength ranges is used. It 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 uniformly irradiate parallel light on the entire exposure surface or to perform a precise position combination between the photomask and the substrate on which the coloring composition layer is formed. It is desirable to do.

A colored patterned coating film is formed on the substrate by developing the colored composition layer after exposure by contacting the developer. By development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. As the developer, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of the alkaline compound in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Moreover, the developer may contain a surfactant.

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

After development, it is preferable to wash with water.

Moreover, it is preferable to post-bake the obtained colored patterned coating film. The post-baking temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-baking time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes.

Since the compound of the present invention has a high absorbance, it is possible to produce a color filter with high brightness especially by a colored curable resin composition using the same. The color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

Example

Hereinafter, the present invention will be described in more detail by examples, but the present invention is not limited by these examples. In the examples, the percentages and parts representing the content to the amount used are based on mass unless otherwise specified.

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

Example 1

The following reaction was performed under nitrogen atmosphere.

36.3 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 at room temperature for 30 minutes. Next, 50.0 parts of benzoic acid chloride (manufactured by Tokyo Kasei Co., Ltd.) was added dropwise over 10 minutes. After completion of dropping, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture on ice, 45.7 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, after ice-cooling the reaction mixture, 34.2 parts of a 30% aqueous 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 was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating reflux. Subsequently, after the reaction mixture was allowed to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, and 200 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped, and after standing for 30 minutes, the organic layer and the water layer were separated. After the water layer was discarded by separating operation, the organic layer was washed with 200 parts of 1 N (一 規定) 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 and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60 ° C. to obtain 52.0 parts of a compound represented by formula (VII-I-1). Yield 50%

The following reaction was performed under nitrogen atmosphere.

To a flask equipped with a cooling tube and a stirring device, 9.3 parts of the compound represented by formula (식 -I-1), 10.0 parts of 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 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. Then, the reaction mixture was cooled to room temperature, and then diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline, and then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped, and after standing for 30 minutes, the organic layer and the water layer were separated. After the water layer was discarded by separating operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a blue-violet solid. Furthermore, the blue-violet solid was dried under reduced pressure at 60 ° C to obtain 19.8 parts of the compound represented by formula (A-II-1). 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 under nitrogen atmosphere.

In a flask equipped with a cooling tube and a stirring device, 10.0 parts of a compound represented by formula (A-II-1), bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.5 parts and N, After adding 100.0 parts of N-dimethylformamide, the mixture was stirred at 50 to 60 ° C for 3 hours. Subsequently, after cooling the reaction mixture to room temperature, dropping it with 2000.0 parts of tap water with stirring for 1 hour gives a dark blue suspension. Filtration of the resulting suspension gave a turquoise solid. Moreover, the turquoise solid was dried under reduced pressure at 60 ° C to obtain 11.3 parts of the compound represented by formula (A-I-1). Yield 82%

0.35 g of the compound represented by formula (A-I-1) 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 2.9 (arbitrary units) at λmax = 628 nm.

Synthesis Example 1

An appropriate amount of nitrogen was flowed into a nitrogen atmosphere in a flask equipped with a reflux cooler, a dropping funnel and a stirrer, and 100 parts of propylene glycol monomethyl ether acetate was added and heated to 85 ° C while stirring. Subsequently, in the flask, 19 parts of methacrylic acid, 3,4-epoxycyclo [5.2.1.0 ^2.6 ] decane-8-ylacrylate and 3,4-epoxycyclo [5.2.1.0 ^2.6 ] decane-9- A mixture of monoacrylate (content ratio is 50:50 in molar ratio) [trade name "E-DCPA", manufactured by Daicel Co., Ltd.) A solution of 171 parts dissolved in 40 parts of propylene glycol monomethyl ether acetate is used as a dropping pump. It was dripped over about 5 hours. On the other hand, a solution in which 26 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 120 parts of propylene glycol monomethyl ether acetate was added to the flask over a period of about 5 hours using a separate dropping pump. Dropped within. After the dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer [resin (Ｂ-1)] having a solid content of 43.5%. The obtained resin (VII-1) had a weight average molecular weight of 8000, a molecular weight distribution of 1.98, and an acid value in terms of solid content of 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 the following conditions by GPC method.

Device: HLC-8120GPC [manufactured by Tosoh Corporation]

Column: TSK-GELG2000HXL

Column temperature: 40 ℃

Solvent: THF

Flow rate: 1.0 mL / min

Concentration of solid content in the test liquid: 0.001 to 0.01 mass%

Injection volume: 50 μL

Detector: RI

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 [manufactured by Tosoh Corporation]

The ratio (Mw / Mn) of the weight average molecular weight and number average molecular weight in terms of polystyrene obtained above was used as the molecular weight distribution.

Synthesis Example 2

To a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 250.4 parts of propylene glycol monomethyl ether acetate was taken, stirred with substitution with nitrogen, and heated to 120 ° C. Subsequently, 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 having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) To that, 6.13 parts of t-butyl hydroperoxide [Perbutyl O, manufactured by Nippon Oil Co., Ltd.] was added. This was dropped from the dropping funnel into the flask over 2 hours, and stirring was continued at 120 ° C. for 2 hours to perform aging. Subsequently, the inside of the flask was replaced with air, 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 process, and the reaction was continued at 120 ° C. for 6 hours, solid content. A solution of a copolymer [resin (Ｂ-2)] of 38.4 mass% and an acid value of 122 mg-KOH / g was obtained. The obtained resin (VII-2) had a weight average molecular weight (Mw) of 10700 and a molecular weight distribution of 2.18. The weight average molecular weight and molecular weight distribution were measured by the same method as the resin (X-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. Furthermore, 15.41 parts of 2,6-dihydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.09 parts of boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) were added and stirred at 65 ° C for 8.5 hours. After the mixture was cooled 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 formula (FC-1-1).

Example 2

The following reaction was performed under nitrogen atmosphere.

After adding 10.0 parts of the compound represented by formula (A-II-1), 5.3 parts of the compound represented by formula (FC-1-1Na) and 100.0 parts of N, N-dimethylformamide into a flask equipped with a cooling tube and a stirring device, , And stirred at 50-60 ° C for 3 hours. Subsequently, after cooling the reaction mixture to room temperature, dropping it with 2000.0 parts of tap water with stirring for 1 hour gives a dark blue suspension. Filtration of the resulting suspension gave a turquoise solid. Moreover, the turquoise solid was dried under reduced pressure at 60 ° C to obtain 12.0 parts of a compound represented by formula (A-I-3). Yield 83%

0.35 g of the compound represented by formula (A-I-3) was dissolved in chloroform to make the volume 250 cm 3, and 2 cm 3 of this was diluted with ion-exchanged water to make the volume 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 units) at λmax = 628 nm.

Example 3

The following reaction was performed under nitrogen atmosphere.

After adding 10.0 parts of the compound represented by formula (A-II-1) to the flask equipped with the cooling tube and the stirring device, 14.1 parts of tungstosilicate hydrate (manufactured by SIGMA-ALDRICH) and 100.0 parts of N, N-dimethylformamide , And stirred at 50-60 ° C for 3 hours. Subsequently, after cooling the reaction mixture to room temperature, dropping it with 2000.0 parts of tap water with stirring for 1 hour gives a dark blue suspension. Filtration of the resulting suspension gave a turquoise solid. Moreover, the turquoise solid was dried under reduced pressure at 60 ° C to obtain 17.3 parts of the compound represented by formula (A-I-4). Yield 83%

0.35 g of the compound represented by formula (A-I-4) was dissolved in chloroform to make the volume 250 cm 3, and 2 cm 3 of this was diluted with ion-exchanged water to make the volume 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 unit) at λmax = 638 nm.

Example 4

The following reaction was performed under nitrogen atmosphere.

32.2 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 at room temperature for 30 minutes. Next, 50.0 parts of 2-fluorobenzoic acid chloride (manufactured by Tokyo Kasei Co., Ltd.) was added dropwise over 10 minutes. After completion of dropping, the mixture was further stirred at room temperature for 2 hours. Subsequently, after ice-cooling the reaction mixture, 40.5 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, after ice-cooling the reaction mixture, 34.2 parts of a 30% aqueous 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 was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating reflux. Subsequently, after the reaction mixture was allowed to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, and 200 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped, and after standing for 30 minutes, the organic layer and the water layer were separated. After the water layer was discarded by 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 and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60 ° C. to obtain 49.9 parts of the compound represented by formula (VII-I-7). Yield 51%

The following reaction was performed under nitrogen atmosphere. To a flask equipped with a cooling tube and a stirring device, 9.9 parts of the compound represented by formula (i-I-7), 10.0 parts of 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 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. Then, the reaction mixture was cooled to room temperature, and then diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline, and then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped, and after standing for 30 minutes, the organic layer and the water layer were separated. After the water layer was discarded by separating operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a blue-violet solid. The obtained blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried under reduced pressure at 60 ° C. to obtain 17.2 parts of the compound represented by formula (A-II-7). 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 under nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 10.0 parts of a compound represented by formula (A-II-7), bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.), 5.7 parts 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, dropping it with 500.0 parts of tap water while stirring for 1 hour gives a dark blue suspension. Filtration of the resulting suspension gave a turquoise solid. Moreover, the turquoise solid was dried under reduced pressure at 60 ° C to obtain 11.9 parts of a compound represented by formula (A-I-7). Yield 86%

0.35 g of the compound represented by formula (A-I-7) 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 absorbance 3.1 (arbitrary units) at λmax = 630 nm.

Example 5

The following reaction was performed under 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 at room temperature for 30 minutes. Next, 50.0 parts of 2-bromobenzoic acid chloride (manufactured by Tokyo Kasei Co., Ltd.) was added dropwise over 10 minutes. After completion of dropping, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture on ice, 29.3 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, after ice-cooling the reaction mixture, 34.2 parts of a 30% aqueous 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 was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating reflux. Subsequently, after the reaction mixture was allowed to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, and 200 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped, and after standing for 30 minutes, the organic layer and the water layer were separated. After the water layer was discarded by 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 and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60 ° C. to obtain 41.6 parts of a compound represented by formula (X-I-X). Yield 45%

The following reaction was performed under nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 12.9 parts of the compound represented by formula (Ｂ-I-８), 10.0 parts of 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 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. Then, the reaction mixture was cooled to room temperature, and then diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline, and then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped, and after standing for 30 minutes, the organic layer and the water layer were separated. After the water layer was discarded by separating operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a blue-violet solid. The obtained blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C under reduced pressure to obtain 17.6 parts of a compound represented by formula (A-II-VII). Yield 80%

Identification of the compound represented by formula (A-II-８)

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

                          Exact Mass: 714.2

The following reaction was performed under nitrogen atmosphere.

To a flask equipped with a cooling tube and a stirring device, 10.0 parts of a compound represented by formula (A-II-８), 5.2 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) 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, dropping it with 500.0 parts of tap water while stirring for 1 hour gives a dark blue suspension. Filtration of the resulting suspension gave a turquoise solid. Moreover, the turquoise solid was dried under reduced pressure at 60 ° C to obtain 12.9 parts of the compound represented by formula (A-I-VII). Yield 96%

0.35 g of the compound represented by formula (A-I-８) was dissolved in chloroform to make the volume 250 cm 3, and 2 cm 3 of this was diluted with ion-exchanged water to make the volume 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 units) at λmax = 632 nm.

Example 6

The following reaction was performed under nitrogen atmosphere.

33.0 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 at room temperature for 30 minutes. Subsequently, 50.0 parts of 2-methylbenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of dropping, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture on ice, 41.6 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, after ice-cooling the reaction mixture, 34.2 parts of a 30% aqueous 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 was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating reflux. Subsequently, after the reaction mixture was allowed to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, and 200 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped, and after standing for 30 minutes, the organic layer and the water layer were separated. After the water layer was discarded by 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 and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60 ° C. to obtain 40.5 parts of a compound represented by formula (X-I-X). Yield 41%

The following reaction was performed under nitrogen atmosphere. To a flask equipped with a cooling tube and a stirring device, 9.7 parts of the compound represented by formula (식 -I-９), 10.0 parts of 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 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. Then, the reaction mixture was cooled to room temperature, and then diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline, and then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped, and after standing for 30 minutes, the organic layer and the water layer were separated. After the water layer was discarded by separating operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a blue-violet solid. The obtained blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried under reduced pressure at 60 ° C to obtain 15.1 parts of a compound represented by formula (A-II-VII). Yield 75%

Identification of the compound represented by formula (A-II-９)

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

                          Exact Mass: 650.3

The following reaction was performed under nitrogen atmosphere. To a flask equipped with a cooling tube and a stirring device, 10.0 parts of a compound represented by formula (A-II-９), 5.7 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) 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, dropping it with 500.0 parts of tap water while stirring for 1 hour gives a dark blue suspension. Filtration of the resulting suspension gave a turquoise solid. Moreover, the turquoise solid was dried under reduced pressure at 60 ° C to obtain 13.2 parts of a compound represented by formula (A-I-X). Yield 96%

0.35 g of the compound represented by formula (A-I-９) was dissolved in chloroform to make the volume 250 cm 3, and 2 cm 3 of this was diluted with ion-exchanged water to make the volume 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 unit) at λmax = 627 nm.

Example 7

The following reaction was performed under nitrogen atmosphere.

After adding 24.5 parts of potassium thiocyanate and 160.0 parts of acetone to a flask equipped with a cooling tube and a stirring device, the mixture was stirred at room temperature for 30 minutes. Next, 50.0 parts of 2-trifluoromethylbenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of dropping, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture on ice, 30.8 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, after ice-cooling the reaction mixture, 34.2 parts of a 30% aqueous 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 was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating reflux. Subsequently, after the reaction mixture was allowed to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, and 200 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped, and after standing for 30 minutes, the organic layer and the water layer were separated. After the water layer was discarded by 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 and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60 ° C. to obtain 31.1 parts of a compound represented by formula (VII-I-10). Yield 36%

The following reaction was performed under nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 11.4 parts of the compound represented by formula (Ｂ-I-10), 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.0 parts 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. Then, the reaction mixture was cooled to room temperature, and then diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline, and then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped, and after standing for 30 minutes, the organic layer and the water layer were separated. After the water layer was discarded by separating operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a blue-violet solid. The obtained blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried under reduced pressure at 60 ° C to obtain 15.2 parts of a compound represented by formula (A-II-1100). Yield 70%

Identification of the compound represented by formula (A-II-1100)

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

                          Exact Mass: 704.3

The following reaction was performed under nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 10.0 parts of a compound represented by formula (A-II-10), bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.1 parts 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, dropping it with 500.0 parts of tap water while stirring for 1 hour gives a dark blue suspension. Filtration of the resulting suspension gave a turquoise solid. Moreover, the turquoise solid was dried under reduced pressure at 60 ° C to obtain 11.4 parts of the compound represented by formula (A-I-10). Yield 85%

0.35 g of the compound represented by formula (A-I-10) 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 1.9 (arbitrary unit) at λmax = 631 nm.

Example 8

The following reaction was performed under nitrogen atmosphere.

33.0 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 at room temperature for 30 minutes. Subsequently, 50.0 parts of 2-methylbenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of dropping, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture on ice, 39.7 parts of dibutylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, after ice-cooling the reaction mixture, 34.2 parts of a 30% aqueous 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 was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating reflux. Subsequently, after the reaction mixture was allowed to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, and 200 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped, and after standing for 30 minutes, the organic layer and the water layer were separated. After the water layer was discarded by 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 and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60 ° C. to obtain 70.0 parts of a compound represented by formula (VII-I-111). Yield 72%

The following reaction was performed under nitrogen atmosphere. To a flask equipped with a cooling tube and a stirring device, 9.6 parts of the compound represented by formula (i-I-111), 10.0 parts of 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 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. Then, the reaction mixture was cooled to room temperature, and then diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline, and then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped, and after standing for 30 minutes, the organic layer and the water layer were separated. After the water layer was discarded by separating operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a blue-violet solid. The obtained blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried under reduced pressure at 60 ° C. to obtain 19.7 parts of the compound represented by formula (A-II-111). Yield 98%

Identification of the compound represented by formula (A-II-11.1)

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

                          Exact Mass: 644.4

The following reaction was performed under nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 10.0 parts of a compound represented by formula (A-II-111), 4.4 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.), 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, dropping it with 500.0 parts of tap water while stirring for 1 hour gives a dark blue suspension. Filtration of the resulting suspension gave a turquoise solid. Moreover, the turquoise solid was dried under reduced pressure at 60 ° C to obtain 11.7 parts of a compound represented by formula (A-I-111). Yield 85%

0.35 g of the compound represented by formula (A-I-111) was dissolved in chloroform to make the volume 250 cm 3, 2 cm 3 of which was diluted with ion-exchanged water to make the volume 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 3.0 (arbitrary units) at λmax = 613 nm.

Example 9

The following reaction was performed under nitrogen atmosphere.

After adding 29.2 parts of potassium thiocyanate and 160.0 parts of acetone to a flask equipped with a cooling tube and a stirring device, the mixture was stirred at room temperature for 30 minutes. Subsequently, 50.0 parts of 2-chlorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of dropping, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture on ice, 43.8 parts of bis (2-ethoxyethyl) amine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, after ice-cooling the reaction mixture, 34.2 parts of a 30% aqueous 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 was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating reflux. Subsequently, after the reaction mixture was allowed to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, and 200 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped, and after standing for 30 minutes, the organic layer and the water layer were separated. After the water layer was discarded by 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 and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60 ° C. to obtain 45.0 parts of the compound represented by formula (VII-I-12). Yield 44%

The following reaction was performed under nitrogen atmosphere. To a flask equipped with a cooling tube and a stirring device, 10.6 parts of the compound represented by formula (i-I-12), 10.0 parts of 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 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. Then, the reaction mixture was cooled to room temperature, and then diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline, and then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped, and after standing for 30 minutes, the organic layer and the water layer were separated. After the water layer was discarded by separating operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a blue-violet solid. The obtained blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried under reduced pressure at 60 ° C. to obtain 21.3 parts of the compound represented by formula (A-II-11.2). Yield 99%

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

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

                          Exact Mass: 696.3

The following reaction was performed under nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 10.0 parts of a compound represented by formula (A-II-1-2), 4.1 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) 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, dropping it with 500.0 parts of tap water while stirring for 1 hour gives a dark blue suspension. Filtration of the resulting suspension gave a turquoise solid. Moreover, the turquoise solid was dried under reduced pressure at 60 ° C. to obtain 11.4 parts of a compound represented by formula (A-I-12). Yield 85%

0.35 g of the compound represented by formula (A-I-12) 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 λmax = 625 nm.

Example 10

The following reaction was performed under nitrogen atmosphere.

To a flask equipped with a cooling tube and a stirring device, 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 thereto, and then 30 at room temperature. Stir for a minute. Then, 2.6 parts of potassium thiocyanate was added over 10 minutes. After completion of the addition, the mixture was further stirred at room temperature for 3 hours. Subsequently, 50.0 parts of tap water was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. The precipitated yellow solid was separated by filtration, and then the obtained yellow solid was purified by column chromatography. The purified yellow solid was dried under reduced pressure at 60 ° C to obtain 1.0 part of a compound represented by formula (VII-II-11.3). Yield 22%

The following reaction was performed under nitrogen atmosphere. To the flask provided with the cooling tube and the stirring device, 5.0 parts of the compound represented by the formula (X-II-13) and 50.0 parts of ethanol were added, followed by stirring at room temperature for 30 minutes. Subsequently, 2.5 parts of piperidine (manufactured by Tokyo Kasei Co., Ltd.) and 1.2 parts of glacial acetic acid were added dropwise over 10 minutes, respectively. After completion of the dropwise addition, the mixture was further stirred under heating reflux for 2 hours. 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. The precipitated yellow solid was separated by filtration, and then the obtained yellow solid was purified by column chromatography. The purified yellow solid was dried under reduced pressure at 60 ° C. to obtain 3.8 parts of the compound represented by formula (VII-I-11.3). Yield 61%

The following reaction was performed under nitrogen atmosphere.

To a flask equipped with a cooling tube and a stirring device, 10.2 parts of the compound represented by formula (i-I-13), 10.0 parts of 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 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. Then, the reaction mixture was cooled to room temperature, and then diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline, and then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped, and after standing for 30 minutes, the organic layer and the water layer were separated. After the water layer was discarded by separating operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a blue-violet solid. The obtained blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried under reduced pressure at 60 ° C to obtain 6.8 parts of the compound represented by formula (A-II-11.3). Yield 33%

Identification of the compound represented by formula (A-II-11.3)

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

                          Exact Mass: 664.3

The following reaction was performed under nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 10.0 parts of a compound represented by formula (A-II-11.3), 4.7 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.), 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, dropping it with 500.0 parts of tap water while stirring for 1 hour gives a dark blue suspension. Filtration of the resulting suspension gave a turquoise solid. Moreover, the turquoise solid was dried under reduced pressure at 60 ° C. to obtain 11.4 parts of a compound represented by formula (A-I-13). Yield 80%

0.35 g of the compound represented by formula (A-I-13) was dissolved in chloroform to make the volume 250 cm 3, and 2 cm 3 of this was diluted with ion-exchanged water to make the volume 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 λmax = 636 nm.

Example 11

The following reaction was performed under nitrogen atmosphere.

To a flask equipped with a cooling tube and a stirring device, 5.0 parts of 4-chlorophenacyl bromide (manufactured by Tokyo Kasei Co., Ltd.) and 50.0 parts of 50% isopropanol aqueous solution were added, followed by stirring at room temperature for 30 minutes. Subsequently, 3.1 parts of potassium thiocyanate was added over 10 minutes. After completion of the addition, the mixture was further stirred at room temperature for 3 hours. Subsequently, 50.0 parts of tap water was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. The precipitated yellow solid was separated by filtration, and then the obtained yellow solid was purified by column chromatography. The purified yellow solid was dried under reduced pressure at 60 ° C. to obtain 4.0 parts of the compound represented by formula (VII-Ⅱ-1４). Yield 89%

The following reaction was performed under nitrogen atmosphere.

To a flask equipped with a cooling tube and a stirring device, 5.0 parts of the compound represented by formula (XII-41) and 50.0 parts of ethanol were added, followed by stirring at room temperature for 30 minutes. Subsequently, 3.0 parts of piperidine (manufactured by Tokyo Kasei Co., Ltd.) and 1.4 parts of glacial acetic acid were added dropwise over 10 minutes, respectively. After completion of the dropwise addition, the mixture was further stirred under heating reflux for 2 hours. 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. The precipitated yellow solid was separated by filtration, and then the obtained yellow solid was purified by column chromatography. The purified yellow solid was dried under reduced pressure at 60 ° C. to obtain 3.7 parts of the compound represented by formula (VII-I-14). Yield 57%

The following reaction was performed under nitrogen atmosphere.

8.8 parts of compound represented by formula (i-I-14), 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.0 parts and toluene in a flask equipped with a cooling tube and a stirring device After adding 20.0 parts, 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100 ° C for 3 hours. Then, the reaction mixture was cooled to room temperature, and then diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline, and then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped, and after standing for 30 minutes, the organic layer and the water layer were separated. After the water layer was discarded by separating operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a blue-violet solid. The obtained blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried under reduced pressure at 60 ° C to obtain 5.3 parts of a compound represented by formula (A-II-1４). Yield 26%

Identification of the compound represented by formula (A-Ⅱ-1４)

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

                          Exact Mass: 620.3

The following reaction was performed under nitrogen atmosphere.

In a flask equipped with a cooling tube and a stirring device, 10.0 parts of a compound represented by formula (A-II-1４), 8.0 parts of potassium tris (trifluoromethanesulfonyl) methide (manufactured by Central Glass Co., Ltd.) 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, dropping it with 500.0 parts of tap water while stirring for 1 hour gives a dark blue suspension. Filtration of the resulting suspension gave a turquoise solid. Moreover, the turquoise solid was dried under reduced pressure at 60 ° C to obtain 13.6 parts of the compound represented by formula (A-I-1４). Yield 85%

0.35 g of the compound represented by formula (A-I-14) was dissolved in chloroform to make the volume 250 cm 3, and 2 cm 3 of this was diluted with ion-exchanged water to make the volume 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 unit) at λmax = 623 nm.

Example 12

The following reaction was performed under nitrogen atmosphere.

33.0 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 at room temperature for 30 minutes. Next, 50.0 parts of benzoic acid chloride (manufactured by Tokyo Kasei Co., Ltd.) was added dropwise over 10 minutes. After completion of dropping, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture on ice, 41.6 parts of N-isopropyl aniline (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, after ice-cooling the reaction mixture, 34.2 parts of a 30% aqueous 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 was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating reflux. Subsequently, after the reaction mixture was allowed to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, and 200 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped, and after standing for 30 minutes, the organic layer and the water layer were separated. After the water layer was discarded by 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 and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60 ° C. to obtain 44.8 parts of the compound represented by formula (VII-I-15). Yield 47%

The following reaction was performed under nitrogen atmosphere.

To a flask equipped with a cooling tube and a stirring device, 9.3 parts of the compound represented by formula (i-I-15), 10.0 parts of 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 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. Then, the reaction mixture was cooled to room temperature, and then diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline, and then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped, and after standing for 30 minutes, the organic layer and the water layer were separated. After the water layer was discarded by separating operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a blue-violet solid. The obtained blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried under reduced pressure at 60 ° C. to obtain 20.5 parts of a compound represented by formula (A-II-15). Yield 100%

Identification of the compound represented by formula (A-Ⅱ-15)

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

                          Exact Mass: 636.3

The following reaction was performed under nitrogen atmosphere.

To a flask equipped with a cooling tube and a stirring device, 10.0 parts of a compound represented by formula (A-II-15), 5.9 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) 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, dropping it with 500.0 parts of tap water while stirring for 1 hour gives a dark blue suspension. Filtration of the resulting suspension gave a turquoise solid. Moreover, the turquoise solid was dried under reduced pressure at 60 ° C to obtain 11.7 parts of a compound represented by formula (A-I-15). Yield 85%

0.35 g of the compound represented by formula (A-I-15) 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 2.8 (arbitrary units) at λmax = 626 nm.

Example 13

A solution of 4,4'-dichlorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) (10 g, 90 mmol) of N, N-dimethylformamide (100 ml) was cooled in an ice bath, and sodium hydroxide (60%, 4.3 g, 90 mmol) was added, stirred for a while, and then compound 2 (6.5 g, 30 mmol) was added little by little. After stirring at room temperature for 5 hours, water was added, dichloromethane was extracted, and purified by silica gel column chromatography to obtain a compound represented by formula (WPF2) (3.1 g, yield 24%).

The following reaction was performed under nitrogen atmosphere.

To a flask equipped with a cooling tube and a stirring device, 7.6 parts of the compound represented by formula (X-I-7), 10.0 parts of the compound represented by formula (XP2) and 20.0 parts of toluene were added, and then 11.4 parts of phosphorus oxychloride were added. It stirred at 95-100 degreeC for 3 hours. Then, the reaction mixture was cooled to room temperature, and then diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline, and then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped, and after standing for 30 minutes, the organic layer and the water layer were separated. After the water layer was discarded by separating operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a blue-violet solid. The obtained blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried under reduced pressure at 60 ° C. to obtain 17.8 parts of the compound represented by formula (A-II-1165). Yield 100%

Identification of the compound represented by formula (A-II-11.6)

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

                          Exact Mass: 750.3

The following reaction was performed under nitrogen atmosphere.

In a flask equipped with a cooling tube and a stirring device, 10.0 parts of a compound represented by formula (A-II-11.6), 5.0 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) 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, dropping it with 500.0 parts of tap water while stirring for 1 hour gives a dark blue suspension. Filtration of the resulting suspension gave a turquoise solid. Moreover, the turquoise solid was dried under reduced pressure at 60 ° C. to obtain 11.9 parts of a compound represented by formula (A-I-16). Yield 90%

0.35 g of the compound represented by formula (A-I-16) 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 2.9 (arbitrary units) at λmax = 622 nm.

Example 14

The following reaction was performed under nitrogen atmosphere.

Into a flask equipped with a cooling tube and a stirring device, 28.9 parts of potassium thiocyanate and 160.0 parts of acetone were added, followed by stirring at room temperature for 30 minutes. Subsequently, 50.0 parts of 2,6-difluorobenzoic acid chloride (manufactured by Tokyo Kasei Co., Ltd.) was added dropwise over 10 minutes. After completion of dropping, the mixture was further stirred at room temperature for 2 hours. Subsequently, 36.4 parts of N-ethyl-o-toluidine (manufactured by Tokyo Kasei Co., Ltd.) was added dropwise after cooling the reaction mixture on ice. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, after ice-cooling the reaction mixture, 34.2 parts of a 30% aqueous 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 was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating reflux. Subsequently, after the reaction mixture was allowed to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, and 200 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped, and after standing for 30 minutes, the organic layer and the water layer were separated. After the water layer was discarded by 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 and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60 ° C. to obtain 25.2 parts of the compound represented by formula (VII-I-17). Yield 27%

The following reaction was performed under nitrogen atmosphere.

To a flask equipped with a cooling tube and a stirring device, 8.1 parts of the compound represented by formula (X-I-7), 10.0 parts of compound represented by formula (XP2) and 20.0 parts of toluene were added, and then 11.4 parts of phosphorus oxychloride were added. It stirred at 95-100 degreeC for 3 hours. Then, the reaction mixture was cooled to room temperature, and then diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline, and then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped, and after standing for 30 minutes, the organic layer and the water layer were separated. After the water layer was discarded by separating operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a blue-violet solid. The obtained blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried under reduced pressure at 60 ° C. to obtain 18.3 parts of the compound represented by formula (A-II-17). Yield 100%

Identification of the compound represented by formula (A-Ⅱ-11.7)

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

                          Exact Mass: 768.3

The following reaction was performed under nitrogen atmosphere.

In a flask equipped with a cooling tube and a stirring device, 10.0 parts of the compound represented by formula (A-II-11.7), 4.9 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) 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, dropping it with 500.0 parts of tap water while stirring for 1 hour gives a dark blue suspension. Filtration of the resulting suspension gave a turquoise solid. Moreover, the turquoise solid was dried under reduced pressure at 60 ° C. to obtain 11.5 parts of a compound represented by formula (A-I-7). Yield 87%

0.35 g of the compound represented by formula (A-I-7) 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 2.6 (arbitrary units) at λmax = 626 nm.

Example 15

The following reaction was performed under nitrogen atmosphere.

In a flask equipped with a cooling tube and a stirring device, 10.0 parts of a compound represented by formula (A-II-7), potassium bis (fluorosulfonyl) imide (manufactured by Mitsubishi Material Electronization Co., Ltd.), 4.3 parts, 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, dropping it with 500.0 parts of tap water while stirring for 1 hour gives a dark blue suspension. Filtration of the resulting suspension gave a turquoise solid. Moreover, the turquoise solid was dried under reduced pressure at 60 ° C to obtain 10.8 parts of a compound represented by formula (A-I-1―). Yield 89%

0.35 g of the compound represented by formula (A-I-1) was dissolved in chloroform to make the volume 250 cm 3, and 2 cm 3 of this was diluted with ion-exchanged water to make the volume 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 λmax = 631 nm.

Example 16

The following reaction was performed under nitrogen atmosphere.

To a flask equipped with a cooling tube and a stirring device, 10.0 parts of a compound represented by formula (A-II-7), cyclohexafluoropropane-1,3-bis (sulfonyl) imide potassium salt [Mitsubishi Material Electronization ( Note) 6.6 parts 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, dropping it with 500.0 parts of tap water while stirring for 1 hour gives a dark blue suspension. Filtration of the resulting suspension gave a turquoise solid. Moreover, the turquoise solid was dried under reduced pressure at 60 ° C to obtain 13.0 parts of a compound represented by formula (A-I-1). Yield 93%

0.35 g of the compound represented by formula (A-I-1) was dissolved in chloroform to make the volume 250 cm 3, and 2 cm 3 of this was diluted with ion-exchanged water to make the volume 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 units) at λmax = 631 nm.

Example 17

The following reaction was performed under nitrogen atmosphere.

10.0 parts of a compound represented by formula (A-II-7) and a bis (nonafluorobutanesulfonyl) imide potassium salt in a flask equipped with a cooling tube and a stirring device [Mitsubishi Material Electronization Co., Ltd. make] 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, dropping it with 500.0 parts of tap water while stirring for 1 hour gives a dark blue suspension. Filtration of the resulting suspension gave a turquoise solid. Moreover, the turquoise solid was dried under reduced pressure at 60 ° C to obtain 15.4 parts of the compound represented by formula (A-I-2200). Yield 84%

0.35 g of the compound represented by formula (A-I-20) 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 2.1 (arbitrary units) at λmax = 630 nm.

Example 18

The following reaction was performed under 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 potassium salt in a flask equipped with a cooling tube and a stirring device [Mitsubishi Material Electronization Co., Ltd. product] 3.9 parts and N, N-dimethylformamide 30.0 parts were added, followed by stirring at 40 ° C for 3 hours. Subsequently, after cooling the reaction mixture to room temperature, dropping it with 500.0 parts of tap water while stirring for 1 hour gives a dark blue suspension. Filtration of the resulting suspension gave a turquoise solid. Moreover, the turquoise solid was dried under reduced pressure at 60 ° C to obtain 10.7 parts of a compound represented by formula (A-I-211). Yield 91%

0.35 g of the compound represented by formula (A-I-211) 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 absorbance 3.0 (arbitrary units) at λmax = 638 nm.

[Preparation of colored curable resin composition]

Example 19

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

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

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

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Mongacure (trademark) OXE-01; Manufactured by BASF; O-acyloxime compounds] 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: Polyether-modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.15 copies

Was mixed to obtain a colored curable resin composition.

Comparative Example 1

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

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

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

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Mongacure (trademark) OXE-01; Manufactured by BASF; O-acyloxime compounds] 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: Polyether-modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.15 copies

Was mixed to obtain a colored curable resin composition.

[Production of color filters]

On the 2-inch glass substrate (# 1737; manufactured by Corning), the colored curable resin composition was applied by a spin coat method, and prebaked at 100 ° C for 3 minutes to form a colored composition layer. After cooling, the exposure machine [TME-150RSK; Topcon Co., Ltd. product, and irradiated with light at an exposure amount of 150 mJ / cm 2 (based on 365 nm) under an atmospheric atmosphere. Moreover, no photomask was used. A color filter (film thickness: 2.8 µm) was produced by subjecting the colored composition layer after exposure to a postbake at 180 ° C. for 20 minutes in an oven.

[Heat resistance evaluation]

The coating film of the colored curable resin composition was heated at 230 ° C. for 20 minutes, and the color difference (ΔEab *) before and after heating of the coating film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). When the above heat resistance evaluation was performed on the coating film obtained in Example 1, the color difference (ΔEab *) was 4.1.

When the above heat resistance evaluation was performed on 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 of the material.

Example 20

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

Example 21

A coloring film of the coloring composition was prepared in the same manner as in Example 19, except that the coloring agent (A-I-1) of Example 19 was changed to a coloring agent (A-I-4). The color difference (ΔEab *) of the coating film of was 6.0.

Example 22

A coloring film of the coloring composition was prepared in the same manner as in Example 19, except that the coloring agent (A-I-1) of Example 19 was changed to a coloring agent (A-I-7). The color difference (ΔEab *) of the coating film of was 2.7.

Example 23

A coloring film of the coloring composition was prepared in the same manner as in Example 19, except that the coloring agent (A-I-1) of Example 19 was changed to a coloring agent (A-I-VII). The color difference (ΔEab *) of the coating film of was 3.8.

Example 24

A coloring film of the coloring composition was prepared in the same manner as in Example 19, except that the coloring agent (A-I-1) of Example 19 was changed to a coloring agent (A-I-VII). The color difference (ΔEab *) of the coating film of was 2.8.

Example 25

A coloring film of the coloring composition was prepared in the same manner as in Example 19, except that the coloring agent (A-I-1) of Example 19 was changed to a coloring agent (A-I-10). The color difference (ΔEab *) of the coating film of was 6.8.

Example 26

A coloring 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 a coloring agent (A-I-111). The color difference (ΔEab *) of the coating film of was 3.9.

Example 27

A coloring film of the coloring composition was prepared in the same manner as in Example 19, except that the coloring agent (A-I-1) of Example 19 was changed to a coloring agent (A-I-12). The color difference (ΔEab *) of the coating film of was 4.1.

Example 28

A coloring film of the coloring composition was prepared in the same manner as in Example 19, except that the coloring agent (A-I-1) of Example 19 was changed to a coloring agent (A-I-13). The color difference (ΔEab *) of the coating film of was 3.2.

Example 29

A coloring film of the coloring composition was prepared in the same manner as in Example 19, except that the coloring agent (A-I-1) of Example 19 was changed to a coloring agent (A-I-14). The color difference (ΔEab *) of the coating film of was 5.7.

Example 30

A coloring 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 a coloring agent (A-I-15). The color difference (ΔEab *) of the coating film of was 3.4.

Example 31

A coloring film of the coloring composition was prepared in the same manner as in Example 19, except that the coloring agent (A-I-1) of Example 19 was changed to a coloring agent (A-I-16). The color difference (ΔEab *) of the coating film of was 1.9.

Example 32

A coloring film of the coloring composition was prepared in the same manner as in Example 19, except that the coloring agent (A-I-1) of Example 19 was changed to a coloring agent (A-I-107). The color difference (ΔEab *) of the coating film of was 2.2.

Example 33

A coloring film of the coloring composition was prepared in the same manner as in Example 19, except that the coloring agent (A-I-1) of Example 19 was changed to a coloring agent (A-I-1). The color difference (ΔEab *) of the coating film of was 2.9.

Example 34

A coloring film of the coloring composition was prepared in the same manner as in Example 19, except that the coloring agent (A-I-1) of Example 19 was changed to a coloring agent (A-I-1). The color difference (ΔEab *) of the coating film of was 3.5.

Example 35

A coloring film of the coloring composition was prepared in the same manner as in Example 19, except that the coloring agent (A-I-1) of Example 19 was changed to a coloring agent (A-I-2). The color difference (ΔEab *) of the coating film of was 3.8.

Example 36

A coloring film of the coloring composition was prepared in the same manner as in Example 19, except that the coloring agent (A-I-1) of Example 19 was changed to a coloring agent (A-I-211). The color difference (ΔEab *) of the coating film was 4.9.

When the colored curable resin composition containing the compound of the present invention is used, a color filter excellent in heat resistance can be provided. The color filter is useful as a color filter that can be used for display devices (for example, liquid crystal display devices, organic EL devices, electronic papers, etc.) and solid-state imaging devices.

Claims (12)

Compound represented by formula (A-I).

[In formula (A-I), X represents an oxygen atom, a nitrogen atom, or a sulfur atom. [Iii] ^m- represents an arbitrary m-valent anion. Each of R ⁴¹ to R ⁴⁶ is independently a hydrogen atom, an amino group, or an alkyl group having 1 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms, which may be substituted with a halogen atom, and oxygen atoms are inserted between carbon atoms constituting the alkyl group. Or an aryl group which may be substituted. R ⁴¹ and R ⁴² may combine to form a ring with the nitrogen atom to which they are attached, R ⁴³ and R ⁴⁴ may combine to form a ring with the nitrogen atom to which they are attached, and R ⁴⁵ and R ⁴⁶ may be They may combine to form a ring together with the nitrogen atom to which they are attached. 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, or an alkyl group having 2 to 8 carbon atoms and forming an oxygen atom between the carbon atoms constituting the alkyl group. Group, but R ⁴⁸ and R ⁵² may combine with each other to form -O-, -NH-, -S- or -SO _2- . R ⁵⁵ represents an aryl group which may be substituted.
Moreover, multiple within a molecule

When is included, these may be the same structure or different structures.
m represents an arbitrary natural number] According to claim 1,
In the formula (A-I), X represents an oxygen atom, a nitrogen atom, or a sulfur atom, [Ｙ] ^m- represents an arbitrary m-valent anion, and R ⁴¹ to R ⁴⁶ are each independently a hydrogen atom or an amino group. Or an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, a group in which an oxygen atom is inserted between carbon atoms constituting the alkyl group having an alkyl group having 2 to 20 carbon atoms, 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, R ⁵⁵ is a compound which represents an aryl group which may be substituted. The method of claim 1 or 2,
The compound [ ^m ] ^m- in the formula (A-I) is an anion containing boron. The method of claim 1 or 2,
The compound [ ^m ] ^m- in the said Formula (A-I) is an anion containing aluminum. The method of claim 1 or 2,
The compound [ ^m ] ^m- in the formula (A-I) is an anion containing fluorine. The method of claim 1 or 2,
[Ｙ] ^m- in the formula (A-I) is a compound which 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 of claim 6,
The compound [ ^m ] ^m- in the formula (A-I) is an anion of a heteropoly acid or isopoly acid containing tungsten as an essential element. The method of claim 7,
The compound [―] ^m- in the formula (A-I) is an anion of tungstophosphoric acid, an anion of tungstosilicic acid, or an anion of tungsten-based isopoly acid. A colored curable resin composition comprising the compound of claim 1 or 2. A coating film formed using the colored curable resin composition of claim 9. A color filter formed using the colored curable resin composition of claim 9. A display device comprising the color filter of claim 11.