JP2016164247A - Colored dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored dispersion comprising a colorant for color filters having improved heat resistance.SOLUTION: A colored dispersion comprises a compound represented by formula (A-I) and solvent [X is O or S; R-Rare H, a saturated hydrocarbon group or the like; R-Rare H, a halogen atom, an alkyl group or the like; Ris H, an aryl group or the like; [Y]is an m-valent anion comprising at least one element selected from tungsten, molybdenum, silicon, and phosphorus, and oxygen as essential elements].SELECTED DRAWING: None

Description

  The present invention relates to a dispersion useful for effectively utilizing dyes.

  A dye is used as a colorant for a color filter included in a liquid crystal display device or a solid-state image sensor. As the dye, for example, Patent Document 1 discloses a compound represented by the formula (A ′).

WO2012 / 053201 pamphlet

  The above known compounds have not been sufficiently satisfactory in heat resistance.

The present invention includes the following inventions.
[1] A colored dispersion containing a compound represented by the formula (AI) and a solvent.

[In the formula (AI), m represents a natural number.
X represents an oxygen atom or a sulfur atom.
R ^{41 to} R ⁴⁶ are each independently an oxygen atom between carbon atoms of a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, or an alkyl group having 2 to 20 carbon atoms. Represents an aryl group which may have a group in which is inserted or a substituent. R ⁴¹ and R ⁴² may be bonded to form a ring with the nitrogen atom to which they are bonded, R ⁴³ and R ⁴⁴ may be bonded to form a ring with the nitrogen atom to which they are bonded, R ⁴⁵ and R ⁴⁶ may be bonded to form a ring together with the nitrogen atom to which they are bonded.
R ^{47 to} R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, an alkyl group having 1 to 8 carbon atoms, or an oxygen atom between carbon atoms of an alkyl group having 2 to 8 carbon atoms. Represents an inserted group.
R ⁵⁵ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aryl group which may have a substituent.
The formula (AI) is a cation moiety.

In a molecule, the plurality of cation moieties may be the same or different.
[Y] ^m− represents an m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen as essential elements. ]

[2] The colored dispersion liquid according to [1], wherein [Y] ^m− in the formula (AI) is an anion of a heteropolyacid or an isopolyacid containing tungsten as an essential element.
[3] The colored dispersion according to [2], wherein [Y] ^m− in the formula (AI) is an anion of phosphotungstic acid, an anion of silicotungstic acid, or an anion of tungsten-based isopolyacid.
[4] The colored dispersion according to any one of [1] to [3], further comprising a dye.
[5] A colored curable resin composition comprising the colored dispersion according to any one of [1] to [4], a resin (B), a polymerizable compound (C), and a polymerization initiator (D). .
[6] The colored curable resin composition according to [5], comprising a dye.
[7] A color filter formed using the colored curable resin composition according to [5] or [6].
[8] A display device including the color filter according to [7].

  In addition, in this specification, when a some component is illustrated in parallel, unless there is particular notice, it means that each element can be used individually or in combination of multiple types.

  In the present invention, the heat resistance can be further enhanced by preparing a color filter by mixing a compound prepared with a specific anion into a dispersion and then mixing with a resin.

<Compound (AI)>
The dispersion of the present invention contains a compound represented by formula (AI) (hereinafter sometimes referred to as compound (AI)). This compound (AI) is excellent in heat resistance. The compound (AI) includes tautomers and salts thereof.

[In the formula (AI), m represents a natural number.
X represents an oxygen atom or a sulfur atom.
R ^{41 to} R ⁴⁶ are each independently an oxygen atom between carbon atoms of a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, or an alkyl group having 2 to 20 carbon atoms. Represents an aryl group which may have a group in which is inserted or a substituent. R ⁴¹ and R ⁴² may be bonded to form a ring with the nitrogen atom to which they are bonded, R ⁴³ and R ⁴⁴ may be bonded to form a ring with the nitrogen atom to which they are bonded, R ⁴⁵ and R ⁴⁶ may be bonded to form a ring together with the nitrogen atom to which they are bonded.
R ^{47 to} R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, an alkyl group having 1 to 8 carbon atoms, or an oxygen atom between carbon atoms of an alkyl group having 2 to 8 carbon atoms. Represents an inserted group.
R ⁵⁵ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aryl group which may have a substituent.
The formula (AI) is a cation moiety.

In a molecule, the plurality of cation moieties may be the same or different.
[Y] ^m− represents an m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen as essential elements. ]

<Cation part>
By adopting a cation partial structure as shown in formula (AI), the heat resistance of the compound can be increased. In the formula (AI), X represents an oxygen atom or a sulfur atom. From the viewpoint of ease of synthesis, a sulfur atom is preferred.

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^{41 to} R ⁴⁶ may be linear, branched or cyclic. Examples of the linear or branched saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, and a decyl group. The saturated hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 6 carbon atoms.

The cyclic saturated hydrocarbon group represented by R ^{41 to} R ⁴⁶ may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group. The cyclic saturated hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 6 to 10 carbon atoms.

The saturated hydrocarbon group of R ^{41 to} R ⁴⁶ may be substituted with an optionally substituted amino group or a halogen atom. Examples of the amino group which may be substituted include an amino group; and alkylamino groups such as a dimethylamino group and a diethylamino group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. When the halogen atom is a fluorine atom, the halogen atom is preferably substituted so as to form a perfluoroalkyl unit such as a trifluoromethyl unit, a pentafluoroethyl unit, or a heptafluoropropyl unit.
Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms substituted with such a substituted amino group or a halogen atom include groups represented by the following formulae. In the following formula, * represents a bond with a nitrogen atom.

Further, when the saturated hydrocarbon group of R ^{41 to} R ⁴⁶ has 2 or more carbon atoms, an oxygen atom may be inserted between the carbon atoms. The carbon number of the saturated hydrocarbon group is preferably 2 to 10, more preferably 2 to 6. When an oxygen atom is inserted, the number of carbon atoms between the terminal and the oxygen atom or between the oxygen atom and the oxygen atom is, for example, 1 to 5, preferably 2 to 3, and more preferably 2 It is. Examples of such a group in which an oxygen atom is inserted between carbon atoms of a saturated hydrocarbon group include an alkoxyalkyl group; or (alkoxyalkoxy) alkyl group, (alkoxyalkoxyalkoxy) alkyl group, and (alkoxyalkoxyalkoxyalkoxy). A polyalkoxyalkyl group such as an alkyl group, (alkoxyalkoxyalkoxyalkoxyalkoxy) alkyl group, (alkoxyalkoxyalkoxyalkoxyalkoxyalkoxy) alkyl group, and the like are included, and the number of repeating alkoxy units is, for example, 1 to 6, preferably 1. -4, more preferably 1-2. More preferred specific examples include groups represented by the following formulae. In the following formula, * represents a bond with a nitrogen atom.

In the aryl group which may have a substituent represented by R ^{41 to} R ⁴⁶ , examples of the aryl group include a phenyl group, a naphthyl group, a tolyl group, and a xylyl group, and a phenyl group is preferable. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and iodine; haloalkyl groups having 1 to 6 carbon atoms such as chloromethyl group and trifluoromethyl group; alkoxy having 1 to 6 carbon atoms such as methoxy group and ethoxy group A hydroxyl group; a sulfamoyl group; an alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group; and the like. Specific examples of the aryl group which may be substituted include groups represented by the following formulas. In the following formula, * represents a bond 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 bonded include nitrogen-containing non-aromatic 4- to 7-membered rings such as a pyrrolidine ring, a morpholine ring, a piperidine ring, and a piperazine ring. Preferably, a 4- to 7-membered ring having only one nitrogen atom as a hetero atom such as a pyrrolidine ring or a piperidine ring is used.
Examples of the ring formed by combining R ⁴³ and R ⁴⁴ together with the nitrogen atom to which they are bonded include nitrogen-containing non-aromatic 4- to 7-membered rings such as a pyrrolidine ring, a morpholine ring, a piperidine ring, and a piperazine ring. Preferably, a 4- to 7-membered ring having only one nitrogen atom as a hetero atom such as a pyrrolidine ring or a piperidine ring is used.
Examples of the ring formed by combining R ⁴⁵ and R ⁴⁶ together with the nitrogen atom to which they are bonded include nitrogen-containing non-aromatic 4- to 7-membered rings such as a pyrrolidine ring, morpholine ring, piperidine ring, piperazine ring, Preferably, a 4- to 7-membered ring having only one nitrogen atom as a hetero atom such as a pyrrolidine ring or a piperidine ring is used.

R ^{41 to} R ⁴⁴ are preferably each independently a saturated hydrocarbon group having 1 to 20 carbon atoms or an optionally substituted aryl group, from the viewpoint of ease of synthesis. A saturated hydrocarbon group having 1 to 8 carbon atoms or an aryl group represented by the following formula is more preferable. In the following formula, * represents a bond with a nitrogen atom.

R ^{45 to} R ⁴⁶ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms, a group having an oxygen atom inserted between carbon atoms of an alkyl group having 2 to 20 carbon atoms, or a substituent. It is preferably a good aryl group, or R ⁴⁵ and R ⁴⁶ are bonded to form a ring together with the nitrogen atom to which they are bonded. More preferably, R ⁴⁵ to R ⁴⁶ are each independently a saturated hydrocarbon group having 1 to 8 carbon atoms, alkylene Koki shea alkyl group or aryl group represented by the following formula, or a R ⁴⁵ In this embodiment, R ⁴⁶ is bonded to form a 4- to 7-membered ring having only one nitrogen atom as a hetero atom. In the following formula, * represents a bond with a nitrogen atom.

Examples of the group in which an oxygen atom is inserted between carbon atoms of the alkyl group having 1 to 8 carbon atoms represented by R ^{47 to} R ⁵⁴ and the alkyl group having 2 to 8 carbon atoms include those of R ^{41 to} R ⁴⁶ . The group which selected the thing with 8 or less carbon atoms from the corresponding group can be illustrated, More preferably, the group represented by a following formula is mentioned. In the following formula, * represents a bond with a carbon atom.

R ^{47 to} R ⁵⁴ are each independently preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, and each independently represents a hydrogen atom or a methyl group. More preferably, they are a fluorine atom or a chlorine atom.

Saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁵⁵ may be linear, it may be either branched or cyclic. Examples of the linear or branched saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, and a decyl group. The saturated hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 6 carbon atoms.

The cyclic saturated hydrocarbon group represented by R ⁵⁵ may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group. The cyclic saturated hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 6 to 10 carbon atoms.

In the optionally substituted aryl group represented by R ⁵⁵ , examples of the aryl group include aromatic hydrocarbon groups such as a phenyl group and a naphthyl group, and a phenyl group is preferable. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and iodine; haloalkyl groups having 1 to 6 carbon atoms such as chloromethyl group and trifluoromethyl group; alkoxy having 1 to 6 carbon atoms such as methoxy group and ethoxy group A hydroxyl group; a sulfamoyl group; an alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group; and the like. Specific examples of the aryl group which may be substituted include groups represented by the following formulas. In the following formula, * represents a bond with a carbon atom.

R ⁵⁵ is preferably a saturated hydrocarbon group having 1 to 8 carbon atoms or an aryl group represented by the following formula, and more preferably an aryl group represented by the following formula, from the viewpoint of ease of synthesis. In the following formula, * represents a bond with a carbon atom.

  As the cation moiety of the formula (AI), a cation having a structure represented by the formula (A-Ia) and having each group shown in Tables 1 to 5 is preferable, and the cations 1 to 12 shown in the table are Particularly preferred. Table 6 shows the meanings of the abbreviations in the table.

  Especially, as a cation part of a formula (AI), the cation 1-cation 6, the cation 11, or the cation 12 is preferable, and the cation 1, the cation 2, or the cation 12 is especially preferable.

  The number m of the cation moiety is appropriately set according to the valence of the anion moiety Y, and can be set, for example, from the range of 1 to 20, preferably from the range of 2 to 10, and more preferably from the range of 3 to 6.

<Anion part>
As [Y] ^m− corresponding to the anion portion, an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen as essential elements is used. A compound using such an anion can improve heat resistance and solvent resistance.
[Y] ^m− corresponding to the anion moiety is preferably an anion of a heteropolyacid or isopolyacid containing tungsten as an essential element, particularly an anion of phosphotungstic acid, silicotungstic acid or tungsten-based isopolyacid.

Examples of the anion of heteropolyacid or isopolyacid containing tungsten as an essential element include Keggin type phosphotungstate ion α- [PW ₁₂ O ₄₀ ] ³⁻ , Dawson type phosphotungstate ion α- [P ₂ W ₁₈ O ₆₂ ] ^6- , β- [P ₂ W ₁₈ O ₆₂ ] ^6- , Keggin-type silicotungstate ion α- [SiW ₁₂ O ₄₀ ] ^4- , β- [SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O ₄₀ ] ⁴⁻ , and other examples include [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 O ₁₁₀ ] ^14- , α- [SiW ₉ O ₃₄ ] ^10- , γ- [SiW ₁₀ O ₃₆ ] ^8- , α- [SiW ₁₁ O ₃₉ ] ^8- , β- [SiW ₁₁ O ₃₉ ] ^{8 -} , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- and mixtures thereof.

[Y] ^m− is also preferably an anion composed of oxygen and at least one element selected from the group consisting of silicon and phosphorus.
Examples of the anion consisting of oxygen and at least one element selected from the group consisting of silicon and phosphorus include SiO ₃ ²⁻ and PO ₄ ³⁻ .

Because of the ease of synthesis and post-treatment, phosphotungstic anions such as Keggin-type phosphotungstate ions and Dawson-type phosphotungstate ions; silicotungstate anions such as Keggin-type phosphotungstate ions, [W ₁₀ O ₃₂ ] ^4- A tungsten isopolyacid anion such as Of these, phosphotungstate anions and tungsten isopolyacid anions are particularly preferred.

  Compound (AI) can be produced according to the method described in JP-A-2015-28121.

<Colored dispersion>
In the present invention, the compound (AI) is mixed with a solvent to form a colored dispersion. When a colored curable resin composition is formed by mixing with a resin (B), a polymerizable compound (C), a polymerization initiator (D), etc. after making a colored dispersion, the heat resistance when it is made into a color filter is further increased. Can be increased.

Any solvent can be used as long as it can be used as the solvent (E) of the colored curable resin composition. A particularly excellent solvent for the purpose of dispersing the compound (AI) is, for example, an ether ester solvent. More preferably, one hydroxy group of alkylene glycol or polyalkylene glycol is etherified, and the remaining hydroxy group is an ester. Solvents such as 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 monoethyl ether acetate, diethylene glycol monobutyl ether acetate And dipropylene glycol methyl ether acetate. These may be contained alone or in combination.
The amount of the solvent is, for example, 1 to 50 parts by mass, preferably 2 to 30 parts by mass, and more preferably 3 to 10 parts by mass with respect to 1 part by mass of the compound (AI).

  In preparing the colored dispersion, it is preferable to use a dispersant. As the dispersant, for example, known pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic can be used. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by BASF), Ajispur (Ajinomoto Fine (Techno Co., Ltd.), Disperbyk (Bic Chemie) and the like.

  The amount of the dispersant is, for example, 1 to 1000 parts by mass, preferably 3 to 100 parts by mass, more preferably 5 to 50 parts by mass, and particularly preferably 10 to 30 parts by mass with respect to 100 parts by mass of the compound (AI). Part by mass.

  Moreover, when the dye (A1) is contained in the colored curable resin composition to be described later, part or all of the dye (A1), preferably all, may be contained in advance as necessary. The amount of the dye (A1) in the colored dispersion is, for example, 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 1 with respect to 100 parts by mass of the compound (AI). -5 parts by mass.

  The colored dispersion may contain a part or all of the resin (B) used in the colored curable resin composition, preferably a part thereof, if necessary. By including the resin (B) in advance, the dispersibility of the colored curable resin composition can be further improved. The solid content conversion amount of the resin (B) in the colored dispersion is, for example, 1 to 300 parts by mass, preferably 10 to 100 parts by mass, more preferably 20 to 100 parts by mass of the compound (AI). 70 parts by mass.

  In preparing the dispersion, it is preferable to finely disperse using a dispersion apparatus after appropriately adding necessary components. A bead mill device can be used as the dispersing device. The beads used are generally hard beads such as zirconia beads, and the particle size thereof is selected from the range of 0.05 mm or more and 20 mm or less, preferably 0.1 to 10 mm, more preferably. 0.1 to 0.5 mm.

<Colored curable resin composition>
<Colorant (A)>
The colored curable resin composition refers to a composition containing a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). The colored curable resin composition can appropriately include a polymerization initiation assistant (D1), a solvent (E), a leveling agent (F), and the like. Hereinafter, each component will be described.

  As the colorant (A), the compound (AI) may be used alone, but for the purpose of toning, that is, for adjusting the spectral characteristics, other dyes (A1) and pigments (P) are used. May be included. By including the other dye (A1), the heat resistance can be further improved.

  Examples of the dye (A1) include oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, sulfonamides of acid dyes, and the like, for example, Color Index (The Society). of Dyers and Colorists) and known dyes described in Dyeing Notes (Color Dyeing). Also, according to chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styryl dye, coumarin dye, quinoline And dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferably used.

Specifically, C.I. I. Solvent Blue 4, 5, 37, 67, 70, 90;
C. I. Solvent Green 1, 4, 5, 7, 34, 35, etc. I. Solvent dyes,
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. I. Acid dyes,

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, 2 5,246,247,248,249,250,251,252,256,257,259,260,268,274,275,293;
C. I. Direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. I. Direct dyes,
C. I. Basic Blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;
C. I. C. such as Basic Green 1; I. Basic dyes,
C. I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
C. I. Modern Blue 1, 2, 3, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61 74, 77, 83, 84;
C. I. Modern Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, etc. I. Modern dyes,
C. I. C. of Bat Green 1 etc. I. Vat dye,
Etc.
Of these, blue dyes and violet dyes are preferred.
These dyes may be used alone or in combination of two or more.

  Moreover, in the classification | category by a chemical structure, it is preferable that it is 1 type selected from the group which consists of a xanthene dye, a triarylmethane dye, an anthraquinone dye, and a tetraazaporphyrin dye, and a xanthene dye is more preferable.

  More preferably, the xanthene dye is a compound represented by the following formula (a1-1) (hereinafter also referred to as compound (a1-1)). The compound (a1-1) may be a tautomer thereof.

[In formula (a1-1), R ^{1 to} R ⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. Represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a methylene group (—CH ₂ —) contained in the saturated hydrocarbon group, —O—, —CO— or It may be replaced by —NR ¹¹ —. R ¹ and R ² may be combined to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be combined to form a ring containing a nitrogen atom.
R ^{5 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ represents NR ⁹ R ¹⁰
R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 5. When m is 2 or more, the plurality of R ⁵ may be the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and four R ¹¹ 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.
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and —CH ₂ contained in the saturated hydrocarbon group — May be replaced by —O—, —CO—, —NH— or —NR ⁸ —, wherein R ⁹ and R ¹⁰ are bonded to each other and are a 3- to 10-membered heterocyclic ring containing a nitrogen atom. May be formed.
R ¹¹ 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. ]

In the formula (a1-1), when —SO ₃ ^— is present, the number is one.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^{1 to} R ⁴ include a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group. Among these, R ¹ and R ⁴ are preferably phenyl groups.

The aromatic hydrocarbon group substituent which may have a halogen ^{atom, -R 8, -OH, -OR 8} , -SO 3 -, -SO 3 H, -SO 3 - Z +, - CO ₂ H, —CO ₂ R ⁸ , —SR ⁸ , —SO ₂ R ⁸ , —SO ₃ R ^8, or —SO ₂ NR ⁹ R ¹⁰ are included, and these substituents are included in the aromatic hydrocarbon group. It is preferable to substitute a hydrogen atom. Among them, as the _{^{substituent, -SO 3 -, -SO 3 H}} , -SO 3 - Z + and preferably _{^{-SO 2 NR 9 R 10, -SO}} 3 - Z + and -SO ₂ NR ⁹ R ¹⁰ Is more preferable. In this case, —SO ₃ ^{− +} N (R ¹¹ ) ₄ is preferable as —SO ₃ ⁻ Z ⁺ . As —SO ₂ NR ⁹ R ¹⁰ , —SO ₂ NHR ⁹ is preferable. When R ^{1 to} R ⁴ are these groups, the colored curable resin composition of the present invention containing the compound (a1-1) can form a color filter with less generation of foreign matters and excellent heat resistance.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ^{1 to} R ⁴ and R ^{8 to} R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Linear alkyl groups such as octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, icosyl group; branched alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group; C3-C20 alicyclic saturated hydrocarbon groups, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group, are mentioned. Among these, R ² and R ³ are preferably propyl groups.
The hydrogen atom contained in the saturated hydrocarbon group in R ^{1 to} R ⁴ may be substituted with, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom as a substituent. Examples of the aromatic hydrocarbon group of R ¹ to R ⁴ saturated hydrocarbon carbon atoms which may be substituted with hydrogen atoms of the groups 6 to 10, having 6 to 10 carbon atoms in R ¹ to R ⁴ aromatic hydrocarbons Examples thereof include the same groups as those exemplified as the group.
The hydrogen atom contained in the saturated hydrocarbon group in R ⁹ and R ¹⁰ may be substituted with, for example, a hydroxy group or a halogen atom as a substituent.

Examples of the ring formed by R ¹ and R ² together and the ring formed by R ³ and R ⁴ together include the following.

Examples of —OR ⁸ include alkyloxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and icosyloxy group. Is mentioned.

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

Examples of —SR ⁸ include alkylsulfanyl groups such as a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.
Examples of —SO ₂ R ⁸ include alkylsulfonyl groups such as a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.
Examples of —SO ₃ R ⁸ include alkyloxysulfonyl groups such as a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group. The R ⁸ in -SO ₃ R ^8, preferably branched chain alkyl group having 3 to 20 carbon atoms, more preferably a branched chain alkyl group having 6 to 12 carbon atoms, 2-ethylhexyl group is more preferred. A color filter with less generation of foreign matters can be formed.

—SO ₂ NR ⁹ R ¹⁰ includes, 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-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3 -Methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1 , 4-Dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethylhexyl) sulfamoyl group, N- (1,1,2,2 -N-substituted sulfamoyl groups such as -tetramethylbutyl) sulfamoyl group;
N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfa Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl And N, N-2-substituted sulfamoyl groups such as a group.
In the N-1 substituted sulfamoyl group, R ⁸ is preferably a branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 6 to 12 carbon atoms, and further preferably a 2-ethylhexyl group. . A color filter with less generation of foreign matters can be formed.

The _{^{R 5, -CO 2 H, -CO}} 2 - Z +, -CO 2 R 8, -SO 3 -, -SO 3 - Z +, -SO 3 H or -SO ₂ NHR ⁹ are preferred, -SO ^{_{3 -, -SO 3 - Z +}} , more preferably -SO ₃ H or -SO ₂ NHR ^9, -SO ₃ ^- is more preferable.
m is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.

The alkyl group having 1 to 6 carbon atoms in R ⁶ and R ^7, among the alkyl groups listed above, include those having 1 to 6 carbon atoms. Among these, as R ⁶ and R ⁷ , a hydrogen atom is preferable.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ¹¹ include a benzyl group, a phenylethyl group, and a phenylbutyl group.
R ¹¹ is preferably a saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group.

Z ⁺ is ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ¹¹ ) ₄ .
As the ⁺ N (R ¹¹ ) ₄ , at least two of the four R ¹¹ are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R ¹¹ is preferably 20 to 80, 20 to 60 is more preferable. When ⁺ N (R ¹¹ ) ₄ is present in the compound (a1-1), when R ¹¹ is any of these groups, the colored curable resin composition of the present invention containing the compound (a1-1) can be used as a foreign substance. A color filter with less can be formed.

The combination of R ^{1 to} R ⁴ is preferably a combination in which R ¹ and R ³ are hydrogen atoms and R ² and R ⁴ are aromatic hydrocarbon groups having a monovalent substituent having 6 to 10 carbon atoms. . The substituent of the aromatic hydrocarbon _{^{group, -SO 3 -, -SO 3 H}} , -SO 3 - Z +, -SO 3 R 8 or -SO ₂ NHR ⁹ are preferred, -SO ₃ ^- Z ⁺ or -SO ₂ NHR ⁹ is more preferable. These substituents shall replace hydrogen atoms contained in the aromatic hydrocarbon group.

As the combination of R ^{1 to} R ^4, a combination in which R ^{1 to} R ⁴ are all monovalent saturated hydrocarbon groups is also preferable. In this case, the saturated hydrocarbon group is preferably a methyl group or an ethyl group.

In addition, as a combination of R ^{1 to} R ⁴ , R ¹ and R ³ are each a saturated hydrocarbon group having 1 to 10 carbon atoms that may have a substituent, and R ² and R ⁴ have a substituent. Also preferred are combinations that are optionally phenyl groups.
In this case, R ¹ may form a ring with a substituent that substitutes the phenyl group of R ² , and R ³ may form a ring with a substituent that substitutes the phenyl group of R ⁴ .
The number of carbon atoms of R ¹ and R ^3, independently of one another, is preferably 1-3. As a substituent of the hydrogen atom contained in the saturated hydrocarbon group of R ¹ and R ³ , an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with an alkoxy group having 1 to 3 carbon atoms, or halogen Atoms are preferred.
As the R ² and the substituent which may be a phenyl group optionally having a R ^4, an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group, or an alkylsulfonyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms Is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group is more preferable. The number of substituents substituting the phenyl groups of R ² and R ⁴ is 0-5, preferably 0-2, more preferably 0 or 1.
Examples of the alkyl group having 1 to 4 carbon atoms that may substitute the phenyl group of R ² and R ⁴ include methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, sec-butyl group, tert. -A butyl group etc. are mentioned.
Examples of the alkylsulfanyl group having 1 to 4 carbon atoms that may substitute the phenyl group of R ² and R ⁴ include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, and an isopropylsulfanyl group. Can be mentioned.
Furthermore, examples of the alkylsulfonyl group having 1 to 4 carbon atoms that may substitute the phenyl group of R ² and R ⁴ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group. Can be mentioned.

When R ¹ and R ⁴ of the compound (a1-1) are aromatic hydrocarbon groups, the compound (a1-1) is a compound represented by the formula (a1-2) (hereinafter “compound (a1-2)”. ) ").) Is preferred. The compound (a1-2) may be a tautomer thereof.

[In Formula (a1-2), R ²¹ and R ²² each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and are included in the saturated hydrocarbon group of R ²¹ and R ^22. The hydrogen atom may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and the hydrogen atom contained in the aromatic hydrocarbon group is substituted with an alkoxy group having 1 to 3 carbon atoms. And —CH ₂ — contained in the saturated hydrocarbon group of R ²¹ and R ²² may be replaced by —O—, —CO— or —NR ¹¹ —.
R ²³ and R ²⁴ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.
R ²¹ and R ²³ may together form a ring containing a nitrogen atom, and R ²² and R ²⁴ may together form a ring containing a nitrogen atom.
p and q represent the integer of 0-5 mutually independently. When p is 2 or more, the plurality of R ²³ may be the same or different, and when q is 2 or more, the plurality of R ²⁴ may be the same or different.
R ¹¹ represents the same meaning as described above. ]

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ²¹ and R ²² include those having 1 to 10 carbon atoms among those in R ⁸ .
Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be present as a substituent include the same groups as those in R ¹ .
As a C1-C3 alkoxy group, a methoxy group, an ethoxy group, a propoxy group etc. are mentioned, for example.
R ²¹ and R ²² are preferably each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group).

Examples of the alkyl group having 1 to 4 carbon atoms in R ²³ and R ²⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ²³ and R ²⁴ include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, and an isopropylsulfanyl group.
Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ²³ and R ²⁴ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group.
R ²³ and R ²⁴ are preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

  p and q are preferably an integer of 0 to 2, and preferably 1 or 2.

As a xanthene dye, the compound represented by Formula (1-1)-Formula (1-43) is mentioned, for example. In the formula, R ⁴⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group.

Among the above compounds, the compounds represented by the formula (1-1) to the formula (1-23) or the formula (1-37) to the formula (1-43) correspond to the compound (a1-2), and the formula ( The compound represented by any one of 1-24) to Formula (1-36) corresponds to the compound (a1-3).
Among these, C.I. I. Acid red 289 sulfonamidation product, C.I. I. Quaternary ammonium salt of Acid Red 289, C.I. I. Acid violet 102 sulfonamidate or C.I. I. The quaternary ammonium salt of Acid Violet 102 is preferred. Examples of such a compound include compounds represented by formula (1-1) to formula (1-8), formula (1-11), or formula (1-12).
In addition, a compound represented by any one of the formulas (1-24) to (1-33) is also preferable, and particularly preferably, the compound is represented by the formula (1-32) in terms of excellent solubility in an organic solvent. A compound.

  As the xanthene dye, a commercially available xanthene dye (for example, “Chugai Aminol Fast Pink R-H / C” manufactured by Chugai Kasei Co., Ltd., “Rhodamin 6G” manufactured by Taoka Chemical Industry Co., Ltd.) can be used. Moreover, it can also synthesize | combine with reference to Unexamined-Japanese-Patent No. 2010-32999 using the commercially available xanthene dye as a starting material.

Triarylmethane Dye The triarylmethane dye is preferably a dye containing a compound having a structure in which three aromatic hydrocarbon groups are bonded to one carbon atom. Examples of the triarylmethane dye include C.I. I. Solvent Blue 2, 4, 5, 43, 124; I. Basic Violet 3, 14, 25; C.I. I. And triarylmethane dyes described in Basic Blue 1, 5, 7, 11, 26 and Japanese Patent No. 4492760.

Anthraquinone dyes As anthraquinone dyes, C.I. I. Solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60,
C. I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139,
C. I. Solvent Green 3, 28, 29, 32, 33,
C. I. Acid Green 25, 27, 28, 41,
C. I. Acid Violet 34,
C. I. Acid Blue 25, 27, 40, 45, 78, 80, 112
C. I. Disperse violet 26, 27,
C. I. Disperse Blue 1, 14, 56, 60,
C. I. Direct Blue 40,
C. I. Modern Blue 8
Etc.

Tetraazaporphyrin dye Tetraazaporphyrin dye is a compound having a tetraazaporphyrin skeleton in the molecule. Further, when the tetraazaporphyrin dye is an acid dye or a basic dye, it may form a salt with any cation or anion.

As other dyes, azo dyes, oxazine dyes, phthalocyanine dyes, and the like may be used, and known dyes are used.
As the azo dye, C.I. I. Direct violet 47, 52, 54, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct Blue 51, 57, 71, 81, 84, 85, 90, 93, 94, 95, 98, 100, 101, 113, 149, 150, 153, 160, 162, 163, 164, 166, 167, 170, 172, 188, 192, 193, 194, 196, 198, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275;
C. I. Direct green 27, 34, 37, 65, 67, 68, 69, 72, 77, 79, 82, etc .;
C. I. Acid Violet 11, 56, 58;
C. I. Acid Blue 92, 102, 113, 117 etc .;
C. I. Basic blue 41, 54, 64, 66, 67, 129 etc. are mentioned.

Examples of the oxazine dye include C.I. I. Direct Blue 97, 99, 106, 107, 108, 109, 190, 293 and the like can be mentioned.
Examples of the phthalocyanine dye include C.I. I. Direct Blue 86, 87, 189, 199, C.I. I. Acid Blue 249, C.I. I. Basic blue 3 etc. are mentioned.

  When the dye (A1) is contained, the xanthene dye is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and still more preferably 80 parts by mass or more, even more in 100 parts by mass of the dye (A1). Preferably it is 90 mass parts or more, Most preferably, it is 99 mass parts or more.

  When the dye (A1) is contained, the colored curable resin composition may be mixed simultaneously with other components, or a colored dispersion containing the dye (A1) may be prepared in advance.

The content rate of a compound (AI) is 1-100 mass% with respect to the total amount of a coloring agent (A), for example, Preferably it is 10-100 mass%. Moreover, 30 mass% or more, Preferably it is 50 mass% or more, More preferably, 70 mass% or more may be sufficient.
When the dye (A1) is included, the content is preferably 0.5% by mass or more and 90% by mass or less, more preferably 40% by mass or more and 80% by mass or less, with respect to the total amount of the colorant (A). It is also preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, and further preferably 1% by mass or more and 5% by mass or less. When the dye (A1) is contained, the mass ratio of the dye (A1) to the compound (AI) is 0.001 to 0.5, more preferably 0.005 to 0.4, and still more preferably 0.007. It is -0.3, More preferably, it is 0.009-0.2. By setting it as the said range, heat resistance can be improved further.
The content 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, and further preferably 5% by mass with respect to the total amount of the solid content. % Or more and 50% by mass or less. When the content of the colorant (A) is within the above range, a desired spectrum and color density can be obtained.

  In this specification, the “total amount of solids” refers to the total amount of components obtained by removing the solvent (E) from the colored curable resin composition of the present invention. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

<Resin (B)>
The resin (B) is preferably an alkali-soluble resin. The alkali-soluble resin is a copolymer containing a structural unit derived from at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride.
The monomer (a) is a monomer (b) having a C2-C4 cyclic ether structure and an ethylenically unsaturated bond, and a monomer (c) copolymerizable with (a). It is preferable to copolymerize with at least one to form a resin (B). When copolymerized with both the monomer (b) and the monomer (c), a carboxylic acid anhydride may be further reacted. Good.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Unsaturated dicarboxylic acids such as maleic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, etc. Bicyclounsaturated compounds containing a carboxy group of
Unsaturated dicarboxylic acid anhydrides such as maleic anhydride;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an alkaline aqueous solution.

(B) is, for example, a polymerizable compound having a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Say.
(B) is preferably a monomer having a C2-C4 cyclic ether and a (meth) acryloyloxy group.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”), etc. Can be mentioned. Preferred (b) is a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond.

  As (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”) And a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”). (B1-2) is more preferable in that the storage stability of the colored curable resin composition is excellent.

  As (b1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6- Examples include tris (glycidyloxymethyl) styrene.

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), a compound represented by Formula (II), and Formula (III) The compound etc. which are represented by these are mentioned.

[In Formula (II) and Formula (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 is substituted with a hydroxy group. May be.
X ^a and X ^b is a single ^{bond, * - R c -, *} - R c -O -, * - represents the R ^c -S- or * -R ^c -NH-.
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

  Examples of the compound represented by the formula (II) include compounds represented by any one of the formulas (II-1) to (II-15). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15) A compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) is more preferred.

  Examples of the compound represented by the formula (III) include compounds represented by any one of the formulas (III-1) to (III-15). Among them, formula (III-1), formula (III-3), formula (III-5), formula (III-7), formula (III-9) or formula (III-11) to formula (III-15) A compound represented by formula (III-1), formula (III-7), formula (III-9) or formula (III-15) is more preferred.

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

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 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 this technical field, it is referred to as “dicyclopentanyl (meth) acrylate” as a common name. In some cases, it is also referred to as “tricyclodecyl (meth) acrylate”), tricyclo [ 5.2.1.0 ^2,6 ] decen-8-yl (meth)
Acrylate (referred to in the art as “dicyclopentenyl (meth) acrylate” as a common name), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (Meth) acrylates such as (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, 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, diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Of these, styrene, vinyltoluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) from the viewpoints of copolymerization reactivity and heat resistance.
Preferred are acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo [2.2.1] hept-2-ene.
Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride, and the like. As for the usage-amount of carboxylic acid anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amount of (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl. Resins such as (meth) acrylate / (meth) acrylic acid copolymer; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic Acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo [ 5.2.1.0 ^2.6] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3-methyl-3- (meth) Resins such as rylloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl (meth) Resin such as acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer; resin obtained by adding glycidyl (meth) acrylate to benzyl (meth) acrylate / (meth) acrylic acid copolymer, tri Resin with glycidyl (meth) acrylate added to cyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer A resin such as a resin obtained by adding glycidyl (meth) acrylate to the coalescence; Resin in which (meth) acrylic acid is reacted with a copolymer of licyclodecyl (meth) acrylate / glycidyl (meth) acrylate, and a copolymer of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate (meth) Resin such as resin reacted with acrylic acid; tetrahydrophthalic anhydride was further reacted with a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid Examples thereof include resins such as resins.

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further 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, the solubility of the unexposed area in the developer is good, and 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 (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

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

  Content of resin (B) becomes like this. Preferably it is 7-65 mass% with respect to the total amount of solid content, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%. When the content of the resin (B) is in the above range, a colored pattern can be formed, and the resolution and remaining film ratio of the colored pattern tend to be improved.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond. Is a (meth) acrylic acid ester compound.

  Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. And the above-mentioned (a), (b) and (c).

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

  Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more of ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) ) Isocyanurate, 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, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

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

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to the total amount of the solid content. is there. The content of the polymerizable compound (C) is also preferably 1 to 65% by mass, more preferably 5 to 50% by mass, and still more preferably 10 to 40% by mass, based on the total amount of the solid content. Especially preferably, it is 12-30 mass%.
Further, the content ratio of the resin (B) and the polymerizable compound (C) [resin (B): polymerizable compound (C)] is based on mass, preferably 20:80 to 80:20, more preferably. Is 35: 65-80: 20.
When the content of the polymerizable compound (C) is within the above range, the remaining film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and 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 compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1- On-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-di) Oxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl- -(2-Methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] -3-cyclopentylpropane-1-one-2-imine and the like. Commercial products such as Irgacure OXE 01, OXE 02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used. Among these, O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1 At least one selected from the group consisting of -on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferred, and N-benzoyloxy -1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred.

  The alkylphenone compound includes 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1- ON, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one, 2-hydroxy-2-methyl-1-phenyl Propan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- (4-Isopropenylphenyl) propan-1-one oligomer, α, α-diethoxyacetophenone, benzyldimethyl ketal Etc. Commercial products such as Irgacure 369, 907, 379 (above, manufactured by BASF) may be used.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4. , 4 ′, 5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -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 (trialkoxy) Phenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), a phenyl group at the 4,4 ′, 5,5′-position is substituted with a carboalkoxy group. Imidazole compounds (see, for example, JP-A-7-10913). Among these, compounds represented by the following formula and mixtures thereof are preferable.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 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-methoxy Styryl) -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-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- 2-methylpheny ) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Examples include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds.
These are preferably used in combination with a polymerization initiation assistant (D1) (particularly amines) described later.

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

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

<Polymerization initiation aid (D1)>
The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator. When the polymerization initiation assistant (D1) is included, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (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, 4 2-dimethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (Ethylmethylamino) benzophenone and the like can be mentioned, among which 4,4′-bis (diethylamino) benzophenone is preferable. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-di. Examples include butoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.

  When using these polymerization initiation assistants (D1), the content thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Preferably it is 1-20 mass parts. When the amount of the polymerization initiation assistant (D1) is within this range, a colored pattern can be formed with higher sensitivity and the productivity of the color filter tends to be improved.

<Solvent (E)>
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (intramolecular) Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O-,- A solvent not containing CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide and the like.

  As ester solvents, 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, butyl butyrate , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

  Ether solvents 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, 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, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate and the like.

  Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone. Etc.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.
Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

These solvents may be used alone or in combination of two or more.
Among them, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, 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 preferable, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether , Ethylene glycol monobutyl ether, dipropylene glycol Ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, N- methylpyrrolidone is more preferred.

  The content of the solvent (E) is preferably 70 to 95% by mass and more preferably 75 to 92% by mass with respect to 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% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is in the above range, the flatness at the time of coating is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good.

<Leveling agent (F)>
Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: manufactured by Toray 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 and TSF4460 (made by Momentive Performance Materials Japan GK) .

  Examples of the fluorosurfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) and E5844 (Daikin Fine Chemical Laboratory Co., Ltd.).

  Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation), and the like can be given.

  When the leveling agent (F) is contained, the content thereof is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002%, based on the total amount of the colored curable resin composition. It is preferably 0.005% by mass or more and 0.07% by mass or less, more preferably 0.001% by mass or more and 0.5% by mass or less, more preferably 0% by mass or more and 0.1% by mass or less. It is 0.002 mass% or more and 0.3 mass% or less, More preferably, it is 0.005 mass% or more and 0.2 mass% or less. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>
The colored curable resin composition of the present invention includes additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., if necessary. May be included.

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention includes, for example, a colored dispersion, a resin (B), a polymerizable compound (C), a polymerization initiator (D), and other than (AI) used as necessary. The colorant (A), the solvent (E), the leveling agent (F), the polymerization initiation assistant (D1) and other components can be mixed.
When the colorant (A) other than the (AI) compound contains the pigment (P), the pigment (P) is mixed with a part or all of the solvent (E) in advance, and the average particle size of the pigment is 0. It is preferable to disperse using a bead mill or the like until it becomes about 2 μm or less. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed.
The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.

<Color filter manufacturing method>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Of these, the photolithographic method is preferable. The photolithographic method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithography method, a colored coating film that is a cured product of the colored composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and the colored coating film thus formed are the color filter of the present invention.
The film thickness of the color filter to be produced is not particularly limited, and can be adjusted as appropriate according to the purpose and application, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5. ~ 6 μm.

  As the substrate, a glass plate, a resin plate, silicon, or an aluminum, silver, silver / copper / palladium alloy thin film formed on the substrate is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

Formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be produced as follows.
First, a colored curable resin composition is applied on a substrate, dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth colored composition layer is obtained.
Examples of the coating method include spin coating, slit coating, and slit and spin coating.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern.
Use an exposure device such as a mask aligner or a stepper because the entire exposure surface can be illuminated with parallel rays uniformly, or the photomask can be accurately aligned with the substrate on which the colored composition layer is formed. Is preferred.

A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide is preferable.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.

  Furthermore, it is preferable to post-bake the obtained colored pattern.

  The compound of this invention can manufacture the color filter excellent in heat resistance especially with the colored curable resin composition using this. 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 image sensors.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.

Hereinafter, the colored curable resin composition of the present invention will be described in more detail by way of examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.
In the following synthesis examples, the compounds were identified by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type) or elemental analysis (VARIO-EL; (Elemental Co., Ltd.)).
Moreover, the measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of polystyrene conversion of resin was performed on condition of the following by GPC method.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: THF
Flow rate: 1.0 mL / min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Reference material for calibration; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Manufactured by Tosoh Corporation)

1. Examination of cation part Synthesis reference example 1
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 36.3 parts of potassium thiocyanate and 160.0 parts of acetone, and then stirred at room temperature for 30 minutes. Next, 50.0 parts of benzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture with 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. Next, after cooling the reaction mixture with ice, 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. Then, 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 and reflux. Next, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 52.0 parts of a compound represented by the formula (BI-1). Yield 50%.

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 9.3 parts of the compound represented by the formula (BI-1), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 0.0 parts and 20.0 parts of toluene were added, and then 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation 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 evaporated using an evaporator to obtain a blue-violet solid. Further, the blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 19.8 parts of a compound represented by the formula (A-II-1). Yield 100%.

Identification of compound represented by formula (A-II-1) (mass spectrometry) ionization mode = ESI +: m / z = 601.3 [M-Cl] ⁺
Exact Mass: 636.3

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-1), bis (trifluoromethanesulfonyl) imidolithium (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.5 And 100.0 parts of N, N-dimethylformamide were added, followed by stirring at 50 to 60 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 2000.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to obtain a blue-green solid. Furthermore, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.3 parts of a compound represented by the formula (AI-1). Yield 82%.

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

Synthesis Reference Example 2
The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-1), 14.1 parts of Tungstosilicic acid hydrate (manufactured by SIGMA-ALDRICH), and N, N -After adding 100.0 parts of dimethylformamide, it stirred at 50-60 degreeC for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 2000.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to obtain a blue-green solid. Furthermore, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 17.3 parts of a compound represented by the formula (AI-4). Yield 83%.

0.35 g of the compound represented by the formula (AI-4) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.00. 028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 1.5 (arbitrary unit) at λmax = 638 nm.

Synthesis Reference Example 3
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 32.2 parts of potassium thiocyanate and 160.0 parts of acetone, and then stirred at room temperature for 30 minutes. Next, 50.0 parts of 2-fluorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture with ice, 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. Next, after cooling the reaction mixture with ice, 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. Then, 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 and reflux. Next, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 49.9 parts of a compound represented by the formula (BI-7). Yield 51%.

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 9.9 parts of the compound represented by the formula (BI-7), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 0.0 parts and 20.0 parts of toluene were added, and then 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation 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 evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 17.2 parts of a compound represented by the formula (A-II-7). Yield 85%.

Identification of compound represented by formula (A-II-7) (mass spectrometry) ionization mode = ESI +: m / z = 619.3 [M-Cl] ⁺
Exact Mass: 654.3

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-7), bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.7 And 30.0 parts of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to obtain a blue-green solid. Further, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.9 parts of a compound of the formula (AI-7). Yield 86%.

0.35 parts of the compound of formula (AI-7) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 3.1 (arbitrary unit) at λmax = 630 nm.

Synthesis Reference Example 4
The following reaction was performed in a nitrogen atmosphere. After charging 23.3 parts of potassium thiocyanate and 160.0 parts of acetone in a flask equipped with a condenser and a stirrer, the mixture was stirred at room temperature for 30 minutes. Next, 50.0 parts of 2-bromobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Next, the reaction mixture was ice-cooled, and 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. Next, after cooling the reaction mixture with ice, 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. Then, 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 and reflux. Next, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 41.6 parts of a compound represented by the formula (BI-8). Yield 45%.

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 12.9 parts of a compound represented by the formula (BI-8), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 0.0 parts and 20.0 parts of toluene were added, and then 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation 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 evaporated using an evaporator to obtain a blue-violet solid. The resulting 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 the formula (A-II-8). Yield 80%.

Identification of 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 in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-8), bis (trifluoromethanesulfonyl) imidolithium (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.2 And 30.0 parts of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to obtain a blue-green solid. Further, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 12.9 parts of a compound of the formula (AI-8). Yield 96%.

0.35 parts of the compound of the formula (AI-8) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.6 (arbitrary unit) at λmax = 632 nm.

Synthesis Reference Example 5
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 33.0 parts of potassium thiocyanate and 160.0 parts of acetone, and then stirred at room temperature for 30 minutes. Next, 50.0 parts of 2-methylbenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture with 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. Next, after cooling the reaction mixture with ice, 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. Then, 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 and reflux. Next, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 40.5 parts of a compound represented by the formula (BI-9). Yield 41%.

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 9.7 parts of the compound represented by the formula (BI-9), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 0.0 parts and 20.0 parts of toluene were added, and then 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation 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 evaporated using an evaporator to obtain a blue-violet solid. The resulting 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 the formula (A-II-9). Yield 75%.

Identification of 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 in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-9), bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.7 And 30.0 parts of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to obtain a blue-green solid. The blue-green solid was further dried at 60 ° C. under reduced pressure to obtain 13.2 parts of the compound of formula (AI-9). Yield 96%.

0.35 parts of the compound of the formula (AI-9) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.7 (arbitrary unit) at λmax = 627 nm.

Synthesis Reference Example 6
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirring device was charged with 24.5 parts of potassium thiocyanate and 160.0 parts of acetone, and then 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 the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Next, the reaction mixture was ice-cooled, and 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. Next, after cooling the reaction mixture with ice, 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. Then, 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 and reflux. Next, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 31.1 parts of a compound represented by the formula (BI-10). Yield 36%.

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 11.4 parts of the compound represented by the formula (BI-10), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 0.0 parts and 20.0 parts of toluene were added, and then 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation 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 evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 15.2 parts of a compound represented by the formula (A-II-10). Yield 70%.

Identification of compound represented by formula (A-II-10) (mass spectrometry) ionization mode = ESI +: m / z = 669.3 [M-Cl] ⁺
Exact Mass: 704.3

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-10), bis (trifluoromethanesulfonyl) imidolithium (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.1 And 30.0 parts of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to obtain a blue-green solid. Further, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.4 parts of a compound of the formula (AI-10). Yield 85%.

Dissolving 0.35 part of the compound of formula (AI-10) in chloroform to a volume of 250 cm ³
Then, 2 cm ³ was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L), and an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 1.9 (arbitrary unit) at λmax = 631 nm.

Synthesis Reference Example 7
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 33.0 parts of potassium thiocyanate and 160.0 parts of acetone, and then stirred at room temperature for 30 minutes. Next, 50.0 parts of 2-methylbenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture with 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. Next, after cooling the reaction mixture with ice, 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. Then, 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 and reflux. Next, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 70.0 parts of a compound represented by the formula (BI-11). Yield 72%.

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 9.6 parts of the compound represented by the formula (BI-11), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 0.0 parts and 20.0 parts of toluene were added, and then 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation 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 evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 19.7 parts of a compound represented by the formula (A-II-11). Yield 98%.

Identification of compound represented by formula (A-II-11) (mass spectrometry) ionization mode = ESI +: m / z = 609.4 [M-Cl] ⁺
Exact Mass: 644.4

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-11), bis (trifluoromethanesulfonyl) imidolithium (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.4 And 30.0 parts of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to obtain a blue-green solid. Further, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.7 parts of a compound of the formula (AI-11). Yield 85%.

Dissolving 0.35 part of the compound of formula (AI-11) in chloroform to a volume of 250 cm ³
Then, 2 cm ³ was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L), and an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 3.0 (arbitrary unit) at λmax = 613 nm.

Synthesis Reference Example 8
The following reaction was performed in a nitrogen atmosphere. After putting 29.2 parts of potassium thiocyanate and 160.0 parts of acetone into a flask equipped with a condenser and a stirrer, the mixture was stirred at room temperature for 30 minutes. Next, 50.0 parts of 2-chlorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture with 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. Next, after cooling the reaction mixture with ice, 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. Then, 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 and reflux. Next, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 45.0 parts of a compound represented by the formula (BI-12). Yield 44%.

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.6 parts of the compound represented by the formula (BI-12), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 0.0 parts and 20.0 parts of toluene were added, and then 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation 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 evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 21.3 parts of a compound represented by the formula (A-II-12). Yield 99%.

Identification of compound represented by formula (A-II-12) (mass spectrometry) ionization mode = ESI +: m / z = 661.3 [M-Cl] ⁺
Exact Mass: 696.3

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-12), bis (trifluoromethanesulfonyl) imidolithium (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.1 And 30.0 parts of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to obtain a blue-green solid. Further, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.4 parts of a compound of the formula (AI-12). Yield 85%.

Dissolving 0.35 part of the compound of formula (AI-12) in chloroform to a volume of 250 cm ³
Then, 2 cm ³ was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L), and an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.5 (arbitrary unit) at λmax = 625 nm.

Synthesis Reference Example 9
The following reaction was performed in a nitrogen atmosphere. After charging 5.0 parts of 2-bromo-4 ′-(methylsulfonyl) acetophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 50.0 parts of 50% isopropanol aqueous solution into a flask equipped with a condenser and a stirrer. The mixture was stirred at room temperature for 30 minutes. Subsequently, 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. Next, 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 filtered off, and the resulting yellow solid was purified by column chromatography. The purified yellow solid was dried at 60 ° C. under reduced pressure to obtain 1.0 part of a compound represented by the formula (B-III-13). Yield 22%.

  The following reaction was performed in a nitrogen atmosphere. Into a flask equipped with a condenser and a stirrer, 5.0 parts of the compound represented by the formula (B-III-13) and 50.0 parts of ethanol were added, followed by stirring at room temperature for 30 minutes. Next, 2.5 parts of piperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.2 parts of glacial acetic acid were added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred for 2 hours with heating under reflux. After allowing the reaction solution 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 filtered off, and the resulting yellow solid was purified by column chromatography. The purified yellow solid was dried at 60 ° C. under reduced pressure to obtain 3.8 parts of a compound represented by the formula (BI-13). Yield 61%.

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.2 parts of the compound represented by the formula (BI-13), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 0.0 parts and 20.0 parts of toluene were added, and then 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation 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 evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 6.8 parts of a compound represented by the formula (A-II-13). Yield 33%.

Identification of compound represented by formula (A-II-13) (mass spectrometry) ionization mode = ESI +: m / z = 629.3 [M-Cl] ⁺
Exact Mass: 664.3

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-13), bis (trifluoromethanesulfonyl) imidolithium (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.7 And 30.0 parts of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to obtain a blue-green solid. Further, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.4 parts of a compound of the formula (AI-13). Yield 80%.

Dissolving 0.35 part of the compound of formula (AI-13) in chloroform to a volume of 250 cm ³
Then, 2 cm ³ was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L), and an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.5 (arbitrary unit) at λmax = 636 nm.

Synthesis Reference Example 10
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 5.0 parts of 4-chlorophenacyl bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 50.0 parts of 50% isopropanol aqueous solution, and then at room temperature for 30 minutes. Stir. Next, 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. Next, 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 filtered off, and the resulting yellow solid was purified by column chromatography. The purified yellow solid was dried at 60 ° C. under reduced pressure to obtain 4.0 parts of a compound represented by the formula (B-III-14). Yield 89%.

  The following reaction was performed in a nitrogen atmosphere. Into a flask equipped with a condenser and a stirrer was charged 5.0 parts of the compound represented by the formula (B-II-14) and 50.0 parts of ethanol, and the mixture was stirred at room temperature for 30 minutes. Subsequently, 3.0 parts of piperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.4 parts of glacial acetic acid were added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred for 2 hours with heating under reflux. After allowing the reaction solution 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 filtered off, and the resulting yellow solid was purified by column chromatography. The purified yellow solid was dried at 60 ° C. under reduced pressure to obtain 3.7 parts of a compound represented by the formula (BI-14). Yield 57%.

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 8.8 parts of the compound represented by the formula (BI-14), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 0.0 parts and 20.0 parts of toluene were added, and then 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation 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 evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 5.3 parts of a compound represented by the formula (A-II-14). Yield 26%.

Identification of 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 in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-14), 8.0 parts of potassium tris (trifluoromethanesulfonyl) methide (manufactured by Central Glass Co., Ltd.) And 30.0 parts of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to obtain a blue-green solid. Further, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 13.6 parts of a compound of the formula (AI-14). Yield 85%.

Dissolving 0.35 part of the compound of formula (AI-14) in chloroform to a volume of 250 cm ³
Then, 2 cm ³ was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L), and an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.7 (arbitrary unit) at λmax = 623 nm.

Synthesis Reference Example 11
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 33.0 parts of potassium thiocyanate and 160.0 parts of acetone, and then stirred at room temperature for 30 minutes. Next, 50.0 parts of benzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Next, the reaction mixture was ice-cooled, and 41.6 parts of N-isopropylaniline (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. Next, after cooling the reaction mixture with ice, 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. Then, 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 and reflux. Next, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 44.8 parts of a compound represented by the formula (BI-15). Yield 47%.

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 9.3 parts of the compound represented by the formula (BI-15), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 0.0 parts and 20.0 parts of toluene were added, and then 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation 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 evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 20.5 parts of a compound represented by the formula (A-II-15). Yield 100%.

Identification of 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 in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-15), bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.9 And 30.0 parts of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to obtain a blue-green solid. Further, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.7 parts of a compound of the formula (AI-15). Yield 85%.

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

Synthesis Reference Example 12
A solution of 4,4′-dichlorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) (10 parts, 90 mmol) in N, N-dimethylformamide (100 ml) was cooled in an ice bath and sodium hydride (60%, 4. 3 parts, 90 mmol) was added, and after stirring for a while, compound 2 (6.5 parts, 30 mmol) was added little by little. After stirring at room temperature for 5 hours, water was added, dichloromethane extraction was performed, and the residue was purified by silica gel column chromatography to obtain the compound represented by the formula (CI-16) (3.1 g, yield 24%). It was.

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 7.6 parts of the compound represented by the formula (BI-7), 10.0 parts of the compound represented by the formula (CI-16) and 20.20 parts of toluene. After adding 0 part, 11.4 parts of phosphorus oxychloride was then added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation 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 evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 17.8 parts of a compound represented by the formula (A-II-16). Yield 100%.

Identification of compound represented by formula (A-II-16) (mass spectrometry) ionization mode = ESI +: m / z = 715.3 [M-Cl] ⁺
Exact Mass: 750.3

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-16), bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.0 And 30.0 parts of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to obtain a blue-green solid. Further, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.9 parts of a compound of the formula (AI-16). Yield 90%.

Dissolving 0.35 part of the compound of formula (AI-16) in chloroform to a volume of 250 cm ³
Then, 2 cm ³ was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L), and an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.9 (arbitrary unit) at λmax = 622 nm.

Synthesis Reference Example 13
The following reaction was performed in a nitrogen atmosphere. After putting 28.9 parts of potassium thiocyanate and 160.0 parts of acetone in a flask equipped with a condenser and a stirrer, the mixture was stirred at room temperature for 30 minutes. Subsequently, 50.0 parts of 2,6-difluorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture with ice, 36.4 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. Next, after cooling the reaction mixture with ice, 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. Then, 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 and reflux. Next, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 25.2 parts of a compound represented by the formula (BI-17). Yield 27%.

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 8.1 parts of the compound represented by the formula (BI-17), 10.0 parts of the compound represented by the formula (CI-16), and 20.20 parts of toluene. After adding 0 part, 11.4 parts of phosphorus oxychloride was then added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation 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 evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 18.3 parts of a compound represented by the formula (A-II-17). Yield 100%.

Identification of compound represented by formula (A-II-17) (mass spectrometry) ionization mode = ESI +: m / z = 733.3 [M-Cl] ⁺
Exact Mass: 768.3

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-17), bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.9 And 30.0 parts of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to obtain a blue-green solid. Further, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.5 parts of a compound of the formula (AI-17). Yield 87%.

Dissolving 0.35 part of the compound of formula (AI-17) in chloroform to a volume of 250 cm ³
Then, 2 cm ³ was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L), and an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.6 (arbitrary unit) at λmax = 626 nm.

Resin synthesis reference example 1
An appropriate amount of nitrogen was passed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to make a nitrogen atmosphere, 100 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85 ° C. with stirring. Next, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2. 1.0 ^2,6 ] decan-9-yl acrylate mixture (content ratio is 50:50 in molar ratio) (trade name “E-DCPA”, manufactured by Daicel Corporation) 171 parts propylene glycol monomethyl ether acetate 40 parts The solution dissolved in was dropped over about 5 hours using a dropping pump. On the other hand, a solution prepared by dissolving 26 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate was placed in a flask over about 5 hours using another dropping pump. It was dripped. After completion of the dropping of the polymerization initiator, the temperature was maintained at the same temperature for about 3 hours, and then cooled to room temperature to obtain a copolymer (resin (B-1a)) solution having a solid content of 43.5%. The obtained resin (B-1a) had a weight average molecular weight of 8,000, a molecular weight distribution (Mw / Mn) of 1.98, and an acid value in terms of solid content of 53 mg-KOH / g.

<Preparation of colored curable resin composition>
Reference example 1
Colorant (A): 26 parts of a compound of formula (A-I-1);
Alkali-soluble resin (B): 53 parts of resin (B-1a) (in terms of solid content);
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 16 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 4 parts;
Solvent (E): 120 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 480 parts of 4-hydroxy-4-methyl-2-pentanone;
In addition, 0.15 part of leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) was mixed to obtain a colored curable resin composition.

Comparative Example 1
Colorant (A): 26 parts of a compound represented by the following formula (A ′);

Alkali-soluble resin (B): 53 parts of resin (B-1a) (in terms of solid content);
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 16 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 4 parts;
Solvent (E): 120 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 480 parts of 4-hydroxy-4-methyl-2-pentanone;
In addition, 0.15 part of leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) was mixed to obtain a colored curable resin composition.

<Production of color filter>
The colored curable resin composition was applied on a 2-inch square glass substrate (# 1737; manufactured by Corning) by spin coating, and then pre-baked at 100 ° C. for 3 minutes to form a colored composition layer. After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.), exposure was performed at an exposure amount (based on 365 nm) of 150 mJ / cm ^{2 in} an air atmosphere. A photomask was not used. The colored composition layer after exposure was post-baked in an oven at 180 ° C. for 20 minutes to produce a color filter (film thickness: 2.8 μm).

<Heat resistance evaluation>
The colored coating is heated at 230 ° C. for 20 minutes, and the xy chromaticity coordinates (x, y) and brightness Y before and after heating of the coating film are measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). From the measured values, the color difference (ΔEab *) was calculated by the method described in JIS Z 8730. As a result of performing the above heat resistance evaluation about the coating film obtained in Reference Example 1, the color difference (ΔEab *) was 4.1.

  As a result of performing the above heat resistance evaluation about the coating film obtained by the comparative example 1, the color difference ((DELTA) Eab *) was 12.1. The color difference (ΔEab *) indicates that the smaller the value, the higher the heat resistance.

Reference example 2
A coating film of the colored composition was prepared in the same manner as in Reference Example 1 except that the compound of the formula (AI-1) in Reference Example 1 was changed to the (AI-4) compound, and the heat resistance was evaluated. As a result, the color difference (ΔEab *) of the coating film of the colored composition was 6.0.

Reference example 3
A coating film of the colored composition was prepared in the same manner as in Reference Example 1 except that the compound of formula (AI-1) in Reference Example 1 was changed to the compound of (AI-7), and the heat resistance was evaluated. As a result, the color difference (ΔEab *) of the coating film of the colored composition was 2.7.

Reference example 4
A coating film of the colored composition was prepared in the same manner as in Reference Example 1 except that the compound of formula (AI-1) in Reference Example 1 was changed to the compound of (AI-8), and the heat resistance was evaluated. As a result, the color difference (ΔEab *) of the coating film of the colored composition was 3.8.

Reference Example 5
A coating film of the colored composition was prepared in the same manner as in Reference Example 1 except that the compound of formula (AI-1) in Reference Example 1 was changed to the compound of (AI-9), and the heat resistance was evaluated. As a result, the color difference (ΔEab *) of the coating film of the colored composition was 2.8.

Reference Example 6
A coating film of the colored composition was prepared in the same manner as in Reference Example 1 except that the compound of formula (AI-1) in Reference Example 1 was changed to the compound of (AI-10), and the heat resistance was evaluated. As a result, the color difference (ΔEab *) of the coating film of the colored composition was 6.8.

Reference Example 7
A coating film of the colored composition was prepared in the same manner as in Reference Example 1 except that the compound of formula (AI-1) in Reference Example 1 was changed to the compound of (AI-11), and heat resistance evaluation was performed. As a result, the color difference (ΔEab *) of the coating film of the colored composition was 3.9.

Reference Example 8
A coating film of the colored composition was prepared in the same manner as in Reference Example 1 except that the compound of formula (AI-1) in Reference Example 1 was changed to the compound of (AI-12), and the heat resistance was evaluated. As a result, the color difference (ΔEab *) of the coating film of the colored composition was 4.1.

Reference Example 9
A coating film of the colored composition was prepared in the same manner as in Reference Example 1 except that the compound of formula (AI-1) in Reference Example 1 was changed to the compound of (AI-13), and the heat resistance was evaluated. As a result, the color difference (ΔEab *) of the coating film of the colored composition was 3.2.

Reference Example 10
A coating film of the colored composition was prepared in the same manner as in Reference Example 1 except that the compound of formula (AI-1) in Reference Example 1 was changed to the compound of (AI-14), and the heat resistance was evaluated. As a result, the color difference (ΔEab *) of the coating film of the colored composition was 5.7.

Reference Example 11
A coating film of the colored composition was prepared in the same manner as in Reference Example 1 except that the compound of formula (AI-1) in Reference Example 1 was changed to the compound of (AI-15), and the heat resistance was evaluated. As a result, the color difference (ΔEab *) of the coating film of the colored composition was 3.4.

Reference Example 12
A coating film of the colored composition was prepared in the same manner as in Reference Example 1 except that the compound of formula (AI-1) in Reference Example 1 was changed to the compound of (AI-16), and the heat resistance was evaluated. As a result, the color difference (ΔEab *) of the coating film of the colored composition was 1.9.

Reference Example 13
A coating film of the colored composition was prepared in the same manner as in Reference Example 1 except that the compound of formula (AI-1) in Reference Example 1 was changed to the compound of (AI-17), and the heat resistance was evaluated. As a result, the color difference (ΔEab *) of the coating film of the colored composition was 2.2.

  2. Examination of dispersion

Synthesis example 1
The following reaction was performed in a nitrogen atmosphere. After charging 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N, N-dimethylformamide into a flask equipped with a condenser and a stirrer, the mixed solution was ice-cooled. 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little over 30 minutes under ice cooling, and then stirred for 1 hour while warming to room temperature. 10.4 parts of 4,4′-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the reaction solution little by little and stirred at room temperature for 24 hours. The reaction solution was added little by little to 200 parts of ice water, and then allowed to stand at room temperature for 15 hours. When the water was removed by decantation, a viscous solid was obtained as a residue. After adding 60 parts of methanol to this viscous solid, it stirred at room temperature for 15 hours. The precipitated solid was filtered off and purified by column chromatography. The purified pale yellow solid was dried at 60 ° C. under reduced pressure to obtain 9.8 parts of a compound represented by the formula (C-I-18).

  The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer is charged with 8.2 parts of the compound represented by the formula (BI-7), 10 parts of the compound represented by the formula (CI-18) and 20 parts of toluene. Then, 12.2 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170 parts of isopropanol. Next, the diluted reaction solution was poured into 300 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation 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 evaporated using an evaporator to obtain a blue-violet solid. Further, the blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 18.4 parts of a compound represented by the formula (A-II-18).

The following reaction was performed in a nitrogen atmosphere. Into a flask equipped with a condenser and a stirrer, 8 parts of the compound represented by the formula (A-II-18) and 396 parts of methanol were added, followed by stirring at room temperature for 30 minutes to prepare a blue solution. Next, after adding 396 parts of water to the blue solution, the mixture was further stirred at room temperature for 30 minutes to obtain a reaction solution.
A beaker is charged with 53 parts of water, and 11.8 parts of Keggin-type phosphotungstic acid (manufactured by Aldrich) and 53 parts of methanol are poured into the water and mixed at room temperature in an air atmosphere to prepare a phosphotungstic acid solution. Prepared.
The obtained phosphotungstic acid solution was dropped into the previously prepared reaction solution over 1 hour. The mixture was further stirred at room temperature for 30 minutes and then filtered to obtain a blue solid. The obtained blue solid was put into 200 parts of methanol and dispersed for 1 hour, followed by filtration twice. The operation of filtering the blue solid obtained by this operation in 200 parts of water and dispersing for 1 hour was repeated twice. The blue solid obtained by this operation was dried at 60 ° C. under reduced pressure to obtain 17.1 parts of a compound represented by the formula (AI-18).

Resin synthesis example 1
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, and 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added. Heat to 70 ° C. with stirring. Next, 60 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (the compound represented by the formula (II-1) and the formula (III-1) Mixture of compounds in a molar ratio of 50:50.) 240 parts by mass was dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the solution was added using a dropping funnel over 4 hours. It was dripped in the flask kept at 70 degreeC. On the other hand, a solution in which 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 225 parts by mass of 3-methoxybutyl acetate was added to a flask over another 4 hours using another dropping funnel. It was dripped in. After dropping of the solution of the polymerization initiator is completed, the resin is kept at 70 ° C. for 4 hours and then cooled to room temperature, and has a solid content of 32.6% by mass and an acid value of 110 mg-KOH / g (in terms of solid content). A B-1b solution was obtained. The obtained resin B-1b had a weight average molecular weight Mw of 13,400 and a molecular weight distribution of 2.50.

Example 1: <Preparation of dispersion>
10 parts of a compound represented by the formula (AI-18), 2 parts of a dispersant (BYK (registered trademark) -LPN6919 (manufactured by Big Chemie Japan)), 4 parts of resin B-1b (in terms of solid content), propylene A dispersion (1) was prepared by mixing 84 parts of glycol monomethyl ether acetate and 300 parts of 0.2 mm zirconia beads and shaking for 6 hours using a paint conditioner (manufactured by Red Devil).

Example 2: <Colored curable resin composition>
Components as shown in Table 7 were mixed to obtain a colored curable resin composition.

Example 3: <Colored curable resin composition>
Components as shown in Table 7 were mixed to obtain a colored curable resin composition.

Example 4: <Preparation of dispersion>
10 parts of a compound represented by the formula (AI-18), 0.4 part of a compound represented by the formula (*), 2 parts of a dispersant (BYK (registered trademark) -LPN6919 (manufactured by Big Chemie Japan)) , 4 parts of resin B-1b (converted to solid content), 84 parts of propylene glycol monomethyl ether acetate and 300 parts of 0.2 mm zirconia beads are mixed and shaken for 6 hours using a paint conditioner (manufactured by Red Devil). A dispersion (2) was prepared.

Example 5: <Colored curable resin composition>
Components as shown in Table 7 were mixed to obtain a colored curable resin composition.

Comparative Example 2: <Colored curable resin composition>
Components as shown in Table 7 were mixed to obtain a colored curable resin composition.

In Table 7, each component is as follows.
Dispersion (1): Dispersion (1) obtained above
Dispersion (2): Dispersion (2) obtained above
Colorant (AI-18): Compound represented by Formula (AI-18) Colorant (*): Compound represented by Formula (*)

Resin (B1): Resin B-1b (solid content conversion)
Polymerizable compound (C1): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA: manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D1): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound)
Solvent (E1): Propylene glycol monomethyl ether acetate Solvent (E2): 4-hydroxy-4-methyl-2-pentanone Leveling agent (F1): Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

<Production of color filter>
After applying the colored curable resin composition obtained in Examples 2, 3, 5 or Comparative Example 2 on a 2-inch square glass substrate (Eagle XG; manufactured by Corning) by spin coating, 100 ° C. And pre-baking for 3 minutes to form a colored composition layer. After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.), exposure was performed at an exposure amount (based on 365 nm) of 150 mJ / cm ^{2 in} an air atmosphere. A photomask was not used. The colored composition layer after exposure was post-baked in an oven at 180 ° C. for 20 minutes to produce a color filter (film thickness: 2.0 μm).
About the color filter obtained from the colored curable resin composition of Example 2 or Comparative Example 2, the color difference between when prebaked at 100 ° C. for 3 minutes and when post-baked at 180 ° C. for 20 minutes is measured by a colorimeter (OSP). -SP-200; manufactured by OLYMPUS). The color difference (ΔEab *) of the color filter produced from the colored curable resin composition obtained in Example 2 is 3.8, and the color filter produced from the colored curable resin composition obtained in Comparative Example 2 The color difference (ΔEab *) was 17.6.

<Evaluation of heat resistance>
The color filter obtained from the colored curable resin composition of Examples 2, 3, 5 or Comparative Example 2 was heated at 230 ° C. for 20 minutes, and the color difference (ΔEab *) before and after heating was measured by a colorimeter (OSP-SP- 200; manufactured by OLYMPUS). The color difference (ΔEab *) of the color filter produced from the colored curable resin composition obtained in Example 2 was 5.0, and the color filter produced from the colored curable resin composition obtained in Example 3 The color difference (ΔEab *) was 2.7, and the color difference (ΔEab *) of the color filter prepared from the colored curable resin composition obtained in Example 5 was 2.2, which was obtained in Comparative Example 2. The color difference (ΔEab *) of the color filter produced from the colored curable resin composition was 8.5.

Claims (8)

A colored dispersion comprising a compound represented by the formula (AI) and a solvent.

[In the formula (AI), m represents a natural number.
X represents an oxygen atom or a sulfur atom.
R ^{41 to} R ⁴⁶ are each independently an oxygen atom between carbon atoms of a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, or an alkyl group having 2 to 20 carbon atoms. Represents an aryl group which may have a group in which is inserted or a substituent. R ⁴¹ and R ⁴² may be bonded to form a ring with the nitrogen atom to which they are bonded, R ⁴³ and R ⁴⁴ may be bonded to form a ring with the nitrogen atom to which they are bonded, R ⁴⁵ and R ⁴⁶ may be bonded to form a ring together with the nitrogen atom to which they are bonded.
R ^{47 to} R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, an alkyl group having 1 to 8 carbon atoms, or an oxygen atom between carbon atoms of an alkyl group having 2 to 8 carbon atoms. Represents an inserted group.
R ⁵⁵ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aryl group which may have a substituent.
The formula (AI) is a cation moiety.

In a molecule, the plurality of cation moieties may be the same or different.
[Y] ^m− represents an m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen as essential elements. ] The colored dispersion according to claim 1, wherein [Y] ^m- in the formula (AI) is an anion of a heteropolyacid or an isopolyacid containing tungsten as an essential element. The colored dispersion according to claim 2, wherein [Y] ^m- in formula (AI) is an anion of phosphotungstic acid, an anion of silicotungstic acid, or an anion of tungsten-based isopolyacid.   Furthermore, the coloring dispersion liquid in any one of Claims 1-3 containing dye.   The colored curable resin composition containing the colored dispersion liquid in any one of Claims 1-4, resin (B), polymeric compound (C), and a polymerization initiator (D).   The colored curable resin composition according to claim 5, comprising a dye.   A color filter formed using the colored curable resin composition according to claim 5.   A display device comprising the color filter according to claim 7.