TW201625745A - Compound and curable coloring resin composition - Google Patents

Abstract

A novel compound that can be suitably used in a color filter and has good heat resistance. The compound is indicated by the formula (A-VI) (in the formula (A-VI): a counter ion Y indicates an m-value anion; R1-8A each independently indicate a hydrogen atom or an alkyl group; R9A and R10A indicate a hydrogen atom, an alkyl group, an aromatic hydrocarbon group, or an aralkyl group; R11A and R12A each independently indicate a halogen atom or an alkyl group; at least either R11A or R12A indicate an alkyl group; R13A and R14A each independently indicate a halogen atom or an alkyl group; at least either R13A or R14A indicate a C1-10 alkyl group; and R15-20A indicate a hydrogen atom or an alkyl group.).

Description

Compound and color hardening resin composition Technical field

The present invention relates to a novel compound and a color hardening resin composition.

Background technique

In the case of International Publication No. 2012/053211, a colored curable resin composition comprising a compound represented by the formula (A-III-1), a binder resin, a solvent, a polymerization initiator, and a curing agent is described. A colored curable resin composition for forming a color filter included in a liquid crystal display device or the like, or a solid-state image sensor.

Conventional technical literature Patent literature

[Patent Document 1] International Publication No. 2012/053211

Summary of invention

The above-mentioned compound known hitherto has insufficient heat resistance, and therefore, the color-curable resin composition containing the compound is not sufficiently satisfactory at a heat-resistant point.

The present invention provides the following items [1] to [11].

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

In the formula (A-VI), the ion Y represents an anion having an m value.

R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R ^9A and R ^10A each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group which may be substituted, or an aralkyl group which may be substituted.

R ^11A and R ^12A each independently represent a halogen atom and an alkyl group having 1 to 10 carbon atoms. However, at least one of R ^11A and R ^12A is an alkyl group having 1 to 10 carbon atoms.

R ^13A and R ^14A each independently represent a halogen atom and an alkyl group having 1 to 10 carbon atoms. However, at least one of R ^13A and R ^14A is an alkyl group having 1 to 10 carbon atoms.

R ^15A , R ^16A , R ^17A , R ^18A , R ^19A and R ^20A each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

In the above R ^1A to R ^20A , the alkyl group may have an oxygen atom interposed between the methylene groups constituting the alkyl group.

A represents an aromatic hydrocarbon group or a heteroaryl group which may have a substituent.

m represents an integer from 1 to 14. ]

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

[In the formula (A-I), the ion Y represents an anion of m-valent.

R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R ^9A and R ^10A each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group which may be substituted, or an aralkyl group which may be substituted.

R ^11A and R ^12A each independently represent a halogen atom and an alkyl group having 1 to 10 carbon atoms. However, at least one of R ^11A and R ^12A is an alkyl group having 1 to 10 carbon atoms.

R ^13A and R ^14A each independently represent a halogen atom and an alkyl group having 1 to 10 carbon atoms. However, at least one of R ^13A and R ^14A is an alkyl group having 1 to 10 carbon atoms.

R ^15A , R ^16A , R ^17A , R ^18A , R ^19A and R ^20A each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

In the above R ^1A to R ^20A , the alkyl group may have an oxygen atom interposed between the methylene groups constituting the alkyl group.

R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group which may be substituted.

R ⁵⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon which may be substituted.

In the above R ⁴⁵ , R ⁴⁶ and R ⁵⁵ , the alkyl group may have an oxygen atom interposed between the methylene groups constituting the alkyl group.

m represents an integer from 1 to 14. ]

[3] The compound according to [1] or [2] wherein the counter ion is a fluorine-containing anion having a fluorine atom.

[4] The compound according to [1] or [2] wherein the counter ion is an anion containing the following element as an essential element: selected from the group consisting of tungsten, molybdenum, rhenium and phosphorus. At least 1 element, as well as oxygen.

[5] A colored curable resin composition comprising the compound (A1), the resin (B), and a polymerizable compound composed of the ion represented by the formula (A-VI) and the counter ion described in the item [1]. (C), a polymerization initiator (D) and a solvent (E).

[6] The colored curable resin composition according to [5], which comprises at least one dye (A2) selected from the group consisting of an anthraquinone dye and a porphyrazine dye.

[7] The colored curable resin composition according to [5] or [6], which comprises a colorless metal complex (F).

[8] The colored curable resin group as described in any one of [5] to [7] A substance, which further contains a blue pigment.

[9] A coating film formed of the colored curable resin composition described in [5] to [8].

[10] A color filter comprising the colored curable resin composition as described in [5] to [8].

[11] A display device comprising the color filter according to [10].

According to the present invention, a novel compound which can be suitably used for a color filter excellent in heat resistance can be obtained.

Form for implementing the invention

The compound represented by the formula (A-VI) related to the present invention can be represented by the following formula.

In the formula (A-VI), the ion Y represents an anion having an m value.

R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R ^9A and R ^10A each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group which may be substituted, or an aralkyl group which may be substituted.

R ^11A and R ^12A each independently represent a halogen atom and an alkyl group having 1 to 10 carbon atoms. However, at least one of R ^11A and R ^12A is an alkyl group having 1 to 10 carbon atoms.

R ^13A and R ^14A each independently represent a halogen atom and an alkyl group having 1 to 10 carbon atoms. However, at least one of R ^13A and R ^14A is an alkyl group having 1 to 10 carbon atoms.

R ^15A , R ^16A , R ^17A , R ^18A , R ^19A and R ^20A each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

In the above R ^1A to R ^20A , the alkyl group may have an oxygen atom interposed between the methylene groups constituting the alkyl group.

A represents an aromatic hydrocarbon group or a heteroaryl group which may have a substituent.

m represents an integer from 1 to 14. ]

The alkyl group represented by R ^1A to R ^20A may be any of a straight chain, a branched chain, and a cyclic group.

The linear or branched alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group or a fluorenyl group. The alkyl group is preferably a carbon number of 1 to 10, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 6 carbon atoms.

The cyclic alkyl group represented by R ^1A to R ^20A may be a single ring or a polycyclic ring. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group and the like. The cyclic alkyl group is preferably a carbon number of 3 to 10, and more preferably a carbon number of 6 to 10.

Specific examples of the alkyl group represented by R ^1A to R ^20A include a group represented by the following formula. In the following formula, * represents a bond.

In the group represented by R ^1A to R ^20A , a group in which an oxygen atom is interposed between the methylene groups constituting the alkyl group is, for example, a group represented by the following formula. In the following formula, * represents a bond.

The group in which the oxygen atom is interposed between the methylene groups constituting the alkyl group is preferably a group having 1 to 10 carbon atoms, and more preferably a group having 1 to 6 carbon atoms. The alkyl group to which the oxygen atom is inserted is preferably a linear alkyl group. Further, the number of carbon atoms between the oxygen atoms is preferably from 1 to 4, more preferably from 2 to 3.

Among the R ^9A to R ^10A , examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.

Among the R ^9A to R ^10A , the aromatic hydrocarbon group in the aralkyl group may, for example, be a phenyl group or a naphthyl group.

In the group represented by R ^9A to R ^10A , the substituent in the aromatic hydrocarbon group and the aralkyl group may be a halogen atom such as a fluorine atom, a chlorine atom or iodine; or a carbon number of a methoxy group or an ethoxy group; Alkoxy group of ~6; hydroxy group; alkyl group having 1 to 6 carbon atoms such as methyl group and ethyl group; alkylsulfonyl group; alkylsulfonyl group having 1 to 6 carbon atoms such as methylsulfonyl group; An alkoxycarbonyl group having 1 to 6 carbon atoms such as an oxycarbonyl group or an ethoxycarbonyl group.

Specific examples of the aromatic hydrocarbon group which may be substituted include a group represented by the following formula. In the following formula, * represents a bond.

Specific examples of the substituted aralkyl group include a group in which a methylene group is bonded to a bond of each of the following specific examples of the aromatic hydrocarbon group.

Further, examples of the group represented by R ^11A to R ^14A include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred.

From the viewpoint of easiness of synthesis, R ^1A to R ^{8A are} preferably each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or a methyl group.

From the viewpoint of easiness of synthesis, R ^9A to R ^{10A are} preferably independently a carbon number of 1 to 10 alkyl groups, a substituted aromatic hydrocarbon group or a substituted aralkyl group, and more preferably a system. Each independently is an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, a phenyl group having a methyl group, a naphthyl group having a methyl group; an unsubstituted or selected from a halogen atom, a methoxy group, an ethoxy group, 1 or more of the aminesulfonyl group, the methylsulfonyl group, the methoxycarbonyl group and the ethoxycarbonyl group, particularly one substituted aralkyl group, and more preferably each independently having a carbon number of 1 to 4 Alkenyl group.

From the viewpoint of heat resistance, at least one of R ^11A to R ^12A is an alkyl group having 1 to 10 carbon atoms, and preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. More preferably, it is more preferably a methyl group, an ethyl group, a n-propyl group or an isopropyl group. When one of R ^11A to R ^12A is an alkyl group, the other may be a halogen atom, and an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 8 carbon atoms is more preferred. The alkyl group having 1 to 4 carbon atoms is more preferable, and more preferably methyl group, ethyl group, n-propyl group or isopropyl group.

From the viewpoint of heat resistance, R ^13A to R ^14A are an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and More preferably, it is a methyl group, an ethyl group, a n-propyl group or an isopropyl group. When one of R ^13A to R ^14A is an alkyl group, the other may be a halogen atom, and preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and The alkyl group having 1 to 4 carbon atoms is more preferable, and more preferably methyl group, ethyl group, n-propyl group or isopropyl group.

From the viewpoint of easiness of synthesis, R ^15A to R ^{20A are} preferably independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The base, and more preferably, each independently is a hydrogen atom or a methyl group.

Among the A, the aromatic hydrocarbon group may, for example, be a phenyl group or a naphthyl group.

Examples of the substituent in the aromatic hydrocarbon group represented by A include a halogen atom such as a fluorine atom, a chlorine atom or iodine, a halogen alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a carbon number of 1 to 4. An alkyl group, a hydroxyl group, a SO ₃ ^- group, a methylsulfonyl group, a dialkylamino group, an anilino group, etc., and the anilino group may also be an alkoxy group having 1 to 4 carbon atoms and an alkyl group having 1 to 4 carbon atoms. The group is substituted with a hydroxyl group, a SO ₃ ^- group, a methylsulfonyl group, a dialkylamino group or the like.

In the above, the aromatic hydrocarbon group which may have a substituent may be a group represented by the following formula. * indicates a bond.

Among them, a group represented by the formula (A1-2) and the formula (A1-7) is preferred.

Among A, the heteroaromatic group may, for example, be a thiazolyl group or an imidazolyl group. An aromatic ring having a nitrogen atom, an oxygen atom or a sulfur atom, such as an azole group.

The substituent in the heteroaromatic group represented by A may, for example, be a phenyl group or an anilino group, and the anilino group may be substituted with an alkyl group having 1 to 4 carbon atoms or the like.

In the above, the heteroaromatic group which may have a substituent may, for example, be a group represented by the following formula (A-2). * indicates a bond.

In the formula (A-2), R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group which may be substituted.

R ⁵⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group which may be substituted.

In the above R ⁴⁵ , R ⁴⁶ and R ⁵⁵ , the alkyl group may have an oxygen atom interposed between the methylene groups constituting the alkyl group. ]

The alkyl group in R ⁴⁵ and R ⁴⁶ may be an alkyl group having 1 to 10 carbon atoms in R ^1A to R ^20A , respectively.

Specific examples of the alkyl group having 1 to 10 carbon atoms among R ⁴⁵ and R ⁴⁶ include a group represented by the following formula. In the following formula, * represents a bond. Among them, an alkyl group having 1 to 8 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is particularly preferred.

Among the R ⁴⁵ and R ⁴⁶ , a group in which an oxygen atom is interposed between the methylene groups constituting the alkyl group is, for example, a group represented by the following formula. In the following formula, * represents a bond.

The group in which the oxygen atom is interposed between the methylene groups constituting the alkyl group is preferably a group having 1 to 10 carbon atoms, and more preferably a group having 1 to 6 carbon atoms. The alkyl group to which the oxygen atom is inserted is preferably a linear alkyl group. Further, the number of carbon atoms between the oxygen atoms is preferably from 1 to 4, more preferably from 2 to 3.

Examples of the aromatic hydrocarbon group in R ⁴⁵ and R ⁴⁶ include a phenyl group and a naphthyl group.

Examples of the substituent in the aromatic hydrocarbon group in R ⁴⁵ and R ⁴⁶ include a halogen atom such as a fluorine atom, a chlorine atom or iodine; a haloalkyl group having 1 to 6 carbon atoms such as a chloromethyl group or a trifluoromethyl group; Alkoxy group having 1 to 6 carbon atoms such as a group or an ethoxy group; a hydroxyl group; an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group; an alkylsulfonyl group; a carbon number of a methylsulfonyl group or the like An alkylsulfonyl group of ~6; an alkoxycarbonyl group having 1 to 6 carbon atoms such as a methoxycarbonyl group; and the like.

Specific examples of the aromatic hydrocarbon group which may be substituted include a group represented by the following formula. In the following formula, * represents a bond.

From the viewpoint of easiness of synthesis, R ⁴⁵ and R ⁴⁶ are each independently an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group which may be substituted, and more preferably an alkyl group having 1 to 8 carbon atoms. Or an aromatic hydrocarbon group substituted by a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or a methylsulfonyl group, and Further, it is more preferably an alkyl group having 1 to 8 carbon atoms or an aromatic hydrocarbon group represented by the following formula. In the following formula, * represents a bond.

The alkyl group in R ⁵⁵ may, for example, be an alkyl group having 1 to 10 carbon atoms in R ^1A to R ^20A .

Among R ⁵⁵ , the alkyl group having 1 to 10 carbon atoms may, for example, be a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, an n-octyl group, a n-decyl group or a n-decyl group. Alkyl group; branched alkyl group such as isopropyl, t-butyl, tert-butyl, isopentyl, 1-methylpentyl, 1-propylbutyl; cyclopropyl, cyclobutyl A cyclic alkyl group such as a cyclopentyl group, a cyclohexyl group or an adamantyl group, and the like, and a group represented by the following formula is exemplified. In the following formula, * represents a bond. Among them, an alkyl group having 1 to 8 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is particularly preferred.

In R ⁵⁵ , a group in which an oxygen atom is interposed between methylene groups constituting the alkyl group is, for example, a group represented by the following formula. In the following formula, * represents a bond.

The aromatic hydrocarbon group in R ⁵⁵ may, for example, be a phenyl group or a naphthyl group, and a phenyl group is preferred.

In R ⁵⁵ , examples of the substituent in the aromatic hydrocarbon group include a halogen atom such as a fluorine atom, a chlorine atom or iodine; a halogen alkyl group having 1 to 6 carbon atoms such as a chloromethyl group or a trifluoromethyl group; methoxy group and B group; An alkoxy group having 1 to 6 carbon atoms such as an oxy group; a hydroxyl group; an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group; an aminesulfonyl group; a carbon number of 1 to 6 such as a methylsulfonyl group; An alkyl sulfonyl group; an alkoxycarbonyl group having 1 to 6 carbon atoms such as a methoxycarbonyl group; and the like. Specific examples of the aromatic hydrocarbon group which may be substituted include a group represented by the following formula. In the following formula, * represents a bond.

From the viewpoint of easiness of synthesis, R ^{55 is} preferably independently an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group which may be substituted, and more preferably an alkyl group having 1 to 8 carbon atoms, or An aromatic hydrocarbon group which may be substituted by a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or a methylsulfonyl group, and is more preferably It is an aromatic hydrocarbon group represented by the following formula. In the following formula, * represents a bond.

The counter ion Y in the formula (A-VI) represents an m-valent anion. Although [Y] ^m- may be a well-known anion, from the viewpoint of heat resistance, a boron-containing anion, an aluminum-containing anion, a fluorine-containing anion, and the like are selected from the group consisting of tungsten, molybdenum and rhenium. At least one element of the group consisting of phosphorus and an anion containing oxygen as an essential element.

The boron-containing anion and the aluminum-containing anion may, for example, be represented by the following formula (4). Expressed anion.

In the formula (4), W ¹ and W ² each independently represent a group having two substituents obtained by releasing a proton from a monovalent proton-donating substituent. M represents boron or aluminum. ]

A group having two substituents derived by releasing a proton from a monovalent proton-donating substituent includes a compound having at least two monovalent proton-donating substituents (for example, a hydroxyl group, a carboxylic acid group, etc.) a group obtained by releasing protons from two proton-donating substituents. The compound is preferably a catechol which may have a substituent, a 2,3-dihydroxynaphthalene which may have a substituent, a 2,2'-biphenol which may have a substituent, or a substituent. 3-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid which may have a substituent, 1-hydroxy-2-naphthoic acid which may have a substituent, binaphthol which may have a substituent, Salicylic acid which may have a substituent, diphenylglycolic acid which may have a substituent, or mandelic acid which may have a substituent.

Among the compounds exemplified above, examples of the substituent include a saturated hydrocarbon group (for example, an alkyl group or a cycloalkyl group), a halogen atom, a halogenated alkyl group, a hydroxyl group, an amine group, a nitro group, an alkoxy group and the like.

Examples of the salicylic acid which may have a substituent include salicylic acid, 3-methylsalic acid, 3-tert-butylsalic acid, 3-methoxysulphate, 3-nitrosulphate, and 4-trifluoromethyl. Salicylic acid, monoamine oleic acid such as 3,5-di-t-butyl sulphate, 3-aminosulphonic acid, 4-aminosalic acid, 5-aminosalic acid, 6-aminosulphate ; 3-hydroxysalic acid (2,3- Dihydroxybenzoic acid), 4-hydroxysalic acid (2,4-dihydroxybenzoic acid), 5-hydroxysalic acid (2,5-dihydroxybenzoic acid), 6-hydroxysalic acid (2,6-dihydroxyl) Monohydroxysulphate such as benzoic acid; dihydroxysulphate such as 4,5-dihydroxysulphate or 4,6-dihydroxysulphate; 3-chlorosulphate, 4-chlorosulphate, 5-chlorosalt Acid, 6-chlorosulphate, 3-bromosuutic acid, 4-bromoslic acid, 5-bromoslic acid, 6-bromoslic acid, etc. monohaloholic acid; 3,5-dichlorosalic acid, 3,5 - dihalosulic acid such as dibromositic acid, 3,5-diiodosalic acid or trihalosulfuric acid such as 3,5,6-trichlorosulphate or the like.

Diphenylglycolic acid which may also have a substituent may be exemplified by:

Almond acids which may also have a substituent may be exemplified by:

Wait.

The preferred anion among the anions represented by the formula (4) is an anion represented by the following formula, and examples thereof include an anion (BC-1) to an anion (BC-24) having a substituent described in Table 1, and Anions (BC-25) to anions (BC-28) represented by the formula (BC-25), the formula (BC-26), the formula (BC-27), and the formula (BC-28), respectively.

The anion represented by the formula (4) is preferably an anion (BC-1), an anion (BC-2), an anion (BC-3), an anion (BC-25), an anion (BC-26), an anion (BC- 27), and more preferably anion (BC-1), anion (BC-2), anion (BC-25), but more preferably anion (BC-1) or anion (BC-2). When it is any of these anions, the salt formed from the ion represented by the formula (A-VI) tends to be excellent in solubility in an organic solvent.

The fluorine-containing anion may, for example, be a group represented by the following formulas (6), (7), (8), and (9).

[In the formula (6), W ³ and W ⁴ each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or together with W ³ and W ⁴ represent a fluorinated alkanediyl group having 1 to 4 carbon atoms; . ]

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

In the formula (8), Y ¹ represents a fluorinated alkanediyl group having 1 to 4 carbon atoms. ]

In the formula (9), Y ² represents a fluorinated alkyl group having 1 to 4 carbon atoms. ]

Among the formulae (6) and (7), a fluorinated alkyl group having 1 to 4 carbon atoms is preferably a perfluoroalkyl group. Examples of the perfluoroalkyl group include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF(CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , and -CF ₂ CF (CF _{3 ). 2} , -C(CF ₃ ) _3, etc.

Among the formula (6), the fluorinated alkanediyl group having 1 to 4 carbon atoms is preferably a perfluoroalkanediyl group, and examples thereof include -CF ₂ -, -CF ₂ CF ₂ -, and -CF ₂ CF ₂ CF _{2 .} -, -C(CF ₃ ) ₂ -, -CF ₂ CF ₂ CF ₂ CF ₂ -, and the like.

Among the formula (8), the fluorinated alkanediyl group having 1 to 4 carbon atoms is preferably a perfluoroalkanediyl group. Examples of the perfluoroalkane group include -CF ₂ -, -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ -, -C(CF ₃ ) ₂ -, -CF ₂ CF ₂ CF ₂ CF ₂ -, and the like.

Among the formula (9), a fluorinated alkyl group having 1 to 4 carbon atoms is preferably a perfluoroalkyl group. Examples of the perfluoroalkyl group include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF(CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF(CF ₃ ). ₂ , -C(CF ₃ ) _3, etc.

The anion represented by the formula (6) (hereinafter sometimes referred to as "anion (6)") may be an anion represented by the formula (6-1) to the formula (6-6) (hereinafter sometimes referred to as "anion ( 6-1)"~ "Anion (6-6)").

An anion (7-1) represented by the following formula is exemplified as the anion represented by the formula (7) (hereinafter referred to as "anion (7)").

The anion represented by the formula (8) (hereinafter sometimes referred to as "anion (8)") may be an anion represented by the formula (8-1) to the formula (8-4) (hereinafter sometimes referred to as "anion ( 8-1)"~ "Anion (8-4)").

The anion represented by the formula (9) (hereinafter referred to as "anion (9)") may be an anion represented by the formula (9-1) to the formula (9-4) (hereinafter sometimes referred to as "anion" 9-1)"~ "Anion (9-4)").

By containing at least one anion selected from the group consisting of anion (6), anion (7), anion (8), and anion (9) (ie, a fluorine-containing anion. Hereinafter referred to as "anion ( 6)~(9)"), the solubility of the salt formed by the ion represented by the formula (A-VI) and the anion to the organic solvent can be improved. Among them, an anion (6-1), an anion (6-2), and an anion (7-1) are preferred, and an anion (6-2) is particularly preferred.

The anion which forms a salt with the ion represented by the formula (A-VI) includes an anion selected from at least one element selected from the group consisting of tungsten, molybdenum, rhodium, and phosphorus, and oxygen as an essential element, and It is preferable to use tungsten as an essential element to contain an anionic polymerization acid or an anion of a homopolymeric acid, and it is preferable to use an anion of a phosphotungstic acid, a tungstic acid, and a tungsten-based polymerization acid.

The anion of the heterogeneous polymeric acid or the homopolymeric acid contained in the tungsten as an essential element may be, for example, Keggin-type phosphotungstic acid ion α-[PW ₁₂ O ₄₀ ] ^3- , Dawson-type phosphotungstic acid ion α-[P ₂ W ₁₈ O ₆₂ ] ^6- , β-[P ₂ W ₁₈ O ₆₂ ] ^6- , Keggin-type lanthanum tungstate ion α-[SiW ₁₂ O ₄₀ ] ^4- , β-[SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O ₄₀ ] ^4- , and other examples include, for example, [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 the like.

Further, among the anions other than the anion of the heterogeneous polymer acid or the homopolymeric acid contained in the tungsten as an essential element, it is preferably an anion composed of at least one element selected from the group consisting of ruthenium and phosphorus and oxygen. .

Examples of the anion composed of at least one element selected from the group consisting of ruthenium and phosphorus and oxygen include SiO ₃ ^2- and PO ₄ ^3- .

In particular, from the viewpoint of easiness of synthesis and post-treatment, a heterogeneous polymeric acid anion such as a Keggin-type phosphotungstic acid ion, a Dawson-type phosphotungstic acid ion, or a Keggin-type lanthanum tungstate ion, [W ₁₀ O ₃₂ ] is preferable. ⁴ -is homopolymeric acid anion.

The cationic moiety of formula (A-VI) can be represented by formula (A-VI-1), (A-I-1) is a cation 1 to a cation 54 etc. which have the substituent shown by the following Table.

Wherein, the cationic moiety represented by the formulae (A-VI-1) and (AI-1) is preferably a cationic moiety represented by the formula (AI-1), and is a cation 25 to a cation 30 and a cation 37 to a cation 54. More preferably, it is particularly excellent in the cation 37 to the cation 42.

Specific examples of the compound represented by the formula (A-VI) include any one of the cations 1 to 54 and anions (BC-1) to (BC-28) and anions (6-1) to (6-6). a combination of any one of anions (7-1), anions (8-1) to (8-4), and anions (9-1) to (9-4), and any of the above cations 1 to 54 a combination of a cation and an anion α-[PW ₁₂ O ₄₀ ] ³ , a combination of any of the above cations 1 to 54 and an anion α-[P ₂ W ₁₈ O ₆₂ ] ^6- , and the aforementioned cation 1 to 54 Any combination of four cations with an anion α-[SiW ₁₂ O ₄₀ ] ^4- or [W ₁₀ O ₃₂ ] ^{4- and} the like.

The compound represented by the formula (A-VI) is preferably a compound represented by the formula (A-I) (hereinafter sometimes referred to as a compound (A-I)). The compound represented by the formula (A-I) also contains a tautomer thereof.

[In the formula (AI), Y, m, R ^1A to R ^20A , R ⁴⁵ , R ⁴⁶ and R ⁵⁵ each have the same meaning as described above. ]

The cationic moiety of formula (A-I) can be represented by formula (A-I-I), respectively, and The cation 19 to the cation 54 and the like are mentioned.

Among them, the cationic portion of the formula (A-I) is preferably a cation 25 to a cation 30 and a cation 37 to a cation 54 and is particularly preferably a cation 37 to a cation 42.

The various anions described above can be exemplified by [Y] ^m- . From the viewpoint of heat resistance, a preferred anionic boron-containing anion, an aluminum-containing anion, a fluorine-containing anion, and at least one element selected from the group consisting of tungsten, molybdenum, rhenium, and phosphorus, and oxygen An anion contained as an essential element.

Examples of the boron-containing anion and the aluminum-containing anion include an anion represented by the above formula (4). Among the anions represented by [Y] ^m- , the anion represented by the above formula (4) is preferably anion (BC-1), anion (BC-2), anion (BC-3), anion (BC-). 25), anion (BC-26), anion (BC-27), and more preferably anion (BC-1), anion (BC-2), anion (BC-25), and more preferably anion (BC) -1), anion (BC-2). When it is such an anion, the compound (AI) of the present invention tends to have excellent solubility in an organic solvent.

Examples of the fluorine-containing anion include anions represented by the above formulas (6), (7), (8), and (9) (hereinafter, each anion may be referred to as anion (6), anion (7), or anion, respectively. (8), anion (9).).

By containing at least one anion selected from the group consisting of anion (6), anion (7), anion (8), and anion (9) (hereinafter sometimes referred to as "anion (6) to (9) ))), the solubility of the salt of the dye represented by the formula (AI) in an organic solvent can be improved. Among them, an anion (6-1), an anion (6-2), and an anion (7-1) are preferred, and an anion (6-2) is particularly preferred.

Among the anions represented by [Y] ^m- , at least one element selected from the group consisting of tungsten, molybdenum, rhenium, and phosphorus, and an anion containing oxygen as an essential element are contained as tungsten as an essential element. The anisotropic polymeric acid or an anion of the homopolymeric acid is preferred, and particularly an anion of a phosphotungstic acid, a tungstic acid, and a tungsten-based polymeric acid.

The anion of the heterogeneous polymeric acid or the homopolymeric acid contained in the tungsten as an essential element may be, for example, Keggin-type phosphotungstic acid ion α-[PW ₁₂ O ₄₀ ] ^3- , Dawson-type phosphotungstic acid ion α-[P ₂ W ₁₈ O ₆₂ ] ^6- , β-[P ₂ W ₁₈ O ₆₂ ] ^6- , Keggin-type lanthanum tungstate ion α-[SiW ₁₂ O ₄₀ ] ^4- , β-[SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O ₄₀ ] ^4- , and other examples include, for example, [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- .

Further, among the anions other than the anion of the heterogeneous polymer acid or the homopolymeric acid contained in the tungsten as an essential element, it is preferably an anion composed of at least one element selected from the group consisting of ruthenium and phosphorus and oxygen. .

Examples of the anion composed of at least one element selected from the group consisting of ruthenium and phosphorus and oxygen include SiO ₃ ^2- and PO ₄ ^3- .

In particular, in view of easiness of synthesis and post-treatment, a heterogeneous polymeric acid anion such as a Keggin-type phosphotungstic acid ion, a Dawson-type phosphotungstic acid ion, a Keggin-type lanthanum tungstate ion, or the like, [W ₁₀ O ₃₂ ] is preferable. ⁴ -is homopolymeric acid anion.

m is usually 1~14, preferably 1~12, 1~10 is better, and 1~6 is better, and it is 1~4.

Examples of the compound (AI) include any one of the cations 19 to 54 and anions (BC-1) to (BC-28), anions (6-1) to (6-6), and anions (7-1). Combination of any one of anions (8-1) to (8-4) and anions (9-1) to (9-4), any three cations of the above cations 19 to 54 and anions α-[PW ₁₂ a combination of O ₄₀ ] ³ , a combination of any six cations of the above cations 19 to 54 and an anion α-[P ₂ W ₁₈ O ₆₂ ] ^6- , any four cations of the above cations 19 to 54 and an anion α-[ SiW ₁₂ O ₄₀ ] ^4- , or a combination of [W ₁₀ O ₃₂ ] ^4- , and the like.

The compound (AI) can be produced by mixing a salt containing a cationic moiety of (AI) (hereinafter sometimes referred to as a compound (A-II)) with an alkali metal salt of an anion [Y] ^m- or a protic acid. The salt containing the cationic moiety of (AI) may, for example, be a hydrochloride, a phosphate, a sulfate, a besylate, a naphthalenesulfonate, a perchlorate, a BF ₄ salt, a PF ₆ salt or the like. Further, examples of the alkali metal include lithium, sodium, potassium, and the like.

The amount of the alkali metal salt or protonic acid of the anion [Y] ^m- relative to the compound (A-II), although the cation of the compound (A-II) and the charge of the anion [Y] ^m- can be mediated by chemistry Although it is added by the measurement ratio, it is preferably 0.5 mol or more and 8 mol or less with respect to the compound (A-II) 1 mol, and more preferably 1 mol or more and 3 mol or less.

The compound (A-II) may be mixed with an alkali metal salt of an anion [Y] ^m- or a protic acid, and the two may be dissolved in the solvent or may be dissolved without being dissolved.

Examples of the solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylhydrazine, acetonitrile, ethyl acetate, toluene, methanol, and ethanol. , isopropanol, acetone, tetrahydrofuran, two Alkanes, water and chloroform.

Among them, preferred are N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylhydrazine, methanol, ethanol, isopropanol and water. In the case of these solvents, the solubility of the alkali metal salt of the compound (A-II) and the anion [Y] ^m- tends to be high.

The amount of the solvent to be used is preferably 1 part by mass or more and 30 parts by mass or less based on 1 part by mass of the compound (A-II), and more preferably 2 parts by mass or more and 20 parts by mass or less.

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

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

When a solvent compatible with water is used, the compound (A-I) can be obtained by mixing the solution and further stirring for 1 to 3 hours as needed, followed by filtration to obtain a precipitate. The obtained compound (A-I) can be washed with ion-exchanged water as needed.

When a solvent which is incompatible with water is used, the reaction mixture and the ion-exchanged water are mixed, and further stirring may be carried out for 1 to 3 hours as needed, and then the organic layer is obtained by liquid separation to obtain a solution containing the compound (AI). . The solution can be washed with ion exchange water as needed. The compound (A-I) can be obtained by removing the solvent from the solution containing the compound (A-I).

The compound (A-II) can be represented, for example, by the formula (B-I) The compound is produced by reacting with a compound represented by the formula (C-I). Such a reaction can be carried out in the presence of an organic solvent or in the absence of a solvent.

[In the formula (BI) and the formula (CI), R ^1A to R ^20A , R ⁴⁵ , R ⁴⁶ and R ⁵⁵ each have the same meaning as described above. ]

Further, the compound (A-II) can be produced by reacting a compound represented by the formula (B-II) with a compound represented by the formula (C-II) and the formula (C-III).

Such a reaction can be carried out in the presence of an organic solvent or in the absence of a solvent.

In the formulae (B-II), (C-II) and (C-III), R ^1A to R ^20A , R ⁴⁵ , R ⁴⁶ and R ⁵⁵ each have the same meaning as defined above. ]

The amount of the compound represented by the formula (CI) is preferably 0.5 mol or more and 8 mol or less per mol of the compound 1 represented by the formula (BI), and is 1 mol or more and 3 mol or less. good.

The total amount of the compound represented by the formula (C-II) and the compound represented by the formula (C-III) is from 0.5 mol to 8 mol per mol of the compound represented by the formula (B-II). The following is preferred, and it is preferably 1 mol or more and 3 mol or less.

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

From the viewpoint of productivity, it is preferred that any of the reactions be carried out in an organic solvent. The organic solvent may, for example, be a hydrocarbon solvent such as toluene or xylene; a halogenated hydrocarbon solvent such as chlorobenzene, dichlorobenzene or chloroform; methanol, ethanol or isopropyl alcohol; An alcohol solvent such as an alcohol or a butanol; a nitro hydrocarbon solvent such as nitrobenzene; a ketone solvent such as methyl isobutyl ketone; or a guanamine solvent such as 1-methyl-2-pyrrolidone. The amount of the organic solvent to be used is preferably 1 part by mass or more and 20 parts by mass or less, and 2 parts by mass or more and 10 parts by mass or less based on 1 part by mass of the compound represented by the formula (BI) or the formula (B-II). Better.

From the viewpoint of productivity, the foregoing reaction is preferably carried out in the presence of a condensing agent. Examples of the condensing agent include phosphoric acid, polyphosphoric acid, phosphorus oxychloride, sulfuric acid, and sulfinium chloride.

The amount of the condensing agent to be used is preferably 0.1 parts by mass or more and 20 parts by mass or less, and preferably 0.2 parts by mass or more and 5 parts by mass or less based on 1 part by mass of the compound represented by the formula (BI) or the formula (B-II). Better.

The method of obtaining the compound (A-II) from the reaction mixture is not particularly limited, and various methods known in the art can be employed. For example, a method in which a reaction mixture is mixed with a solvent such as an alcohol (for example, methanol or the like) and the precipitated crystals are collected by filtration. The reaction mixture is preferably added to a solvent such as the aforementioned alcohol. The temperature at which the reaction mixture can be added is preferably -100 ° C or more and 50 ° C or less, and more preferably -80 ° C or more and 0 ° C or less. Further, after that, it is preferably stirred at the same temperature for about 0.5 to 2 hours. The filtered crystals are preferably washed with water or the like, followed by drying. Further, it may be further purified by a well-known method such as recrystallization, if necessary.

The method for producing the compound (B-I) and the compound (B-II) can be exemplified by various methods, for example, the method described in the German Patent Application No. P3928243.0.

Examples of the production methods of the compounds (C-II) and (C-III) include international companies. Various methods known as the methods described in the opening of the 2012/053211 document.

The compound (CI), when R ^9A and R ^10A are an alkyl group or an aralkyl group, can give a compound represented by the formula (C-IV) (hereinafter sometimes referred to as a compound (C-IV)) and an alkylating agent. Or the aralkylating agent is reacted to produce, and the compound (C-IV) can be represented by the compound represented by the formula (CV) (hereinafter sometimes referred to as the compound (CV)) and the formula (C-VI). The compound (hereinafter sometimes referred to as compound (C-VI)) is reacted to produce. Further, the compound (CI) may be directly produced from the compound (CV) and the compound (C-VI) depending on the type of R ^9A and R ^10A .

(wherein R ^1A to R ^20A are the same as defined above. R ^1B is the same as R ^9A and R ^10A ; R ^2B is the same as R ^11A and R ^13A ; R ^3B is the same as R ^12A and R ^14A ; and R ^4B is the same and R ^15A, the same as R ^18A; R ^5B system and the R ^16A, the same as R ^19A; R ^6B based and R ^17A, R ^20A the same .R ^7B, R ^8B is a halogen atom).

As the alkylating agent, an alkylating agent known as a halogenated alkyl group, a sulfate ester or the like can be used, and in particular, a halogenated alkyl group is preferred from the viewpoint of ease of availability, and a level of ease of synthesis is considered. The alkyl iodide is particularly preferred. As the aralkylating agent, a halogenated benzyl group or the like can be used.

Specific examples of the alkylating agent include methyl iodide, ethyl iodide, n-butyl iodide, ethyl bromide, n-butyl bromide, dimethyl sulfate, diethyl sulfate, and the like. Specific examples of the aralkylating agent include iodinated benzyl group, brominated benzyl group and the like.

The amount of the alkylating agent or the aralkylating agent used is preferably 2 mol or more and 6 mol or less, and 2 mol, respectively, based on the compound 1 mol expressed by the formula (C-IV). More than 4 moles above is better.

The reaction temperature is preferably from 20 ° C to 180 ° C, and more preferably from 30 ° C to 50 ° C. The reaction time is preferably from 10 minutes to 10 hours, and more preferably from 30 minutes to 2 hours.

From the viewpoint of productivity, it is preferred that any of the reactions be carried out in an organic solvent. Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; and nitrohydrocarbons such as nitrobenzene. a solvent; a ketone solvent such as methyl isobutyl ketone; a guanamine solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or 1-methyl-2-pyrrolidone; Wait. The amount of the organic solvent used is 1 part by mass or more based on 1 part by mass of the compound represented by the formula (C-IV). The parts by mass are preferably the following, and more preferably 2 parts by mass or more and 10 parts by mass or less.

From the viewpoint of productivity, the foregoing reaction is preferably carried out in the presence of a basic compound. Examples of the basic compound include sodium hydride, LDA, DIBAL, and potassium tributoxide.

The amount of the basic compound to be used is preferably 2 mol or more and 6 mol or less per mol of the compound 1 mol represented by the formula (C-IV), and more preferably 2 mol or more and 4 mol or less.

The method for obtaining the compound (C-IV) from the reaction mixture is not particularly limited, and various methods known in the art can be employed. For example, a method in which a reaction mixture is mixed with a solvent such as an alcohol (for example, methanol or the like) and the precipitated crystals are collected by filtration. The reaction mixture is preferably added to a solvent such as the aforementioned alcohol. The temperature at which the reaction mixture can be added is preferably -100 ° C or more and 50 ° C or less, and more preferably -80 ° C or more and 0 ° C or less. Further, it is preferably stirred at the same temperature for about 0.5 to 2 hours. The filtered crystals are preferably washed with water or the like, followed by drying. Further, it may be further purified by a well-known method such as recrystallization, if necessary.

The above compound (C-IV) can be produced by reacting the compound (C-V) with the compound (C-VI) as described above. Further, the compound (C-I) can be produced by reacting the compound (C-V) with the compound (C-VI) as described above.

In the formula (C-VI), the halogen atom represented by R ^7B and R ^8B may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a fluorine atom or a chlorine atom may be used from the viewpoint of easiness of obtaining a raw material. It is better.

The amount of the compound (C-V) to be used is preferably 2 mol or more and 5 mol or less per mol of the compound (C-VI), and more preferably 2 mol or more and 3 mol or less.

The reaction temperature is preferably from 20 ° C to 180 ° C, and more preferably from 30 ° C to 50 ° C. The reaction time is preferably from 10 minutes to 10 hours, and more preferably from 30 minutes to 2 hours.

From the viewpoint of productivity, it is preferred that any of the reactions be carried out in an organic solvent. Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; and nitrohydrocarbons such as nitrobenzene. a solvent; a ketone solvent such as methyl isobutyl ketone; a guanamine solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or 1-methyl-2-pyrrolidone; Wait. The amount of the organic solvent to be used is preferably 1 part by mass or more and 20 parts by mass or less based on 1 part by mass of the compound represented by the formula (C-VI), and more preferably 2 parts by mass or more and 10 parts by mass or less.

From the viewpoint of productivity, the above reaction is preferably carried out in the presence of a palladium compound, a phosphine compound and a basic compound.

Palladium compounds include palladium (II) acetate, palladium (II) chloride, palladium (II) bromide, bis(2,4-pentanedione)palladium (II), bis(diphenyleneacetone)palladium. (0), ginseng (diphenylideneacetone) dipalladium (0), and the like.

The amount of the palladium compound to be used is preferably 0.0001 mol or more and 0.5 mol or less per mol of the compound (C-VI) 1 mol, and more preferably 0.001 mol or more and 0.1 mol or less.

Examples of the phosphine compound include dppf, Xantphos, BINAP, XPhos, SPhos, MePhos, and the like.

The amount of the phosphine compound used is preferably 0.001 mol or more and 0.5 mol or less per mol of the compound (C-VI) 1 mol, and more preferably 0.003 mol or more and 0.1 mol or less.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, sodium tributoxide, and potassium third potassium hydride.

The amount of the basic compound to be used is preferably 1 mol or more and 5 mol or less per mol of the compound (C-VI), and more preferably 1 mol or more and 3 mol or less.

The method for obtaining the compound (C-IV) from the reaction mixture is not particularly limited, and various methods known in the art can be employed. For example, a method in which a reaction mixture is mixed with an alcohol (for example, methanol or the like) and the precipitated crystals are collected by filtration. The reaction mixture is preferably added to the aforementioned alcohol. The temperature at which the reaction mixture can be added is preferably -100 ° C or more and 50 ° C or less, and more preferably -80 ° C or more and 0 ° C or less. Further, it is preferably stirred at the same temperature for about 0.5 to 2 hours. The filtered crystals are preferably washed with water or the like, followed by drying. Further, it may be further purified by a well-known method such as recrystallization, if necessary.

The alkali metal salt of the anion represented by the formula (4) can also be used, for example, by the Japanese Patent No. 4,097, 704, the Japanese Patent No. 4341251, and the Journal of The Electrochemical Society, No. 148, No. 1, , 2001. The method described in the manufacture.

The alkali metal salt of the anion represented by the formula (6), the formula (7), the formula (8) or the formula (9) can also be used as a commercially available product, and can be obtained by International Patent No. 2008/075672, JP2010-280586. It is produced by the method described in the publication.

An alkali metal salt of an anion which is selected from at least one element selected from the group consisting of tungsten, rhenium and phosphorus and oxygen as an essential element can be produced by a conventional method, but can also be used directly. Sale. Such a compound may, for example, be a corresponding anisotropic polymeric acid salt, a homopolymeric acid salt or a decanoate, a decanoate or the like. When these various salts are monovalent metal salts such as sodium, lithium, and potassium, they are preferred because they are excellent in water solubility and are easy to synthesize and post-treat.

The colored curable resin composition of the present invention contains a compound (A1), a resin (B), and a polymerizable compound (C) composed of an ion represented by the formula (A-VI) as a coloring agent (A). , a polymerization initiator (D) and a solvent (E).

The colored curable resin composition of the present invention may further contain at least one dye (A2) selected from the group consisting of an anthraquinone dye and a porphyrazine dye as a coloring agent (A).

Preferred compositions of the color-curable resin composition of the present invention include color hardening of the compound (A1), the resin (B), the polymerizable compound (C), the polymerization initiator (D), and the solvent (E). The resin composition 0 includes at least one dye (A2), a resin (B), and a polymerizable compound (C) selected from the group consisting of an anthraquinone dye and a porphyrazine dye. a coloring curable resin composition 1 of a polymerization initiator (D) and a solvent (E); A color-curable resin composition containing the compound (A1), the resin (B), the polymerizable compound (C), the polymerization initiator (D), the solvent (E), and the colorless metal complex (F)

Wait.

The coloring curable resin composition 1 contains the compound (A1) as the coloring agent (A) and at least one dye (A2) selected from the group consisting of an anthraquinone dye and a porphyrazine dye (hereinafter) Sometimes called dye (A2).).

Anthraquinone dyes can also be used as well known substances. The hydrazine dye may, for example, be CISOLVENT YELLOW 117 (hereinafter, the description of CISOLVENT YELLOW is omitted, and only the number is described), 163, 167, 189, CISOLVENT ORANGE 77, 86, CISOLVENT RED 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247, CISOLVENT VIOLET 11, 13, 14, 26, 31, 36, 37, 38 45, 47, 48, 51, 59, 60, CISOLVENT 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, CISOLVENT GREEN 3, 28, 29, 32, 33, CIACID RED 80, CIACID GREEN 25, 27 28, 41, CIACID VIOLET 34, CIACID BLUE 25, 27, 40, 45, 78, 80, 112 C. I. DISPERSE YELLOW 51, CIDISPERSE VIOLET 26, 27, CIDISPERSE BLUE 1, 14, 56, 60, CIDIRECT BLUE 40 , CIMORDANT RED 3, 11, CIMORDANT BLUE 8

Wait. The anthraquinone dye is preferably one which is soluble in an organic solvent, and is preferably a blue, violet or red anthraquinone dye.

Among them, the anthraquinone dye is preferably a compound represented by the formula (1b) (hereinafter sometimes referred to as "compound (1b)").

In the formula (1b), R ⁹¹ and R ⁹² each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and an alicyclic ring having 3 to 10 carbon atoms which may have a substituent. Hydrocarbyl group, or formula (1b')

(In the formula (1b'), R ⁹³ represents an alkyl group having 1 to 6 carbon atoms, a halogen atom, -SO ₃ H, -CO ₂ H, -CO ₂ R ⁹⁴ , -NHCOR ⁹⁴ , -SO ₃ R ⁹⁴ or - SO ₂ NR ⁹⁴ R ⁹⁵ .

R ⁹⁴ represents an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a halogen atom, a hydroxyl group or an amine group, or an alicyclic hydrocarbon group having 3 to 10 carbon atoms which may be substituted by a halogen atom, a hydroxyl group or an amine group.

R ⁹⁵ represents a hydrogen atom and a saturated hydrocarbon group having 1 to 10 carbon atoms.

r represents an integer from 0 to 5. When r is 2 or more, the plural R ⁹³ may be the same or different.

X ⁹¹ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms. )

The group indicated. ]

When the compound (1b) has -SO ₃ H and/or -CO ₂ H, it may also form a salt (for example, a Na salt or a K salt).

Among R ⁹¹ and R ⁹² , the aliphatic hydrocarbon group having 1 to 10 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group or a different group. Propyl, isobutyl, t-butyl, tert-butyl, isopentyl, neopentyl, 2-ethylhexyl and the like.

Examples of the substituent which the aliphatic hydrocarbon group may have include a hydroxyl group, a halogen atom and the like.

Examples of the alicyclic hydrocarbon group having 3 to 10 carbon atoms represented by R ⁹¹ , R ⁹² and R ⁹⁴ include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group.

Examples of the substituent which the alicyclic hydrocarbon group may have include a hydroxyl group, a halogen atom and the like.

The alkyl group having 1 to 6 carbon atoms represented by R ⁹³ may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a second butyl group or a third butyl group. , isoamyl, neopentyl and the like.

The aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ⁹⁴ and R ⁹⁵ may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group or a different group. Propyl, isobutyl, t-butyl, tert-butyl, isopentyl, neopentyl, 2-ethylhexyl and the like.

Examples of the -CO ₂ R ⁹⁴ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a third butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

Examples of the -NHCOR ⁹⁴ include an N-ethinylamino group, an N-propyl fluorenyl group, and an N-butyl fluorenyl group (amine group, N-isobutyl fluorenyl group, an amine group, and an N-p-pentylamino group.

-SO ₃ R ⁹⁴ may, for example, be a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a third butoxysulfonyl group, a hexyloxysulfonyl group or a hexyloxysulfonate. Base.

-SO ₂ NR ⁹⁴ R ⁹⁵ may, for example, be N-methylaminesulfonyl, N-ethylaminesulfonyl, N-propylaminesulfonyl, N-isopropylaminesulfonyl, N-butyl Aminesulfonyl, N-isobutylamine sulfonyl, N-butylbutylsulfonyl, N-t-butylamine sulfonyl, N-pentylamine sulfonyl, N-(1 -ethylpropyl)aminesulfonyl, N-(1,1-dimethylpropyl)aminesulfonyl, N-(1,2-dimethylpropyl)aminesulfonyl, N-( 2,2-Dimethylpropyl)aminesulfonyl, N-(1-methylbutyl)aminesulfonyl, N-(2-methylbutyl)aminesulfonyl, N-(3- Methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, N-cyclohexylamine sulfonyl, N-hexylamine sulfonyl, N-(1,3-dimethylbutyl) Aminesulfonyl, N-(3,3-dimethylbutyl)aminesulfonyl, N-heptylaminesulfonyl, N-(1-methylhexyl)aminesulfonyl, N-(1 ,4-dimethylpentyl)amine sulfonyl, N-octylamine sulfonyl, N-(2-ethylhexyl)amine sulfonyl, N-(1,5-dimethyl)hexylamine N-1 substituted amine sulfonyl group such as sulfonyl, N-(1,1,2,2-tetramethylbutyl)amine sulfonyl, N-(5-aminopentyl)amine sulfonyl N,N-dimethylaminesulfonyl, N,N-ethylmethylaminesulfonyl, N,N- Diethylamine sulfonyl, N,N-propylmethylamine sulfonyl, N,N-isopropylmethylamine sulfonyl, N,N-t-butylmethylamine sulfonyl, N, N,N-2 substituted amines such as N-butylethylamine sulfonyl, N,N-bis(1-methylpropyl)amine sulfonyl, N,N-heptylmethylamine sulfonyl Sulfonyl and the like.

Among X ⁹¹ , alkanediyl having 1 to 6 carbon atoms may, for example, be a methylene group, an ethyl group, a propane-1,3-diyl group, a propane-1,2-diyl group or a butane-1,4-diene group. Base, pentane-1,5-diyl, hexane-1,6-diyl, ethane-1,1-diyl, butane-1,3-diyl, 2-methylpropane-1, 3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, and the like.

R ⁹³ is preferably an alkyl group having 1 to 5 carbon atoms which may have a hydroxyl group, -SO ₃ R ⁹⁴ or -SO ₂ NR ⁹⁴ R ⁹⁵ , and more preferably -SO ₂ NR ⁹⁴ R ⁹⁵ and -SO ₂ NHR ^{94 is} better (in each case, R ⁹⁴ and R ⁹⁵ are the same as defined above).

The compound (1b) may, for example, be a compound represented by the formula (3-1) to the formula (3-11).

The anthraquinone dye is a compound represented by the formula (1b), and R ⁹¹ and R ⁹² are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group which may have a halogen atom, and a formula (1b'). The compound of the group is preferred, and the compound represented by the formula (3-4) and the formula (3-11) is more preferable. When it is such an anthraquinone dye, a coating film or a pattern having a high contrast ratio, a small amount of foreign matter, and a coating film or pattern excellent in light resistance can be formed.

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

Among them, a dye containing a structure represented by the formula (1c) (hereinafter sometimes referred to as a compound (1c)) is preferably used as the tetraazaporphyrin dye.

[In the formula (1c), R ⁷¹ to R ⁷⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group. Aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted phenylalkoxy, substituted or unsubstituted amine; M represents 2 hydrogen atoms, 2 monovalent metal atoms, divalent metal An atom, a trivalent substitution metal atom or an oxidized metal atom.

In the formula (1c), the aryl group means a carbocyclic aromatic group such as a phenyl group or a naphthyl group, a heterocyclic aromatic group such as a furyl group, a thienyl group or a pyridyl group, and a carbocyclic aromatic group is preferred.

In the formula (1c), R ⁷¹ to R ⁷⁸ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, and a carbon number of 1 to 24; a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 4 to 30 carbon atoms, or a substituted or unsubstituted benzene having 7 to 30 carbon atoms Alkoxy group, substituted amino group having 1 to 30 carbon atoms.

R ⁷¹ to R ⁷⁸ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, or a substituted or unsubstituted carbon number of 1 to 16. Substituted alkoxy group, substituted or unsubstituted aryl group having 6 to 24 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 24 carbon atoms, substituted or unsubstituted phenylalkoxy group having 7 to 24 carbon atoms A substituted amine group having 1 to 16 carbon atoms.

R ⁷¹ to R ^{78 are} more preferably independently a hydrogen atom, a fluorine atom, a bromine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted carbon number of 1 to 10. Alkoxy group, substituted or unsubstituted aryl group having 6 to 16 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 16 carbon atoms, substituted or unsubstituted phenylalkoxy group having 7 to 16 carbon atoms, carbon Substituted amine groups of 1 to 12.

In the formula (1c), specific examples of R ⁷¹ to R ⁷⁸ are as follows.

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

The unsubstituted alkyl group may, for example, be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, n-pentyl, isopentyl or neopentyl. , third amyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, 1-methyl Heptyl, 2-ethylhexyl, 2-propylpentyl, n-decyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5- Trimethylhexyl, n-decyl, 1-ethyloctyl, n-undecyl, 1-methylindolyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, positive Hexadeca, 1-heptyloctyl, n-hexadecyl, n-heptadedecyl, 1-octyldecyl, n-octadecyl, 1-indenylthio, 1-indolyl eleven, n-octayl , Twenty-two base, n-tetrakisyl, 1-adamantyl, cyclopentyl, cyclohexyl, descending A linear, branched or cyclic alkyl group consisting of only carbon atoms and hydrogen atoms.

Examples of the substituent in the alkyl group include alkoxy groups having 1 to 16 carbon atoms, alkoxyalkoxy groups, phenylalkoxy groups, aryloxy groups, alkylthio groups, halogen atoms, halogenated alkoxy groups, aryloxy groups, and the like. .

Specific examples of the alkyl group having a substituent include a methoxymethyl group, an ethoxymethyl group, a n-butoxymethyl group, a n-hexyloxymethyl group, a (2-ethylbutoxy)methyl group, and a n-octyl group. Oxymethyl, n-decyloxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-propoxyethyl, 2-isopropoxyethyl, 2-n-butyl Oxyethyl, 2-n-pentyloxyethyl, 2-n-hexyloxyethyl, 2-(2'-ethylbutoxy)ethyl, 2-n-heptyloxyethyl, 2-n-octyl Oxyethyl, 2-(2'-ethylhexyloxy)ethyl, 2-n-decyloxyethyl, 2-n-dodecyloxyethyl, 2-n-tetradecyloxyethyl, 2 - cyclohexyloxyethyl, 2-methoxypropyl, 3-methoxypropyl, 3-ethoxypropyl, 3-n-propoxypropyl, 3-isopropoxypropyl, 3-(n-butoxy)propyl, 3-(n-pentyloxy)propyl, 3-(n-hexyloxy)propyl, 3-(2'-ethylbutoxy)propyl, 3-( n-Octyloxy)propyl, 3-(2'-ethylhexyloxy)propyl, 3-(n-decyloxy)propyl, 3-(n-dodecyloxy)propyl, 3-(positive Tetradecyloxypropyl, 3-cyclohexyloxypropyl, 4-methoxybutyl, 4-ethoxybutyl, 4-n-propoxybutyl, 4- Propyloxybutyl, 4-n-butoxybutyl, 4-n-hexyloxybutyl, 4-n-octyloxybutyl, 4-n-decyloxybutyl, 4-n-dodecyloxybutyl , 5-methoxypentyl, 5-ethoxypentyl, 5-n-propoxypentyl, 6-ethoxyhexyl, 6-isopropoxyhexyl, 6-n-butoxyhexyl, 6 -n-hexyloxyhexyl, 6-n-decyloxyhexyl, 4-methoxycyclohexyl, 7-ethoxyheptyl, 7-isopropoxyheptyl, 8-methoxyoctyl, 10-methyl Oxycarbonyl group, 10-n-butoxycarbonyl group, 12-ethoxydodecyl group, 12-isopropoxy Alkyl group having an alkoxy group; (2-methoxyethoxy)methyl, (2-ethoxyethoxy)methyl, (2-n-butyl) Oxyethoxyethyl)methyl, (2-n-hexyloxyethoxy)methyl, (3-methoxypropoxy)methyl, (3-ethoxypropoxy)methyl, (3 -n-butoxypropoxy)methyl, (3-n-pentyloxypropoxy)methyl, (4-methoxybutoxy)methyl, (6-methoxyhexyloxy)methyl , (10-ethoxymethoxy)methyl, 2-(2'-methoxyethoxy)ethyl, 2-(2'-ethoxyethoxy)ethyl, 2-( 2'-n-butoxyethoxy)ethyl, 3-(2'-ethoxyethoxy)propyl, 3-(2'-methoxypropoxy)propyl, 3-(2 '-Isopropoxypropoxy)propyl, 3-(3'-methoxypropoxy)propyl, 3-(3'-ethoxypropoxy)propyl, etc. An alkyl group of alkoxy group; for example, benzyloxymethyl, 2-benzyloxyethyl, 2-phenylethoxyethyl, 2-(4'-methylbenzyloxy)ethyl, 2-(2'-methylbenzyloxy)ethyl, 2-(4'-fluorobenzyloxy)ethyl, 2-(4'-chlorobenzyloxy)ethyl, 3-phenyl Oxypropyl, 3-(4'-methoxy Benzyloxy)propyl, 4-benzyloxybutyl, 2-(benzyloxymethoxy)ethyl, 2-(4'-methylbenzyloxymethoxy)ethyl, etc. An alkyl group having a phenylalkoxy group; a phenoxymethyl group, a 4-methylphenoxymethyl group, a 3-methylphenoxymethyl group, a 2-methylphenoxymethyl group, a 4-methoxy group Phenoxymethyl, 4-fluorophenoxymethyl, 4-chlorophenoxymethyl, 2-chlorophenoxymethyl, 2-phenoxyethyl, 2-(4'-methyl Phenoxy)ethyl, 2-(4'-ethylphenoxy)ethyl, 2-(4'-methoxyphenoxy)ethyl, 2-(4'-chlorophenoxy)B , 2-(4'-bromophenoxy)ethyl, 2-(1'-naphthyloxy)ethyl, 2-(2'-naphthyloxy)ethyl, 3-phenoxypropyl, 3-(2'-naphthyloxy)propyl, 4-phenoxybutyl, 4-(2'-ethylbenzene Oxy)butyl, 5-(4'-tert-butylphenoxy)pentyl, 6-(2'-chlorophenoxy)hexyl, 8-phenoxyoctyl, 10-phenoxyhydrazine , 10-(3'-chlorophenoxy)indolyl, 2-(2'-phenoxyethoxy)ethyl, 3-(2'-phenoxyethoxy)propyl, 4- An alkyl group having an aryloxy group such as (2'-phenoxyethoxy)butyl; n-butylthiomethyl, n-hexylthiomethyl, 2-methylthioethyl, 2-ethylthio Base, 2-n-butylthioethyl, 2-n-hexylthioethyl, 2-n-octylthioethyl, 2-n-decylthioethyl, 3-methylthiopropyl, 3-ethylsulfide Propyl, 3-n-butylthiopropyl, 4-ethylthiobutyl, 4-n-propylthiobutyl, 4-n-butylthiobutyl, 5-ethylthiopentyl, 6-methyl An alkyl group having an alkylthio group such as thiohexyl, 6-ethylthiohexyl, 6-n-butylthiohexyl or 8-methylsulfenyl; fluoromethyl, 3-fluoropropyl, 6-fluorohexyl , 8-fluorooctyl, trifluoromethyl, 1,1-dihydro-perfluoroethyl, 1,1-dihydro-perfluoro-n-propyl, 1,1,3-trihydro-perfluoro- N-propyl, 2-hydro-perfluoro-2-propyl, 1,1-dihydro-perfluoro-n-butyl, 1,1-dihydro-perfluoro-n-pentyl, 1,1-dihydro -Perfluoro-positive , 6-fluorohexyl, 4-fluorocyclohexyl, 1,1-dihydro-perfluoro-n-octyl, 1,1-dihydro-perfluoro-n-decyl, 1,1-dihydro-perfluoro- N-dodecyl, 1,1-dihydro-perfluoro-n-tetradecyl, 1,1-dihydro-perfluoro-n-hexadecyl, perfluoroethyl, perfluoro-n-propyl, perfluoro- N-pentyl, perfluoro-n-hexyl, 2,2-bis(trifluoromethyl)propyl, dichloromethyl, 2-chloroethyl, 3-chloropropyl, 4-chlorocyclohexyl, 7-chloro An alkyl group having a halogen atom such as heptyl, 8-chlorooctyl or 2,2,2-trichloroethyl; fluoromethoxymethyl, 3-fluoro-n-propoxymethyl, 6-fluoro- n-Hexyloxymethyl, trifluoromethoxymethyl, 1,1-dihydro-perfluoroethoxymethyl, 1,1-dihydro-perfluoro-n-propoxymethyl, 2-hydrogen- Perfluoro-2-propoxymethyl, 1,1-dihydro- Perfluoro-n-butoxymethyl, 1,1-dihydro-perfluoro-n-pentyloxymethyl, 1,1-dihydro-perfluoro-n-hexyloxymethyl, 1,1-dihydro- Perfluoro-n-octyloxymethyl, 1,1-dihydro-perfluoro-n-decyloxymethyl, 1,1-dihydro-perfluoro-n-tetradecyloxymethyl, 2,2-double (Trifluoromethyl)propoxymethyl, 3-chloro-n-propoxymethyl, 2-(8-fluoro-n-octyloxy)ethyl, 2-(1,1-dihydro-perfluoro Ethoxy)ethyl, 2-(1,1,3-trihydro-perfluoro-n-propoxy)ethyl, 2-(1,1-dihydro-perfluoro-n-pentyloxy)ethyl , 2-(6-fluoro-n-hexyloxy)ethyl, 2-(1,1-dihydro-perfluoro-n-octyloxy)ethyl, 3-(4-fluorocyclohexyloxy)propyl, 3-(1,1-Dihydro-perfluoroethoxy)propyl, 3-(1,1-dihydro-perfluoro-n-dodecyloxy)propyl, 4-(perfluoro-n-hexyloxy) Butyl, 4-(1,1-dihydro-perfluoroethoxy)butyl, 6-(2-chloroethoxy)hexyl, 6-(1,1-dihydro-perfluoroethoxy An alkyl group having a haloalkoxy group such as hexyl; phenoxymethyl, 4-methylphenoxymethyl, 3-methylphenoxymethyl, 2-methylphenoxymethyl, 4- Ethylphenoxymethyl, 4-n-propylphenoxymethyl, 4-n-butylphenoxymethyl, 4- Butylphenoxymethyl, 4-n-hexylphenoxymethyl, 4-n-octylphenoxymethyl, 4-n-decylphenoxymethyl, 4-methoxyphenoxymethyl 4-ethoxyphenoxymethyl, 4-butoxyphenoxymethyl, 4-n-pentyloxyphenoxymethyl, 4-fluorophenoxymethyl, 3-fluorophenoxy Methyl, 2-fluorophenoxymethyl, 3,4-difluorophenoxymethyl, 4-chlorophenoxymethyl, 2-chlorophenoxymethyl, 4-phenylphenoxymethyl , 1-naphthyloxymethyl, 2-naphthyloxymethyl, 2-furanyloxymethyl, 1-phenoxyethyl, 2-phenoxyethyl, 2-(4'-methyl Phenoxy)ethyl, 2-(4'-ethylphenoxy)ethyl, 2-(4'-n-hexylphenoxy)ethyl, 2-(4'-methoxyphenoxy) Ethyl, 2-(4'-n-butoxyphenoxy)ethyl, 2-(4'-fluorophenoxy)ethyl , 2-(4'-chlorophenoxy)ethyl, 2-(4'-bromophenoxy)ethyl, 2-(1'-naphthyloxy)ethyl, 2-(2'-naphthalene Oxy)ethyl, 2-phenoxypropyl, 3-phenoxypropyl, 3-(4'-methylphenoxy)propyl, 3-(2'-naphthyloxy)propyl, 4-phenoxybutyl, 4-(2'-ethylphenoxy)butyl, 4-phenoxypentyl, 5-phenoxypentyl, 5-(4'-tert-butylbenzene Oxy)pentyl, 6-phenoxyhexyl, 6-(2'-chlorophenoxy)hexyl, 8-phenoxyoctyl, 10-phenoxyindolyl, 10-(3'-methyl An alkyl group having an aryloxy group such as a phenoxy)indenyl group.

The unsubstituted alkoxy group may, for example, be an alkoxy group derived from a specific example of the aforementioned alkyl group. The substituent in the substituted alkoxy group may be the same as the above-mentioned alkyl group.

Examples of the unsubstituted aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-fluorenyl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 1-fluorenyl group, and a 2-fluorenyl group. 2-indenyl, 3-indenyl, 2-propadienyl indenyl, 3-propadienyl indenyl, 7-propadienyl indenyl, 8-propadienyl indenyl.

Examples of the substituent in the substituted aryl group include an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryloxy group, an aryl group, and a halogen atom.

Specific examples of the aryl group having a substituent include 1-methyl-2-indenyl group, 2-methylphenyl group, 4-ethylphenyl group, 4-tert-butylphenyl group, 4-(4'- Tert-butylcyclohexyl)phenyl, 3-cyclohexylphenyl, 2-cyclohexylphenyl, 4-ethyl-1-naphthyl, 6-n-butyl-2-naphthyl, 2,4-di An alkyl group having an alkyl group; 4-methoxyphenyl, 3-ethoxyphenyl, 2-ethoxyphenyl, 4-n-propoxyphenyl, 3-n-propyl Oxyphenyl, 4-isopropoxyphenyl, 3-isopropoxyphenyl, 2-isopropoxyphenyl, 2-secondbutoxyphenyl, 4-n-pentyloxybenzene An aryl group having an alkoxy group and an aryloxy group such as 4-isopentyloxyphenyl, 2-methyl-5-methoxyphenyl or 2-phenoxyphenyl; 4-phenylbenzene , 3-phenylphenyl, 2-phenylphenyl, 2,6-diphenylphenyl, 4-(2'-naphthyl)phenyl, 2-phenyl-1-naphthyl, 1- An aryl group having an aryl group such as a phenyl-2-naphthyl group or a 7-phenyl-1-fluorenyl group; a 4-fluorophenyl group, a 3-fluorophenyl group, a 2-fluorophenyl group, a 4-chlorophenyl group, 4-bromophenyl, 2-chloro-5-methylphenyl, 2-chloro-6-methylphenyl, 2-methyl-3-chlorophenyl, 2-methoxy-4-fluorophenyl An aryl group having a halogen atom such as 2-fluoro-4-methoxyphenyl; further, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl , 3,5-bistrifluoromethylphenyl, 4-perfluoroethylphenyl, 4-methylthiophenyl, 4-ethylthiophenyl, 4-cyanophenyl, 3-cyanobenzene Base.

The unsubstituted aryloxy group may, for example, be an aryloxy group derived from a specific example of the above aryl group. The substituent in the substituted aryl group may be the same as the above-exemplified aryl group.

The substituted or unsubstituted phenylalkoxy group may, for example, be benzyloxy, α-methylbenzyloxy, phenethyloxy, α-methylphenylethoxy, α,α-dimethylbenzyloxy. Unsubstituted or benzene having an alkyl group such as α,α-dimethylphenylethoxy, 4-methylphenylethoxy, 4-methylbenzyloxy or 4-isopropylbenzyloxy Alkoxy; phenylalkoxy having an aryl or aralkyl group such as 4-benzylmethylbenzyloxy, 4-phenylethylbenzyloxy, 4-phenylbenzyloxy, etc.; 4-A Oxybenzyloxy, 4-n-tetradecyloxybenzyloxy, 4-n-heptadecaoxybenzyloxy, 3,4-dimethoxybenzyloxy, 4-methoxymethyl Benzomethoxy, 4-vinyloxymethylbenzene a phenylalkoxy group having a substituted oxy group such as a methoxy group, a 4-benzyloxybenzyloxy group, a 4-phenylethoxybenzyloxy group, or the like; a 4-hydroxybenzyloxy group, a 4-hydroxy-3 group a phenylalkoxy group having a hydroxyl group such as a methoxybenzyloxy group; a halogen atom having a 4-fluorobenzyloxy group, a 3-chlorobenzyloxy group, a 3,4-dichlorobenzyloxy group or the like Phenyloxy; 2-mercaptooxy, diphenylmethoxy, 1-naphthylmethoxy, 2-naphthylmethoxy, and the like.

Specific examples of the amine group having a substituent include N-methylamino group, N-ethylamino group, N-n-butylamino group, N-cyclohexylamino group, N-n-octylamino group, N- An amine group having an alkyl group such as n-methylamino group; N-benzylamino group, N-anilino group, N-(3-methylphenyl)amino group, N-(4-methylphenyl group) Amino, N-(4-n-butylphenyl)amino, N-(4-methoxyphenyl)amine, N-(3-fluorophenyl)amine, N-(4-chlorobenzene Amino group having an aralkyl group or an aryl group such as an amine group, an N-(1-naphthyl)amino group or an N-(2-naphthyl)amino group; having 2 N,N-dimethylamines , N,N-diethylamino, N,N-di-n-butylamino, N,N-di-n-hexylamino, N,N-di-n-octylamino, N,N -di-n-decylamino, N,N-di-n-dodecylamino, N-methyl-N-ethylamino, N-ethyl-N-n-butylamino, N- An alkyl group or an aralkyl group such as a N-anilinyl group, an N-ethyl-N-anilino group or an N-n-butyl-N-anilino group, or an amine group as a substituent; having 2 N, N groups -diphenylamino, N,N-bis(3-methylphenyl)amino, N,N-bis(4-methylphenyl)amino, N,N-bis(4-ethylphenyl) Amine, N,N-bis(4-t-butylphenyl)amine, N,N- (4-n-hexyl phenyl) amine, N, N- bis (4-methoxyphenyl) amine, N, N- bis (4-ethoxyphenyl) amino, N, N- two (4-n-butoxyphenyl)amino, N,N-bis(4-n-hexyloxyphenyl)amino, N,N-di(1-naphthyl)amine, N,N-di ( 2-naphthyl)amino, N-phenyl-N-(3-methylphenyl)amino, N-phenyl-N-(4-methylphenyl)amino, N-phenyl-N -(4-octylphenyl)amino, N-phenyl-N-(4-methoxyphenyl)amino, N-phenyl-N-(4-ethoxyphenyl)amine, N-phenyl-N-(4-n-hexyloxyphenyl)amino, N-phenyl-N-(4-fluorophenyl)amino, N-phenyl-N-(1-naphthyl)amine , N-phenyl-N-(2-naphthyl)amino, N-phenyl-N-(3-phenylphenyl)amino, N-phenyl-N-(4-phenylphenyl An aryl group such as an amine group, an amine group or the like as a substituent.

In the formula (1c), M represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent substituted metal atom or an oxidized metal atom, more preferably two hydrogen atoms, and a divalent A metal atom or an oxidized metal atom is more preferably a divalent metal atom or an oxidized metal atom.

Examples of the monovalent metal atom represented by M include Na, K, and Li.

Examples of the divalent metal atom represented by M include Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Mg, Ti, Be, Ca, Ba, Cd, Hg, Pb, and Sn.

The trivalent substituted metal atom represented by M may, for example, be Al-Cl, Ga-Br, Ga-I, In-Cl, Al-C ₆ H ₅ , In-C ₆ H ₅ , Mn(OH), Mn [OSi (CH ₃ ) ₃ ], Fe-Cl, and the like.

Examples of the oxidized metal atom represented by M include VO, MnO, TiO, and the like.

Among the formulas (1c), M is more preferably Cu, Zn, Fe, Co, Ni, Pd, Mn, Mg, VO, and TiO, and is more preferably Cu, Ni, Pd, and VO, and Cu, Pd. And VO is especially good.

Specific examples of the compound (1c) include the formula (2-1) to the formula (2-38). The compound represented.

The porphyrazine dye is preferably a compound represented by the formula (2-29).

If the composition containing the porphyrazine dye is contained, a coating film or pattern having a high contrast can be formed, and the generation of foreign matter is small.

The content of the compound (A1) is preferably 0.5% by mass or more and 80% by mass or less based on the total amount of the coloring agent (A), and more preferably 40% by mass or more and 80% by mass or less.

The content of the dye (A2) is preferably from 1 to 100 parts by mass, more preferably from 10 to 100 parts by mass, per 100 parts by mass of the compound (A1).

<Colorless metal complex (F)>

The colored curable resin composition 2 may also contain a colorless metal complex (F). Further, the colored curable resin composition 1 of the present invention may further comprise a colorless metal complex (F).

The colorless metal complex (F) is exemplified by the zinc complex represented by the formula (10).

[In the formula (10), R ⁸¹ to R ⁸⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a hydroxyl group]

The alkyl group in R ⁸¹ to R ⁸⁴ may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a second butyl group or a third butyl group. Specific examples of the zinc complex represented by the formula (10) include a substituent having a substituent shown in the following table. Among them, the zinc complex (10)-18 is preferred from the viewpoint of improving heat resistance.

In the above table, ^-t C ₄ H ₉ represents a third butyl group.

The content of the colorless metal complex is preferably 0.1 parts by mass or more and 40 parts by mass or less based on 100 parts by mass of the coloring agent (A), and more preferably 0.1 parts by mass or more and 30 parts by mass or less, and further preferably 0.5 mass%. More than 15 parts by mass or less is more preferred.

The colored curable resin composition 0 contains the compound (A1) as the colorant (A), and may further contain the resin (B), the polymerizable compound (C), and the polymerization. Starter (D) and solvent (E).

The colored curable resin composition 1 is characterized in that the compound (A1) and at least one dye (A2) selected from the group consisting of an anthraquinone dye and a porphyrazine dye are contained as a coloring agent (A), and Further, the resin (B), the polymerizable compound (C), the polymerization initiator (D), and the solvent (E) may be further included.

The coloring curable resin composition 2 contains the compound (A1) as a coloring agent (A), and may further contain a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and Colorless metal complex (F).

The colored curable resin composition preferably further contains a polymerization initiation aid (D1), a leveling agent (H), and an antioxidant (J).

In the present specification, the compounds exemplified as the respective components may be used singly or in combination of plural kinds unless otherwise specified.

<Colorant (A)>

In addition to the compound (A1) and the dye (A2) of the present invention, the colored curable resin composition of the present invention may further contain other dyes for coloring, that is, for adjusting the spectral characteristics. , a mixture of pigments (P) or the like.

The dye may, for example, be a dye such as an oil-soluble dye, an acid dye or a basic dye, and may be any of a direct dye and a mordant dye. The acid dye may be an amine salt, a sulfonamide derivative or the like.

The dye may, for example, be a dye which is classified into a dye by a color index (published by The Society of Dyers and Colourists), and a dye known as Dyeing Note (Dyeing Note). Specifically, an azo may be mentioned. Dye, anthocyanin dye, triphenylmethane dye, oxon dye Materials, phthalocyanine dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, methine azo dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes , quinoline dyes and nitro dyes. Among them, organic solvent-soluble dyes are preferably used.

More specifically, CISOLVENT RED 45, 49, 125, 130, 218; CISOLVENT BLUE 4, 5, 37, 67, 70; CIACID RED 1, 4, 8, 14, 17, 18, 26 , 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133 , 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261 , 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 422, 426 CIACID VIOLET 6, 7, 9, 30, 102; CIACID BLUE 18, 29, 42, 59, 60, 70, 72, 74, 82, 92, 102, 113, 117, 120, 126, 131, 142 , 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 242, 243, 256, 259, 267, 285, 296, 315, 335 ; CIACID dyes, CIDIRECT RED 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173 176,177,179,182,184,204,207,211,213,218,221,222,232,233, 243, 246, 250; CIDIRECT VIOLET 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CIDIRECT BLUE 1, 2, 6, 8, 15, 22, 25, 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, 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, 212, 213, 214, 222 , 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 274, 275, 293 CIBASIC RED 1, 10; CIBASIC BLUE 3, 9, 24, 25, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68; etc. CIBASIC dye, CIREACTIVE RED 36; CIREACTIVE dyes, CIMORDANT RED 1, 9, 12, 14, 17, 18, 19, 22, 23, 24, 26, 27, 30, 32, 33, 36, 37 , 38, 39, 41, 43, 46, 48, 53, 56, 71, 74, 85, 86, 88, 90, 94, 95; CIMORDANT VIOLET 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 47, 48, 53, 58; CIMORDANT BLUE 1, 2, 3, 7, 9, 13, 15, 16 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 77, 83; etc. C.I.MORDANT dye.

Among them, blue dye, purple dye and red dye are preferred.

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

Further, by classification of the chemical structure, it is preferred to use a xanthene dye.

As the xanthene dye, a well-known substance can be used. The xanthene dye is preferably a compound represented by the formula (1) (hereinafter, this compound may be referred to as "compound (1)").

In the formula (1), R ¹ and R ² each independently represent a phenyl group which may have a substituent.

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

R ¹ and R ³ together with the nitrogen atom to which they are bonded may represent a ring containing a nitrogen atom, and R ² and R ⁴ together with the nitrogen atom to which they are bonded may represent a ring containing a nitrogen atom.

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

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 from 0 to 4. When m is an integer of 2 or more, the plural R ⁵ may be the same or different.

R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom.

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

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or may represent a 3 to 10 member nitrogen-containing heterocyclic ring together with a nitrogen atom.

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

Among ^the R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ of R ⁵ , the monovalent saturated hydrocarbon group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group or a fluorene group. a linear alkyl group having 1 to 20 carbon atoms such as a thiol group, a fluorenyl group, a dodecyl group, a hexadecanyl group and a hexyl group; an isopropyl group, an isobutyl group, a second butyl group, a tert-butyl group, and an isopenic group a branched alkyl group having 3 to 20 carbon atoms such as a group, a neopentyl group and a 2-ethylhexyl group; a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a tricyclodecyl group; An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms.

Therefore, among R ⁵ , -CO ₂ R ⁸ may, for example, be a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a third butoxycarbonyl group, a hexyloxycarbonyl group or an icosyloxycarbonyl group.

-SO ₃ R ⁸ may, for example, be a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a third butoxysulfonyl group, a hexyloxysulfonyl group or an icosylsulfonyl group. Base.

-SO ₂ NR ⁹ R ¹⁰ may include an amine sulfonyl group; N-methylamine sulfonyl group, N-ethylamine sulfonyl group, N-propylamine sulfonyl group, N-isopropylamine sulfonyl group , N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-tert-butylamine sulfonyl, N-tert-butylamine sulfonyl, N-pentylamine sulfonyl , N-(1-ethylpropyl)aminesulfonyl, N-(1,1-dimethylpropyl)aminesulfonyl, N-(1,2-dimethylpropyl)aminesulfonate , N-(2,2-dimethylpropyl)amine sulfonyl, N-(1-methylbutyl)amine sulfonyl, N-(2-methylbutyl)amine sulfonyl, N-(3-methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, N-hexylamine sulfonyl, N-(1,3-dimethylbutyl)amine sulfonyl , N-(3,3-dimethylbutyl)amine sulfonyl, N-heptylamine sulfonyl, N-(1-methylhexyl)amine sulfonyl, N-(1,4-di Methyl amyl sulfonyl, N-octylamine sulfonyl, N-(2-ethylhexyl)amine sulfonyl, N-(1,5-dimethyl)hexylamine sulfonyl, N-substituted amine sulfonyl group of N-(1,1,2,2-tetramethylbutyl)amine sulfonyl group; N,N-dimethylamine sulfonyl, N,N-ethyl Methylamine sulfonyl, N,N-diethylamine sulfonyl, N,N-propylmethylamine Indenyl, N,N-isopropylmethylaminesulfonyl, N,N-t-butylmethylaminesulfonyl, N,N-butylethylaminesulfonyl, N,N-double (1 N, N-2 substituted amine sulfonyl group, etc., such as methylpropyl)aminesulfonyl, N,N-heptylmethylaminesulfonyl or the like.

In R ⁸ , the hydrogen atom contained in the monovalent saturated hydrocarbon group may be substituted by a halogen atom, and the -CH ₂ - contained in the saturated hydrocarbon group may be substituted by -O-, -CO- or -NR ¹¹ - .

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

The saturated hydrocarbon group substituted by a halogen atom may, for example, be a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group or a chlorobutyl group.

R ⁹ and R ¹⁰ together with a nitrogen atom represent a 3 to 10 member nitrogen-containing heterocyclic ring. The heterocyclic ring may, for example, be the following.

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

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

As the above ⁺ N(R ¹¹ ) ₄ , among the four R ¹¹ , at least two are preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ¹¹ is preferably from 20 to 80, and more preferably from 20 to 60.

The phenyl group representing R ¹ and R ² may have a substituent. Examples of the substituent include a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ and -SO ₂ NR ⁹ R ¹⁰ . Among these substituents, -R ^{8 is} preferred, and a saturated hydrocarbon group having a valence of from 1 to 10 carbon atoms is more preferred. At this time, -SO ₃ ^- Z ^{+ is} preferably -SO ₃ ^-+ N(R ¹¹ ) ₄ .

-R ⁸ , -CO ₂ R ⁸ , -SO ₃ R ⁸ , -SO ₂ NR ⁹ R ¹⁰ are the same as described above.

-OR ⁸ may, for example, be a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group or a hexyloxy group. .

The -SR ⁸ may, for example, be a methylthio group, an ethylthio group, a butylthio group, a hexylthio group, a mercaptothio group or a decylthio group.

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

Among the R ³ and R ⁴ , the monovalent saturated hydrocarbon group may be a carbon number of a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group or a fluorenyl group. a linear alkyl group of 10; a branched chain having a carbon number of 3 to 10 such as isopropyl, isobutyl, t-butyl, t-butyl, isopentyl, neopentyl or 2-ethylhexyl An alkyl group; an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or a cyclooctyl group.

In R ³ and R ⁴ , the hydrogen atom contained in the monovalent saturated hydrocarbon group may be substituted by a halogen atom, and the -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO- or -NR ¹¹ - replaced.

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

The saturated hydrocarbon group substituted by a halogen atom may, for example, be a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group or a chlorobutyl group.

R ³ and R ^{4 are} preferably an unsubstituted saturated hydrocarbon group having a monovalent number of carbon atoms of 1 to 10, and more preferably a saturated hydrocarbon group having a valence of 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group.

R ¹ and R ³ may form a ring together with a nitrogen atom to which they are bonded, and R ² and R ⁴ may form a ring together with a nitrogen atom to which they are bonded, respectively. The ring containing a nitrogen atom may, for example, be the following.

Examples of the alkyl group having 1 to 6 carbon atoms of R ⁶ and R ⁷ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a second butyl group, and a third butyl group. Base, isopentyl and neopentyl.

R ⁵ is preferably -SO ₃ H, -SO ₃ ^- Z ^{+ or} -SO ₂ NR ⁹ R ¹⁰ .

R ⁶ and R ⁷ are preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom.

The m system is preferably an integer of 0 to 2, and more preferably 0 or 1.

The compound (1) is preferably a compound represented by the formula (2).

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

The p and q are each independently representing an integer from 0 to 5. When p is 2 or more, the plural R ²³ may be the same or different, and when q is 2 or more, the plural R ²⁴ may be the same or different. ]

The alkyl group having 1 to 4 carbon atoms represented by R ²¹ , R ²² , R ²³ and R ²⁴ may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or a second butyl group. Tributyl and the like.

R ²¹ and R ^{22 are} preferably each independently a methyl group and an ethyl group. R ²³ and R ²⁴ are more preferably a methyl group.

The compound (1) is preferably a compound represented by the formula (3).

In the formula (3), R ³¹ and R ³² each independently represent an alkyl group having 1 to 4 carbon atoms.

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

The alkyl group having 1 to 4 carbon atoms represented by R ³¹ , R ³² , R ³³ and R ³⁴ may be the same as defined above.

R ³¹ and R ^{32 are} preferably each independently methyl or ethyl. R ³³ and R ³⁴ are each preferably independently a hydrogen atom or a methyl group.

The compound (1) may, for example, be a compound represented by the formula (1-1) to the formula (1-7). Among them, from the viewpoint of excellent solubility in an organic solvent, a compound represented by the formula (1-1) is preferred.

The pigment (P) can be used without any particular limitation, and examples thereof include pigments classified into pigments according to a color index (published by The Society of Dyers and Colourists).

Examples of the pigment (P) include: CIPIGMENT YELLOW 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, Yellow pigments of 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, etc.; CIPIGMENT ORANGE 13, 31, 36, 38, 40, 42, 43, 51, 55 Orange pigments such as 59, 61, 64, 65, 71, 73; CIPIGMENT RED 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. ; CIPIGMENT BLUE 15, 15:3, 15:4, 15:6, 60, etc. blue pigment; CIPIGMENT VIOLET 1, 19, 23, 29, 32, 36, 38, etc. purple pigment; CIPIGMENT GREEN 7 , green pigments such as 36, 58; brown pigments such as CIPIGMENT BROWN 23, 25; black pigments such as CIPIGMENT BLACK 1, 7, etc.

The pigment (P) is preferably a phthalocyanine pigment and two The pigment is more preferably at least one selected from the group consisting of CIPIGMENT BLUE 15, 15:3, 15:4, 15:6, and PIGMENT VIOLET 23, and more preferably selected from CIPIGMENT BLUE 15: 6 and at least one of the groups formed by PIGMENT VIOLET 23. By including the aforementioned pigment, the optimization of the breakthrough spectrum can be easily performed, and the heat resistance, light resistance, and chemical resistance of the color filter can be made good.

The colored curable resin composition of the present invention preferably contains a blue pigment.

The pigment may be subjected to the following treatments as needed: rosin treatment, surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, graft treatment of a pigment surface by a polymer compound or the like, and sulfuric acid particles. Micronization treatment by a chemical method or the like, or a washing treatment by an organic solvent for removing impurities, water, or the like, or ion exchange by ionic impurities Removal processing or the like by changing the method or the like. The particle size of the pigment is preferably uniform.

As the pigment, a pigment dispersion liquid obtained by uniformly dispersing a pigment in a solvent can also be used.

The pigment dispersion can be obtained by mixing a pigment and a pigment dispersant in a solvent.

In the above mixing, when two or more kinds of pigments are mixed, they may be used alone or in combination of plural kinds.

The pigment dispersant may be any of a cationic, anionic, nonionic, or amphoteric dispersant, and examples thereof include a polyester-based, polyamine-based, and acrylic-based pigment dispersant.

These pigment dispersants may be used singly or in combination of two or more. Examples of the pigment dispersant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOWLEN (manufactured by Kyoeisha Chemical Co., Ltd.), SOLSPERSE (manufactured by ZENECA Co., Ltd.), EFKA (manufactured by BASF Corporation), and AJISPER (Azure). It is a fine chemical (manufactured by BYK Chemical Co., Ltd.).

The solvent is not particularly limited, and examples thereof include the same solvents as those in the colored curable resin composition of the present invention.

When the pigment dispersant is used, the amount thereof is preferably 100 parts by mass or less based on 100 parts by mass of the pigment, and more preferably 5 parts by mass or more and 50 parts by mass or less. When the amount of the pigment dispersant used is in the above range, there is a tendency that a pigment dispersion liquid in which a pigment is uniformly dispersed in a solvent is obtained.

The content of the colorant (A) is preferably 5% by mass or more and 70% by mass or less based on the total amount of the solid portion, and is 5% by mass or more and 60% by mass. It is more preferably 5% or less, and more preferably 5% by mass or more and 50% by mass or less. When the content of the coloring agent (A) is within the above range, a desired spectral and color concentration can be obtained.

In the present specification, the "total amount of the solid portion" means the total amount of the components from which the solvent (E) is removed from the colored curable resin composition of the present invention. The total amount of the solid portion and the content of each component relative thereto can be measured, for example, by a known analytical means such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) is not particularly limited, but an alkali-soluble resin (B) is preferred. The alkali-soluble resin (B) (hereinafter sometimes referred to as "resin (B)")) is derived from at least one monomer selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) a copolymer of structural units.

Examples of the resin (B) include the following resins [K1] to [K6].

The resin [K1] is selected from at least one monomer (a) (hereinafter sometimes referred to as "(a)")) composed of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and has a carbon number of 2 to 4 a copolymer of a cyclic ether structure and an ethylenically unsaturatedly bonded monomer (b) (hereinafter sometimes referred to as "(b)"); Resin [K2] (a), (b) and monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter sometimes referred to as "(c)" Copolymer; resin [K3] copolymer of (a) and (c); resin [K4] resin obtained by reacting (b) the copolymer of (a) and (c); resin [K5] (a) a resin obtained by reacting the copolymers of (b) and (c); the resin [K6] reacts (a) with the copolymer of (b) and (c), and then reacts the carboxylic anhydride The resin that should be made of it.

(a) Specific examples thereof include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid; maleic acid and fumaric acid; Coke citrate, methyl fumaric acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1 , 2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1, 4-cyclohexene dicarboxylic acid, etc., unsaturated dicarboxylic 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, 5-carboxy-5-methyl Bicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2- a carboxy-containing bicyclic unsaturated compound such as a olefin or a 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, pyroic anhydride, itaconic anhydride, 3-vinyl Phthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyl Tetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[ 2.2.1] an unsaturated form of an unsaturated dicarboxylic acid such as hept-2-ene anhydrate; succinic acid mono [2-(methyl) propylene methoxyethyl], phthalic acid mono [2-(methyl) An unsaturated mono[(meth)propenyloxyalkyl]ester of a polyvalent carboxylic acid having a valence of 2 or more, such as propylene methoxyethyl]; or the like, as in α-(hydroxymethyl)acrylic acid An unsaturated acrylate having a hydroxyl group and a carboxyl group in the molecule.

Among them, from the viewpoint of copolymerization reactivity and the obtained resin to alkaline water From the viewpoint of solubility of the solution, acrylic acid, methacrylic acid, maleic anhydride or the like is preferred.

(b) A cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an oxirane ring, an oxindole ring, and a tetrahydrofuran ring) and ethylenic unsaturation Bonded polymeric compound.

(b) It is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group.

In the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The contents of "(meth)acrylonitrile" and "(meth)acrylate" have the same meaning.

(b) A monomer (b1) having an ethylene oxide group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a single having an oxonium group and an ethylenically unsaturated bond The body (b2) (hereinafter sometimes referred to as "(b2)"), the monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)")).

(b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)")) A monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-2)").

(b1-1) may, for example, be dehydroglyceryl (meth) acrylate, β-methyl deglycidyl (meth) acrylate, β-ethyl deglycidyl (meth) acrylate, or dehydrated Glyceryl vinyl ether, o-vinylbenzyl deglycidyl ether, m-vinylbenzyl dehydroglyceryl ether, p-vinylbenzyl dehydroglyceryl ether, α-methyl-o-vinyl Benzyl dehydroglyceryl ether, α-methyl-inter-B Alkenylbenzyl dehydroglyceryl ether, α-methyl-p-vinylbenzyl dehydroglyceryl ether, 2,3-bis(dehydroglyceryloxymethyl)styrene, 2,4- Bis(dehydroglyceryloxymethyl)styrene, 2,5-bis(dehydroglyceryloxymethyl)styrene, 2,6-bis(dehydroglyceryloxymethyl)styrene, 2,3,4-gin (dehydroglyceryloxymethyl)styrene, 2,3,5-gin (dehydroglyceryloxymethyl)styrene, 2,3,6-gin (dehydrated) Glyceryloxymethyl)styrene, 3,4,5-glycol (dehydroglyceryloxymethyl)styrene, 2,4,6-gin (degaffinyloxymethyl)styrene, etc. .

(b1-2), vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by Daicel Co., Ltd.), 3,4-epoxy ring Hexylmethyl (meth) acrylate (for example, CYCLOMER A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, CYCLOMER M100; manufactured by Daicel Co., Ltd.) A compound represented by the formula (II), a compound represented by the formula (III), and the like.

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

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

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

* indicates a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, and a third butyl group.

The alkyl group in which the hydrogen atom is substituted by a hydroxyl group may, for example, be a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group or a 1-hydroxy-1- Methyl ethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

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

Examples of the alkyl group having 1 to 6 carbon atoms include a methylene group, an ethyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane group. 1,5-diyl, hexane-1,6-diyl and the like.

X ^a and X ^{b are} preferably a single bond, a methylene group, an ethylidene group, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, and more preferably a single bond, *-CH ₂ CH ₂ -O- (* indicates the bond with O).

The compound represented by the formula (II) may, for example, be a compound represented by any one of the formulae (II-1) to (II-15). Preferably, it is a formula (II-1), a formula (II-3), a formula (II-5), a formula (II-7), a formula (II-9) or a formula (II-11) to a formula (II- 15) The compound represented, and more preferably a compound represented by the formula (II-1), the formula (II-7), the formula (II-9) or the formula (II-15).

The compound represented by the formula (III) may, for example, be a compound represented by any one of the formulae (III-1) to (III-15). Preferably, it is a formula (III-1), a formula (III-3), a formula (III-5), a formula (III-7), a formula (III-9) or a formula (III-11) to a formula (III- 15) The compound represented, and more preferably a compound represented by the formula (III-1), the formula (III-7), the formula (III-9) or the formula (III-15).

The compound represented by the formula (II) and the compound represented by the formula (III) may be used singly or in combination with the compound represented by the formula (II) and the compound represented by the formula (III). When it is equal, the content of the compound represented by the formula (II) and the compound represented by the formula (III) is preferably from 5:95 to 95:5 and from 10:90 to 90 on a molar basis. 10 is better, and 20:80~80:20 is even better.

(b2) is more preferably a monomer having an oxo group and a (meth) acryloxy group. (b2) may, for example, be 3-methyl-3-methylpropenyloxymethyloxanium, 3-methyl-3-propenyloxymethyloxime, or 3-ethyl-3-methylpropene Oxylated Base oxonium, 3-ethyl-3-propenyloxymethyloxanium, 3-methyl-3-methylpropenyloxyethyloxyanthracene, 3-methyl-3-acryloxyloxy Anthraquinone, 3-ethyl-3-methylpropenyloxyethyloxyanthracene, 3-ethyl-3-propenyloxyethyloxyanthracene, and the like.

(b3) is more preferably a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group. (b3) Specific examples thereof include tetrahydrofurfuryl acrylate (for example, Viscoat V #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

From the viewpoint of further improving the reliability of heat resistance and chemical resistance of the obtained color filter, (b) is preferably (b1). In addition, from the viewpoint of excellent storage stability of the colored curable resin composition, (b1-2) is more preferable.

(c) may be exemplified by methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, and tert-butyl (A) Acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl ( Methyl) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ]decane-8-yl (meth) acrylate (In the technical field, it is commonly used as "dicyclopentyl (meth) acrylate". Also known as "tricyclodecyl (meth) acrylate".), tricyclic [5.2. 1.0 ^2,6 ]decene-8-yl (meth) acrylate (known in the art as "dicyclopentenyl (meth) acrylate"), dicyclopentyloxy B Base (meth) acrylate, different (meth) acrylate, adamantyl (meth) acrylate, aryl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (a (meth) acrylates such as acrylates and benzyl (meth) acrylates; hydroxyl groups such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate Containing (meth) acrylates; dicarboxylates such as diethyl maleate, diethyl fumarate, diethyl itaconate; bicyclo [2.2.1] g-2 - alkene, 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-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2. 1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-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-t-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 (p. a bicyclic unsaturated compound such as tributoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; -Phenylmethyleneimine, N-cyclohexylmethyleneimine, N-benzylmethyleneimine, N-succinimide-3-pentene Yttrium imide benzoate, N-succinimide-4-butylimide butyrate, N-succinimide-6-m-butyleneimine hexanoate, N-succinimide-3-oxenimide propionate, dicarbonyl quinone imine derivatives such as N-(9-acridinyl) maleimide; styrene , α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinyl chloride, Acrylamide, methacrylamide, vinyl acetate, 1, 3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among them, from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyl toluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6} ] decane is preferred. -8-yl (meth) acrylate, N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, bicyclo [ 2.2.1] Hept-2-ene.

Among the resins [K1], in the entire structural unit constituting the resin [K1], the ratio of the structural units respectively derived from the resin is preferably:

From the structural unit of (a); 2~60 mol%

From the structural unit of (b); 40~98 mol%

And better yet:

From the structural unit of (a); 10~50 mol%

The structural unit derived from (b); 50 to 90 mol%.

When the ratio of the structural unit in the resin [K1] is within the above range, the storage stability of the colored curable resin composition, the development property when the colored pattern is formed, and the solvent resistance of the obtained color filter are obtained. Excellent tendency.

Resin [K1] can refer to the method described in the "Experimental Method for Polymer Synthesis" (Dazu Takashi, Institute of Chemicals, the first edition of the first brush, issued on March 1, 1972) and the literature. The cited documents are manufactured.

In the specific production method of the resin [K1], a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and oxygen is used instead of oxygen to form a deoxidizing atmosphere. The method of heating and keeping warm while stirring.

In addition, the polymerization initiator, solvent, and the like used herein are not particularly limited, and those generally used in the field can be used. Examples of the polymerization initiator include an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), and an organic peroxide (benzene). The solvent (E) of the colored curable resin composition of the present invention may be a solvent to be described later, and the solvent may be used as long as it is a solvent.

Further, the obtained copolymer may be directly used as a solution after the reaction, or a solution obtained by concentration or dilution, or a solid (powder) obtained by reprecipitation or the like may be used. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent in the polymerization, the solution after the reaction can be directly used in the preparation of the color-curable resin composition of the present invention. The process of the color hardening resin composition of the present invention can be simplified.

Among the resins [K2], in the entire structural unit constituting the resin [K2], the ratio of the structural units respectively derived from the resin is preferably:

From the structural unit of (a); 2~45 mol%

From the structural unit of (b); 2~95 mol%

From the structural unit of (c); 1 to 65 mol%,

And better yet:

From the structural unit of (a); 5~40 mol%

From the structural unit of (b); 5~80 mol%

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

When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the colored curable resin composition, the development property when a colored pattern is formed, and the solvent resistance of the obtained color filter are obtained. The heat resistance and mechanical strength tend to be excellent.

The resin [K2] can be produced in the same manner as the method described in the production method of the resin [K1], except that the predetermined amount (c) is further used.

Among the resins [K3], in the entire structural unit constituting the resin [K3], the ratio of the structural units respectively derived from the resin is preferably:

From the structural unit of (a); 2~60 mol%

From the structural unit of (c); 40~98 mol%,

And better yet:

From the structural unit of (a); 10~50 mol%

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

The resin [K3] can be produced in the same manner as the method described in the production method of the resin [K1], except that (c) is used instead of (b).

The resin [K4] can be obtained by obtaining the copolymer of (a) and (c) and adding the cyclic ether having 2 to 4 carbon atoms which is contained in (b) to the carboxylic acid (a) and/or Manufactured on the carboxylic acid anhydride.

First, the copolymers (a) and (c) are produced in the same manner as described in the method for producing the resin [K1]. At this time, the ratio of the structural units derived from the respective sources is preferably the same as that of the resin [K3].

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

Continuing the manufacture of the copolymers of (a) and (c), replacing the ambient gas in the flask from nitrogen to air, and reacting the catalyst (b), carboxylic acid or carboxylic anhydride with a cyclic ether (for example, dimethyl (dimethyl) Aminomethyl) phenol or the like and a polymerization inhibitor (for example, hydroquinone) are placed in a flask and reacted at, for example, 60 to 130 ° C for 1 to 10 hours to produce a resin [K4].

The amount of use (b) is preferably 5 to 80 m for (a) 100 m, and more preferably 10 to 75 m. When it is set in this range, the storage stability of the colored curable resin composition, the development property at the time of pattern formation, and the balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern become Good tendency. The (b) used in the resin [K4] is preferably (b1) and more preferably (b1-1), since the reactivity of the cyclic ether is high and the unreacted (b) is difficult to remain.

The amount of the reaction catalyst to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c).

The reaction conditions such as the feeding method, the reaction temperature, and the time can be appropriately adjusted by the amount of heat generated by the production equipment, polymerization, or the like. In addition, in the same manner as the polymerization conditions, the feed method and the reaction temperature can be appropriately adjusted in consideration of heat generation amount due to production equipment, polymerization, and the like.

In the first step of the resin [K5], the copolymer of (b) and (c) was obtained in the same manner as in the above-mentioned method for producing the resin [K1]. In the same manner as described above, the obtained copolymer may be directly used as a solution after the reaction, or may be concentrated or diluted. The solution to be released may be obtained by forming a solid (powder) by a method such as reprecipitation.

The ratio of the structural unit derived from (b) and (c) to the total number of moles of the entire structural unit constituting the copolymer is preferably:

From the structural unit of (b); 5~95 mol%

From the structural unit of (c); 5 to 95 mol%,

And better yet:

From the structural unit of (b); 10~90 mol%

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

Further, the carboxylic acid or carboxylic anhydride having the (a) copolymer (b) and (c) may be derived from (b) by the same conditions as in the production method of the resin [K4]. The cyclic ether is reacted, whereby a resin [K5] is obtained.

The amount of (a) used for the reaction of the above copolymer is preferably from 5 to 80 moles based on (b) 100 moles. Since the reactivity of the cyclic ether is high and it is difficult to remain unreacted (b), (b) used in the resin [K5] is preferably (b1), and more preferably (b1-1).

The resin [K6] is a resin obtained by further reacting a carboxylic acid anhydride with a resin [K5].

The carboxylic anhydride is reacted with a hydroxyl group produced by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride.

Examples of the carboxylic acid anhydride include maleic anhydride, pyrophosphanic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, and 3,4,5,6-tetrahydroortylene. Dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydrate Wait. The amount of the carboxylic anhydride to be used is preferably from 0.5 to 1 mol per mol of the amount used in (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate/(meth)acrylic acid copolymer, and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ] Resin of thiol (meth) acrylate / (meth) acrylate copolymer [K1]; dehydroglyceryl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer , dehydrated (meth) acrylate / styrene / (meth) acrylate copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / ( Methyl)acrylic acid/N-cyclohexylmethylene iodide copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate / (meth)acrylic acid / Vinyl toluene copolymer, resin such as 3-methyl-3-(meth)acryloxymethyloxanium/(meth)acrylic acid/styrene copolymer [K2]; benzyl (methyl) Acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer, benzyl (meth)acrylate/tricyclodecyl (meth)acrylate/(meth)acrylic acid copolymer Resin [K3]; addition of dehydroglyceryl (meth) acrylate to benzyl (meth) acrylate / (meth) propylene a resin obtained by using an acid copolymer, a resin obtained by adding a decarboxylated (meth) acrylate to a tricyclodecyl (meth) acrylate/styrene/(meth)acrylic acid copolymer, and allowing A resin such as a resin obtained by adding a glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylate copolymer [K4] a resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth) acrylate/dehydroglyceryl (meth) acrylate, and (meth)acrylic acid to tricyclic fluorenyl ( a resin such as a resin obtained by reacting a copolymer of methyl acrylate/styrene/dehydroglyceryl (meth) acrylate [K5]; a (meth)acrylic acid to tricyclodecyl (meth) acrylate a resin obtained by reacting a copolymer of de-glycidyl (meth) acrylate, and a resin such as a resin [K6] obtained by reacting tetrahydrophthalic anhydride.

The resin (B) is preferably selected from the group consisting of the resin [K1], the resin [K2], and the resin [K3], and more preferably selected from the resin [K2] and the resin [K3]. One of the groups formed. When it is such a resin, the coloring curable resin composition is excellent in developability.

From the viewpoint of the adhesion of the colored pattern to the substrate, the resin [K2] is more preferable.

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 still more preferably 5,000 to 30,000. When the molecular weight is within the above range, the coating film hardness is increased, the residual film ratio is high, the solubility of the unexposed portion to the developing solution 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 from 1.1 to 6, more preferably from 1.2 to 4.

The acid value (solid portion) 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 by the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass, based on the total amount of the solid portion. If the content of the resin (B) is within the above range, a colored pattern can be formed. Moreover, the resolution of the colored pattern and the residual film rate tend to increase.

<Polymerizable compound (C)>

a polymerizable compound (C-based compound which can be polymerized by an active radical and/or an acid generated from the polymerization initiator (D), and examples thereof include a polymerizable ethylenically unsaturated bond compound, and the like. A (meth) acrylate compound is preferred.

Examples of the polymerizable compound having one ethylenically unsaturated bond include decyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, and 2 - hydroxyethyl acrylate, N-vinyl pyrrolidone, and the like, and the above (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, and neopentyl glycol di(methyl). Acrylate, triethylene glycol di(meth)acrylate, bis(acryloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, and the like.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol. Penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaniol octa (meth) acrylate, tripentyltetraol hexa(meth) acrylate, tetraxin Tetraol (meth) acrylate, tetrapentaerythritol 九 (meth) acrylate, gin (2-(methyl) propylene methoxyethyl) isocyanate, ethylene glycol modified pentaerythritol IV (Meth) acrylate, ethylene glycol modified dipentaerythritol hexa(meth) acrylate, propylene glycol modification Pentaerythritol tetra (meth) acrylate, propylene glycol modified dineopentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modification Dipentaerythritol hexa(meth) acrylate or the like is preferably a neopentyl pentaerythritol penta (meth) acrylate and dine pentaerythritol hexa (meth) acrylate.

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

The content of the polymerizable compound (C) is preferably 7 to 65% by mass based on the total amount of the solid portion, more preferably 13 to 60% by mass, and still more preferably 15 to 55% by mass.

The content ratio of the resin (B) and the polymerizable compound (C) [resin (B): polymerizable compound (C)] is preferably 20:80 to 80:20, and 35:65 to 80 by mass. :20 is better.

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

<Polymerization initiator (D)>

The polymerization initiator (D) is particularly limited as long as it is a living radical, an acid or the like which is generated by the action of light or heat, and a polymerization initiator which is well known can be used.

The polymerization initiator (D) may, for example, be an O-indenyl hydrazine compound, an alkylphenol compound, a biimidazole compound, or the like. a compound, a mercaptophosphine oxide compound, and the like.

The above O-indenyl ruthenium compound is a compound having a structure represented by the formula (d1).

Hereinafter, * indicates a bond.

The aforementioned O-indenyl hydrazine compound may, for example, be N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzylformyloxy- 1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylthiophenyl)-3-cyclopentyl Propane-1-keto-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzomethyl)-9H-indazol-3-yl]ethane -1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolyl) Methyloxy)benzhydryl}-9H-indazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methyl Benzyl hydrazino)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylidene-1-(9-ethyl-6-(2-methyl) Benzomethylene)-9H-indazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as IRGACURE OXEO1, OXE02 (above, BASF Corporation, N-1919 (made by Adeka)) can also be used. Wherein the O-indenyl hydrazine compound is preferably selected from the group consisting of N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzoic acid醯oxy-1-(4-phenylthiophenyl)octane-1-one-2-imine and N-benzylideneoxy-1-(4-phenylthiophenyl)-3 At least one selected from the group consisting of cyclopentylpropan-1-one-2-imine, and more preferably N-benzylidene-1-(4-phenylthiophenyl)octane 1-keto-2-imine. If it is such an O-indenyl ruthenium compound, there is a tendency to obtain a high-intensity color filter.

The aforementioned alkylphenol compound has a moiety represented by the formula (d2) A structure or a compound of a partial structure represented by the formula (d3). In these partial structures, the benzene ring may also have a substituent.

The compound having a structure represented by the formula (d2) may, for example, be 2-methyl-2- Lolinyl-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1-(4- Polinylphenyl)-2-benzylidenebutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4 - Polinyl)phenyl]butan-1-one and the like. Commercial products such as IRGACURE 369, 907, and 379 (above, manufactured by BASF Corporation) can also be used.

The compound having a structure represented by the formula (d3) includes 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1-[4-(2-hydroxyl) Oligomerization of ethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one , α,α-diethoxyacetophenone, benzyldimethylketal, and the like.

From the viewpoint of sensitivity, the alkylphenol compound is preferably a compound having a structure represented by the formula (d2).

The biimidazole compound may, for example, be a compound represented by the formula (d5).

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

Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a benzenedimethyl group, an ethylphenyl group, and a naphthyl group, and a phenyl group is preferred.

Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferred. The alkoxy group having 1 to 4 carbon atoms may, for example, be a methoxy group, an ethoxy group, a propoxy group or a butoxy group, and a methoxy group is preferred.

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, Japanese Patent Laid-Open No. Hei 6-75372, Japanese Patent Laid-Open No. Hei 6-75373, etc.), 2, 2'-double ( 2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis Oxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-double (2-Chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, Japanese Patent Publication No. Sho 48-38403, Japanese Patent Laid-Open No. Hei 62-174204 The imidazole compound in which the phenyl group at the 4, 4', 5, 5'-position is substituted with a carboalkoxy group (see, for example, Japanese Patent Laid-Open Publication No. Hei 7-10913, etc.). Among them, preferred are compounds represented by the following formulas and mixtures thereof.

The aforementioned three The compound may be exemplified by 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-tri , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-tri Wait.

The above mercaptophosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide.

Further, the polymerization initiator (D) may, for example, be a benzoin compound such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or benzoin isobutyl ether. Benzophenone, methyl ortho-benzoylbenzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3', 4, a benzophenone compound such as 4'-tetrakis(t-butylperoxycarbonyl)benzophenone or 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethyl Anthraquinone, anthraquinone, etc.; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, and the like.

These are preferably used in combination with a polymerization initiation aid (D1) (particularly an amine) to be described later.

The polymerization initiator (D) preferably comprises a compound selected from the group consisting of alkylphenol compounds, three A polymerization initiator of at least one of the group consisting of a compound, a mercaptophosphine oxide compound, an O-mercaptopurine compound, and a biimidazole compound, and more preferably a polymerization initiator containing an O-mercaptopurine compound.

The content of the polymerization initiator (D) is preferably 0.01 to 40 parts by mass, more preferably 0.05 to 35 parts by mass, per 100 parts by mass of the total of the resin (B) and the polymerizable compound (C), and more preferably 0.05 to 35 parts by mass. It is preferably 0.1 to 32 parts by mass, and more preferably 1 to 30 parts by mass.

<Polymerization starter (D1)>

The polymerization initiation aid (D1) is a compound or a sensitizer used to promote polymerization of a polymerizable compound which starts polymerization by a polymerization initiator. When the polymerization initiator (D1) is contained, it is generally used in combination with the polymerization initiator (D).

The polymerization initiation aid (D1) may, for example, be an amine compound, an alkoxy ruthenium compound or 9-oxo-sulfur Compounds, carboxylic acid compounds, and the like.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamino group. Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'- Bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethyl Methylamino)benzophenone, etc., of which 4,4'-bis(diethylamino) Benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

The alkoxy ruthenium compound may, for example, be 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene or 2-ethyl-9. 10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

The aforementioned 9-oxygen sulfur The compound can be exemplified by 2-isopropyl-9-oxosulfur 4-isopropyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-dichloro-9-oxosulfur 1-chloro-4-propoxy-9-oxosulfur Wait.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, and methoxy group. Phenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N -naphthylglycine, naphthyloxyacetic acid, and the like.

When the polymerization initiator (D1) is used, the content is preferably 0.1 to 30 parts by mass, and 1 to 20, based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). Better quality. When the amount of the polymerization starting aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and there is a tendency to improve the productivity of the color filter.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent generally used in the field can be used. For example, an ester solvent (a solvent containing -COO- in the molecule and containing no -O-), an ether solvent (a solvent containing -O- in the molecule and containing no -COO-), an ether ester solvent (in the case of a solvent) a solvent containing -COO- and -O- in the molecule), a ketone solvent a solvent containing -CO- and containing no -COO-), an alcohol solvent (a solvent containing OH in the molecule and containing no -O-, -CO- and -COO-), an aromatic hydrocarbon solvent, guanamine Solvent, dimethyl hydrazine, and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, and propionic acid. Butyl ester, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclohexanol Acid ester, γ-butyrolactone, and the like.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol single Ethyl 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-two Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, benzo Ether, phenethyl ether, methyl anisole, and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-methoxypropionate. Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropanoate, 2-ethoxyl Ethyl 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 the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, Cyclopentanone, cyclohexanone, isophorone, and the like.

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

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

Examples of the guanamine 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, preferred are propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and Ethylene 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., and more preferably propylene glycol monomethyl ether acetate, 4-hydroxy-4-methyl-2-pentanone, Propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 3 Methyl methoxypropionate, ethyl 3-ethoxypropionate, N-methylpyrrolidone.

The content of the solvent (E) is preferably from 70 to 95% by mass, more preferably from 75 to 92% by mass, based on the total amount of the colored curable resin composition. In other words, the solid portion of the colored curable resin composition is 5 to 30% by mass. Good, and better than 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 improved, and the color density is not insufficient when the color filter is formed, so that the display characteristics tend to be good.

<Leveling agent (H)>

Examples of the leveling agent (H) include an anthrone-based surfactant, a fluorine-based surfactant, and an anthrone-based surfactant having a fluorine atom. They may also have a polymerizable group on the side chain.

The anthrone-based surfactant may, for example, be a surfactant having a siloxane coupling in the molecule. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: Toray Dow-Corning) , KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan LLC) .

The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain in the molecule. Specifically, FLUORAD (registered trademark) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (DIC), EFTOP (registered trademark) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (Mitsubishi Materials Electronics Co., Ltd.), SURFLON (registered trademark) S381, SURFLON S382, SURFLON SC101, SURFLON SC105 (made by Asahi Glass Co., Ltd.) and E5844 (made by Daikin Fine Chemical Research Institute Co., Ltd.).

The anthrone-based surfactant having a fluorine atom may, for example, be a surfactant having a siloxane coupling and a fluorocarbon chain in the molecule. Specific examples include MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, and MEGAFAC F443 (manufactured by DIC).

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

<Antioxidant (J)>

From the viewpoint of improving the heat resistance and light resistance of the coloring agent, it is preferred to use two or more kinds of antioxidants alone or in combination. The antioxidant is not particularly limited as long as it is an industrially used antioxidant, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, or the like can be used.

Examples of the phenolic antioxidant include Irganox 1010 (nepentaerythritol [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Co., Ltd.), Irganox 1076 (Octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, manufactured by BASF), Irganox 1330 (3,3',3'',5, 5',5''-hexa-t-butyl-a, a', a''-(mesitylene-2,4,6-triyl)tri-p-cresol, BASF (manufactured by BASF) Irganox 3114 (1,3,5-gin(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione, BASF (manufactured by BASF), Irganox 3790 (1,3,5-para ((4-tert-butyl-3-hydroxy-2,6) - Benzyl)methyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione, manufactured by BASF (shares), Irganox 1035 (thiodiethylidene bis[3-(3,5-di-t-butyl-4-) Hydroxyphenyl)propionate], manufactured by BASF Co., Ltd., Irganox 1135 (phenylpropionic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxyl, C7-C9 side alkane Base ester, manufactured by BASF Co., Ltd., Irganox 1520L (4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF Co., Ltd.), Irganox 3125 (manufactured by BASF Co., Ltd.), Irganox 565 (manufactured by BASF Co., Ltd.) 2,4-bis(n-octylthio)-6-(4-hydroxy 3',5'-di-t-butylanilino)-1,3,5-three , BASF (share) system, ADEKA STAB AO-80 (3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propenyloxy)- 1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, manufactured by ADEKA), Sumilizer BHT (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GA-80 (Sumitomo Chemical Co., Ltd.), Sumilizer GS (Sumitomo Chemical Co., Ltd.), Cyanox 1790 (made by CYTEC), and Vitamin E (Essence).

Examples of the phosphorus-based antioxidant include Irgafos 168 (parameter (2,4-di-t-butylphenyl) phosphite, manufactured by BASF Co., Ltd.), Irgafos 12 (see [2-[[2, 4, 8) , 10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphino-6-yl]oxy]ethyl]amine, manufactured by BASF Co., Ltd., Irgafos 38 (bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl ester phosphoric acid, manufactured by BASF Co., Ltd.), ADEKA STAB 329K (manufactured by ADEKA) ADEKA STAB PEP36 (made by Adeka), ADEKA STAB PEP-8 (made by Adeka), Sandstab P-EPQ (manufactured by Clariant), Weston 618 (manufactured by GE), Weston 619G (manufactured by GE), Ultranox 626 (manufactured by GE), and Sumilizer GP (6-[3-(3-tert-butyl-4) -hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenzo[d,f][1.3.2]dioxaphosphonium) (Sumitomo Chemical (share) system, etc.

The sulfur-based antioxidant may, for example, be a dialkylthiodipropionate compound such as dilauryl thiodipropionate, dimyristyl ester or distearyl ester, or hydrazine [methylene (3-dodecylthio)). Propionate] A β-alkylmercaptopropionate compound of a polyol such as methane.

<Other ingredients>

The color-curable resin composition of the present invention may contain additives such as a filler, another polymer compound, an adhesion promoter, a light stabilizer, a chain transfer agent, and the like, which are well known in the art, as needed.

<Method for Producing Colored Curable Resin Composition>

The colored curable resin composition 0 of the present invention can be used by mixing the compound (A1), the resin (B), the polymerizable compound (C), the polymerization initiator (D), and the solvent (E), and can be used as needed The leveling agent (H), the polymerization starting aid (D1), the antioxidant (J) and other ingredients are prepared.

The colored curable resin composition 1 of the present invention can be obtained by mixing the compound (A1), the dye (A2), the resin (B), the polymerizable compound (C), the polymerization initiator (D), and the solvent (E). It can be prepared according to the leveling agent (H), the polymerization starting aid (D1), the antioxidant (J) and other components which are used as needed.

The colored curable resin composition 2 of the present invention can be obtained by mixing the compound (A1), the resin (B), the polymerizable compound (C), the polymerization initiator (D), and colorless. The metal complex (F) and the solvent (E), and the leveling agent (H), the polymerization starting aid (D1), the antioxidant (J), and other components can be used as needed.

The pigment containing the pigment (P) is preferably partially or completely mixed with one of the solvents (E) in advance, and dispersed by using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. At this time, part or all of the above-mentioned pigment dispersant and resin (B) may be blended as needed. In the pigment dispersion liquid thus obtained, the remaining components are mixed to have a predetermined concentration, whereby the intended color-curable resin composition can be prepared.

The coloring agent (A) such as the compound (A1) or the dye (A2) is preferably dissolved in a part or all of the solvent (E) to prepare a solution. Preferably, the solution is filtered through a filter having a pore diameter of about 0.01 to 1 μm.

It is preferable to filter the mixed color-curable resin composition by a filter having a pore diameter of about 0.01 to 10 μm.

<Method of Manufacturing Color Filter>

The method of producing a colored pattern from the colored curable resin composition of the present invention includes photolithography, an inkjet method, a printing method, and the like. Among them, photomicrography is preferred. Photolithography is a method in which the colored curable resin composition is applied onto a substrate and dried to form a colored composition layer, and the colored composition layer is exposed through a photomask to develop a pattern. In photolithography, a cured film of the coloring composition layer, that is, a colored coating film, can be formed by not using a photomask during exposure and/or without developing. The colored pattern and the colored coating film thus formed are the color filters of the present invention.

The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted depending on the purpose, use, and the like, and is usually 0.1 to 30 μm and 0.1 to 20 Μm is preferred, and more preferably 0.5 to 6 μm.

The substrate may be a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass coated with cerium oxide, polycarbonate, polymethyl methacrylate or polyethylene terephthalate. A resin plate or the like of a diester or the like is formed on the substrate to form an aluminum, silver, silver/copper/palladium alloy film or the like. Other color filter layers, resin layers, transistors, circuits, and the like may also be formed on the substrates.

The formation of each color pixel by photolithography can be performed using conventional or conventional devices, conditions, and the like. For example, it can be produced as follows.

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

Examples of the coating method include a spin coating method, a slit coating method, a slit coating method, and a spin coating method.

The temperature at the time of heat drying is preferably 30 to 120 ° C, and more preferably 50 to 110 ° C. Further, the heating time is preferably from 10 seconds to 60 minutes, and more preferably from 30 seconds to 30 minutes.

When drying under reduced pressure, it is preferably carried out at a temperature of from 50 to 150 Pa and at a temperature of from 20 to 25 °C.

The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected depending on the film thickness of the intended color filter.

Next, the colored composition layer is exposed through a photomask for forming a desired coloring pattern. The pattern on the reticle is not particularly limited, but Use a pattern that is intended for the purpose.

The light source used for the exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, a filter that cuts off a wavelength region of less than 350 nm can be used to cut off the light in the wavelength region, or a band that can be taken out in the vicinity of 436 nm, near 408 nm, and around 365 nm can be selectively taken out of the filter. The light of the district. Specifically, examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, and the like.

In order to uniformly illuminate the entire surface of the exposed surface, or to perform correct alignment of the mask and the base on which the colored composition layer is formed, it is preferable to use a mask alignment exposure machine and a stepper. Device.

The coloring pattern can be formed on the substrate by causing the exposed coloring composition layer to be in contact with the developing liquid to develop the image. By developing, the unexposed portion of the colored composition layer is dissolved in the developing solution and removed.

The developing solution is preferably an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide. The concentration in the aqueous solution of the basic compound is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. In addition, the developer may also contain a surfactant.

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

It is preferred to carry out water washing after development.

Further, it is preferred to post-bake the obtained colored pattern. The post-baking temperature is preferably 150 to 250 ° C, and more preferably 160 to 235 ° C. The post-baking time is preferably from 1 to 120 minutes, and more preferably from 10 to 60 minutes.

By using the color hardening resin composition of the present invention, It is a color filter that can produce high brightness. This color filter is useful as a color filter system used for display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the invention should not be construed as limited. In the examples, the % and the parts indicating the content or even the usage amount are the mass basis unless otherwise specified.

Hereinafter, the structure of the compound is obtained by NMR (400-MR manufactured by Agilent), mass spectrometry (LC; Model 1200 manufactured by Agilent, MASS; LC/MSD manufactured by Agilent), and UV-VIS (V-650 manufactured by JASCO Corporation). confirm.

Synthesis Example 1

The following reaction was carried out under a nitrogen atmosphere. After placing 32.2 parts of potassium thiocyanate and 160.0 parts of acetone into a flask having a cooling tube and a stirring device, the mixture was stirred at room temperature for 30 minutes. Next, 50.0 parts of 2-fluorobenzhydryl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise for 10 minutes. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Next, after the reaction mixture was ice-cooled, 40.5 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. After the completion of the dropwise addition, the mixture was stirred at room temperature for further 30 minutes. Next, after the reaction mixture was ice-cooled, 34.2 parts of a 30% aqueous sodium hydroxide solution was added. After the completion of the dropwise addition, the mixture was stirred at room temperature for further 30 minutes. Next, 31.3 parts of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred under heating and reflux for 7 hours. Next, after the reaction mixture was left to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, and then 200 parts of toluene was added and stirred for 30 minutes. Then, the stirring was stopped, and after standing for 30 minutes, the organic layer and the aqueous layer were separated. Dispensing After the waste water layer was operated, the organic layer was washed with 200 parts of 1 N hydrochloric acid, then washed with 200 parts of tap water, and finally washed with 200 parts of saturated brine. After adding an appropriate amount of Glauber's salt to the organic layer and stirring for 30 minutes, it was filtered to obtain a dried organic layer. The obtained organic layer was subjected to solvent distillation with 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 under reduced pressure at 60 ° C to give 49.9 parts of the compound of formula (B-I-2).

The yield was 51%.

The following reaction was carried out under a nitrogen atmosphere. 0.13 parts of ginseng (diphenylideneacetone) dipalladium (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.27 parts of XPhos (made by Aldrich Co., Ltd.), and 30.2 parts of sodium tributoxide (manufactured by Tokyo Chemical Industry Co., Ltd.), 4, 4' 24.0 parts of dichlorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.), 23.2 parts of 2,6-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), and 123.3 parts of toluene (manufactured by Nacalai Tesque Co., Ltd.) were placed in a cooling tube and stirred. After the flask was placed in the apparatus, the reaction solution was adjusted by stirring at room temperature for 30 minutes. Next, the reaction solution was heated at 80 ° C and stirred for 2 hours. After the reaction solution was ice-cooled, the precipitated solid was filtered to give a yellow solid. After 123.9 parts of toluene was added to the filtrate to adjust the organic layer, the organic layer was repeatedly subjected to a liquid separation operation by 123.9 parts of tap water. Will be washed After the organic layer was dehydrated with magnesium sulfate, the solvent was distilled off by an evaporator to obtain a yellow solid. The obtained yellow solid 1 and yellow solid 2 were purified by column chromatography, respectively. The purified yellow solid was dried under reduced pressure at 60 ° C to give 37.2 parts (yield: 93%) of the compound of formula (C-IV-2).

Identification of compounds represented by formula (C-IV-2)

( ¹ H NMR; 400 MHz; δ value (ppm, TMS basis); DMSO); 2.14 (12H, s), 6.42 (4H, m), 7.08-7.15 (6H, m), 7.52 (4H, br.d, J=7.1Hz), 8.05 (2H, br.s)

(mass spectrometry) ionization mode = ESI +: m / z = 421.5 [M + H] ⁺

Exact Mass: 420.2

The following reaction was carried out under a nitrogen atmosphere. After 10.0 parts of the compound represented by the formula (C-IV-2) and 74.7 parts of N,N-dimethylformamide were placed in a flask equipped with a cooling tube and a stirring device, the mixed solution was ice-cooled. After 8.0 parts of potassium tert-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in small portions for 30 minutes under ice cooling, the mixture was stirred under ice cooling for 1 hour. 11.1 parts of ethyl iodide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise in small portions, and the mixture was stirred at room temperature for 2 hours. After 300 parts of tap water and 300 parts of ethyl acetate were added to the reaction solution, a liquid separation operation was carried out to obtain an organic layer. After the obtained organic layer was dried over magnesium sulfate, the solvent was evaporated to give a yellow solid. The obtained yellow solid was purified by column chromatography. Under reduced pressure 60 The purified yellow solid was dried at ° C to give 9.2 parts (yield 81%) of the compound of formula (C-I-2).

Identification of compounds represented by formula (C-I-2)

(mass spectrometry) ionization mode = ESI +: m / z = 477.5 [M + H] ⁺

Exact Mass: 476.3

The following reaction was carried out under a nitrogen atmosphere. 6.7 parts of the compound represented by the formula (BI-2), 10.0 parts of the compound represented by the formula (CI-2), and 50.0 parts of toluene were placed in a flask having a cooling tube and a stirring device, followed by addition of phosphorus oxychloride 25.5 parts and stirred at 95~100 ° C for 3 hours. Then, the reaction mixture was cooled to room temperature, and then diluted with 170.0 parts of isopropyl alcohol. 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. Then, the stirring was stopped, and after standing for 30 minutes, the organic layer and the aqueous layer were separated. After the water layer was discarded by liquid separation operation, the organic layer was washed with 300 parts of saturated brine. After adding an appropriate amount of Glauber's salt to the organic layer and stirring for 30 minutes, it was filtered to obtain a dried organic layer. The obtained organic layer was subjected to solvent distillation with an evaporator to give a blue-purple solid. Further, the blue-violet solid was dried under reduced pressure at 60 ° C to obtain 16.9 parts of a compound represented by formula (A-II-2) (yield 100%).

Identification of compounds represented by formula (A-II-2)

( ¹⁹ F NMR; 380 MHz; δ value (ppm, based on hexafluorobenzene); DMSO); -109.0 (1F, br.s)

The following reaction was carried out under a nitrogen atmosphere. 10.0 parts of the compound represented by the formula (A-II-2), lithium bis(trifluoromethanesulfonyl) phthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.6 parts, and N,N-dimethylformamidine After 100.0 parts of the amine was placed in a flask having a cooling tube and a stirring device, the mixture was stirred at 50 to 60 ° C for 3 hours. Next, the reaction mixture was cooled to room temperature, and the mixture was stirred for 1 hour while stirring 2000.0 parts of tap water to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. The resulting blue-green solid was purified by column chromatography. The purified blue-green solid was dried under reduced pressure at 60 ° C to give 6.3 parts (yield: 48%) of the compound of formula (A-I-2).

Identification of compounds represented by formula (A-I-2)

( ¹⁹ F NMR; 380 MHz; δ value (ppm, based on hexafluorobenzene); DMSO); -74.7 (6F, s), -109.0 (1F, br.s)

(UV-VIS)

0.10 g of the compound represented by the formula (AI-2) was dissolved in chloroform to have a volume of 100 cm ³ , and 2 cm ³ of the compound was diluted with chloroform to have a volume of 250 cm ³ (concentration: 0.008 g/L), and spectrophotometry was used. The absorption spectrum was measured by a quartz cell (length of light; 1 cm). This compound showed an absorbance of 0.7 (arbitrary unit) at λ max = 618 nm.

Synthesis Example 2

An appropriate amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to prepare a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was added thereto, and the mixture was heated to 85 ° C while stirring. Next, in the flask, using a drip pump, it took about 5 hours to drip 19 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and 3 , a mixture of 4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-9-yl acrylate (containing a molar ratio of 50:50) (trade name "E-DCPA", Daicel shares) 171 parts of a solution prepared by dissolving 40 parts of propylene glycol monomethyl ether acetate. On the other hand, using a different drip pump in the flask takes about 5 hours to drip the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) 26 parts in propylene glycol monomethyl A solution of 120 parts of ether acetate. After the completion of the dropwise addition 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 of 43.5% of the solid portion (hereinafter, the copolymer is sometimes referred to as "resin (B-1)". ")). The obtained resin (B-1) had a weight average molecular weight of 8,000, a molecular weight distribution of 1.98, and an acid value of 53 mg-KOH/g in terms of a solid portion.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene of the resin was carried out by the GPC method under the following conditions.

Device; HLC-8120GPC (TOSOH system)

Pipe string; TSK-GELG2000HXL

Column temperature; 40 ° C

Solvent; THF

Flow rate; 1.0mL/min

The concentration of the solid portion of the liquid to be tested; 0.001 to 0.01% by mass

Injection volume; 50μL

Detector; RI

Standard material for calibration; TSK standard styrene F-40, F-4, F-288, A-2500, A-500 (manufactured by TOSOH)

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

Synthesis Example 3

An appropriate amount of nitrogen was introduced into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace nitrogen gas, and 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added, and the mixture was heated to 85 ° C while stirring. . Next, it took 5 hours to drip a mixture of 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.02,6]癸-8 or/and 9-yl acrylate (trade name "E-DCPA", Daicel shares). 25 parts, a mixed solution of 137 parts of cyclohexylmethyleneimine, 50 parts of 2-hydroxyethyl methacrylate, and 338 parts of propylene glycol monomethyl ether acetate. On the other hand, a mixed solution obtained by dissolving 5 parts of 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was used for 6 hours. After the completion of the dropwise addition, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer having a B-type viscosity (23 ° C) of 23 mPas, a solid portion of 25.6% by weight, and a solution acid value of 28 mg-KOH/g (hereinafter sometimes This copolymer is referred to as "resin (B-2)"). The resulting resin (B-2) had a weight average molecular weight Mw of 8,000 and a molecular weight distribution of 2.1.

Synthesis Example 4

The following reaction was carried out under a nitrogen atmosphere. After 10.0 parts of the compound represented by the formula (C-IV-2) and 74.7 parts of N,N-dimethylformamide were placed in a flask equipped with a cooling tube and a stirring device, the mixed solution was ice-cooled. After 8.0 parts of potassium tert-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in small portions for 30 minutes under ice cooling, the mixture was stirred under ice cooling for 1 hour. A small amount of 13.1 parts of n-butyl iodide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise in a small amount, and the mixture was stirred at room temperature for 2 hours. After 300 parts of tap water and 300 parts of ethyl acetate were added to the reaction solution, a liquid separation operation was carried out to obtain an organic layer. After the obtained organic layer was dried over magnesium sulfate, the solvent was evaporated to give a yellow solid. The obtained yellow solid was purified by column chromatography. The purified yellow solid was dried under reduced pressure at 60 ° C to give 8.3 (yield: 66%) of the compound of formula (C-I-3).

The following reaction was carried out under a nitrogen atmosphere. 6.0 parts of the compound represented by the formula (BI-2), 10.0 parts of the compound represented by the formula (CI-3), and 50.0 parts of toluene were placed in a flask having a cooling tube and a stirring device, followed by addition of phosphorus oxychloride. 22.8 parts and stirred at 95 to 100 ° C for 3 hours. Then, the reaction mixture was cooled to room temperature, and then diluted with 170.0 parts of isopropyl alcohol. 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. Then, the stirring was stopped, and after standing for 30 minutes, the organic layer and the aqueous layer were separated. After the water layer was discarded by liquid separation operation, the organic layer was washed with 300 parts of saturated brine. After adding an appropriate amount of Glauber's salt to the organic layer and stirring for 30 minutes, it was filtered to obtain a dried organic layer. The obtained organic layer was subjected to solvent distillation with an evaporator to give a blue-purple solid. Further, the blue-violet solid was dried under reduced pressure at 60 ° C to obtain 16.2 parts of the compound represented by formula (A-II-3) (yield 100%).

Identification of compounds represented by formula (A-II-3)

( ¹⁹ F NMR; 380 MHz; δ value (ppm, based on hexafluorobenzene); DMSO); -74.7 (6F, s), -109.1 (1F, br.s)

The following reaction was carried out under a nitrogen atmosphere. 10.0 parts of the compound represented by the formula (A-II-3), lithium bis(trifluoromethanesulfonyl) phthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.3 parts, and N,N-dimethylformamidine After 100.0 parts of the amine was placed in a flask having a cooling tube and a stirring device, the mixture was stirred at 50 to 60 ° C for 3 hours. Next, the reaction mixture was cooled to room temperature, and the mixture was stirred for 1 hour while stirring 2000.0 parts of tap water to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. The resulting blue-green solid was purified by column chromatography. The purified blue-green solid was dried under reduced pressure at 60 ° C to give 9.5 parts (yield: 74%) of the compound of formula (A-I-3).

Identification of compounds represented by formula (A-I-3)

( ¹⁹ F NMR; 380 MHz; δ value (ppm, based on hexafluorobenzene); DMSO); -74.8 (6F, s), -109.1 (1F, br.s)

(UV-VIS)

0.10 g of the compound represented by the formula (AI-3) was dissolved in chloroform to have a volume of 100 cm ³ , and 2 cm ³ of the compound was diluted with chloroform to have a volume of 250 cm ³ (concentration: 0.008 g/L), and spectrophotometry was used. The absorption spectrum was measured by a quartz cell (length of light; 1 cm). This compound showed an absorbance of 0.8 (arbitrary unit) at λ max = 621 nm.

Reference Synthesis Example 1

The following reaction was carried out under a nitrogen atmosphere. 0.13 parts of ginseng (diphenylideneacetone) dipalladium (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.27 parts of XPhos (made by Aldrich Co., Ltd.), and 30.2 parts of sodium tributoxide (manufactured by Tokyo Chemical Industry Co., Ltd.), 4, 4' -24.0 parts of dichlorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.), 20.5 parts of o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.), and toluene (Nacalai Tesque Co., Ltd.) After 123.3 parts of the flask was placed in a flask having a cooling tube and a stirring device, the reaction solution was adjusted by stirring at room temperature for 30 minutes. Next, the reaction solution was heated at 80 ° C and stirred for 2 hours. After the reaction solution was ice-cooled, the precipitated solid was filtered to give a yellow solid. After 123.9 parts of toluene was added to the filtrate to adjust the organic layer, the organic layer was repeatedly subjected to a liquid separation operation by 123.9 parts of tap water. After the washed organic layer was dehydrated with magnesium sulfate, the solvent was evaporated to give a yellow solid. The obtained yellow solid 1 and yellow solid 2 were purified by column chromatography, respectively. The purified yellow solid was dried under reduced pressure at 60 ° C to give 16.2 parts (yield 43%) of the compound of formula (C-IV-4).

Identification of compounds represented by formula (C-IV-4)

(mass spectrometry) ionization mode = ESI +: m / z = 393.5 [M + H] ⁺

Exact Mass: 392.2

The following reaction was carried out under a nitrogen atmosphere. After 10.0 parts of the compound represented by the formula (C-IV-4) and 80.1 parts of N,N-dimethylformamide were placed in a flask equipped with a cooling tube and a stirring device, the mixed solution was ice-cooled. After 8.6 parts of potassium tributoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in small portions for 30 minutes under ice cooling, the mixture was stirred under ice cooling for 1 hour. 11.9 parts of ethyl iodide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise in small portions, and the mixture was stirred at room temperature for 2 hours. Add 300 parts of tap water and 300 parts of ethyl acetate to the reverse After the solution was applied, a liquid separation operation was carried out to obtain an organic layer. After the obtained organic layer was dried over magnesium sulfate, the solvent was evaporated to give a yellow solid. The obtained yellow solid was purified by column chromatography. The purified yellow solid was dried under reduced pressure at 60 ° C to give 11.1 part (yield 97%) of the compound of formula (C-I-4).

Identification of compounds represented by formula (C-I-4)

( ¹ H NMR; 400 MHz; δ value (ppm, TMS basis); DMSO); 1.13 (6H, br.t, J = 7.0 Hz), 2.04 (6H, s), 3.64 (4H, m), 6.42 (4H , br.d, J=9.0Hz), 7.14 (2H, br.dd, J=7.4, 1.4Hz), 7.27 (4H, m), 7.36 (2H, br.d, J=7.2, 2.0Hz), 7.50 (4H, br.d, J=9.0Hz)

The following reaction was carried out under a nitrogen atmosphere. 7.1 parts of the compound represented by the formula (BI-2), 18.1 parts of the compound represented by the formula (CI-4), and 50.0 parts of toluene were placed in a flask having a cooling tube and a stirring device, followed by addition of phosphorus oxychloride. 10.7 parts and stirred at 95 to 100 ° C for 3 hours. Then, the reaction mixture was cooled to room temperature, and then diluted with 170.0 parts of isopropyl alcohol. 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. Then, the stirring was stopped, and after standing for 30 minutes, the organic layer and the aqueous layer were separated. After the water layer was discarded by liquid separation operation, the organic layer was washed with 300 parts of saturated brine. Add an appropriate amount of thenardite to the organic layer and After stirring for 30 minutes, it was filtered to give a dried organic layer. The obtained organic layer was subjected to solvent distillation with an evaporator to give a blue-purple solid. Further, the blue-violet solid was dried under reduced pressure at 60 ° C to obtain 17.4 parts of the compound represented by the formula (A-II-4) (yield 100%).

Identification of compounds represented by formula (A-II-4)

( ¹⁹ F NMR; 380 MHz; δ value (ppm, based on hexafluorobenzene); DMSO); -109.0 (1F, br.s)

The following reaction was carried out under a nitrogen atmosphere. 10.0 parts of the compound represented by the formula (A-II-4), lithium bis(trifluoromethanesulfonyl) phthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.8 parts, and N,N-dimethylformamidine After 100.0 parts of the amine was placed in a flask having a cooling tube and a stirring device, the mixture was stirred at 50 to 60 ° C for 3 hours. Next, the reaction mixture was cooled to room temperature, and the mixture was stirred for 1 hour while stirring 2000.0 parts of tap water to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. The resulting blue-green solid was purified by column chromatography. Drying at 60 ° C under reduced pressure The blue-green solid was obtained to obtain 3.0 parts of a compound represented by the formula (A-I-4) (yield 23%).

Identification of compounds represented by formula (A-I-4)

( ¹⁹ F NMR; 380 MHz; δ value (ppm, based on hexafluorobenzene); DMSO); -74.7 (6F, s), -108.9 (1F, br.s)

(UV-VIS)

0.10 g of the compound represented by the formula (AI-4) was dissolved in chloroform to have a volume of 100 cm ³ , and 2 cm ³ of the compound was diluted with chloroform to have a volume of 250 cm ³ (concentration: 0.008 g/L), and spectrophotometry was used. The absorption spectrum was measured by a quartz cell (length of light; 1 cm). This compound showed an absorbance of 0.5 (arbitrary unit) at λ max = 619 nm.

Reference Synthesis Example 2

The following reaction was carried out under a nitrogen atmosphere. 0.13 parts of ginseng (diphenylideneacetone) dipalladium (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.27 parts of XPhos (made by Aldrich Co., Ltd.), and 30.2 parts of sodium tributoxide (manufactured by Tokyo Chemical Industry Co., Ltd.), 4, 4' -Dichlorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 24.0 parts, 2-isopropyl 25.8 parts of aniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 123.3 parts of toluene (manufactured by Nacalai Tesque Co., Ltd.) were placed in a flask equipped with a cooling tube and a stirring device, and then stirred at room temperature for 30 minutes to adjust the reaction solution. Next, the reaction solution was heated at 80 ° C and stirred for 2 hours. After the reaction solution was ice-cooled, the precipitated solid was filtered to give a yellow solid. After 123.9 parts of toluene was added to the filtrate to adjust the organic layer, the organic layer was repeatedly subjected to a liquid separation operation by 123.9 parts of tap water. After the washed organic layer was dehydrated with magnesium sulfate, the solvent was evaporated to give a yellow solid. The obtained yellow solid 1 and yellow solid 2 were purified by column chromatography, respectively. The purified yellow solid was dried under reduced pressure at 60 ° C to give 27.2 parts (yield: 64%) of the compound of formula (C-IV-5).

Identification of compounds represented by formula (C-IV-5)

( ¹ H NMR; 400 MHz; δ value (ppm, TMS basis); DMSO); 1.14 (12H, d, J = 6.8 Hz), 3.23 (2H, br.qq, J = 6.8, 6.8 Hz), 6.73 (4H , br.d, J = 8.8 Hz), 7.19 (6H, m), 7.38 (2H, m), 7.55 (4H, br.d, J = 8.8 Hz), 8.16 (2H, br.s) (mass mass spectrometry) Ionization mode = ESI +: m / z = 449.2 [M + H] ⁺ = ESI -: m / z = 447.2 [MH] ^-

Exact Mass: 448.3

The following reaction was carried out under a nitrogen atmosphere. After 10.0 parts of the compound represented by the formula (C-IV-5) and 70.1 parts of N,N-dimethylformamide were placed in a flask equipped with a cooling tube and a stirring device, the mixed solution was ice-cooled. After 7.5 parts of potassium tributoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in small portions for 30 minutes under ice cooling, the mixture was stirred under ice cooling for 1 hour. A small amount of 12.3 parts of iodinated butyl (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise in a small amount, and the mixture was stirred at room temperature for 2 hours. After 300 parts of tap water and 300 parts of ethyl acetate were added to the reaction solution, a liquid separation operation was carried out to obtain an organic layer. After the obtained organic layer was dried over magnesium sulfate, the solvent was evaporated to give a yellow solid. The obtained yellow solid was purified by column chromatography. The purified yellow solid was dried under reduced pressure at 60 ° C to give 12.2 parts (yield 98%) of the compound of formula (C-I-5).

Identification of compounds represented by formula (C-I-5)

(mass spectrometry) ionization mode = ESI +: m / z = 561.3 [M + H] ⁺

Exact Mass: 560.4

The following reaction was carried out under a nitrogen atmosphere. 5.7 parts of the compound represented by the formula (B-I-2), 10.0 parts of the compound represented by the formula (C-I-5), and 50.0 parts of toluene were placed in a flask having a cooling tube and a stirring device, followed by 21.7 parts of phosphorus oxychloride was added and stirred at 95 to 100 ° C for 3 hours. Then, the reaction mixture was cooled to room temperature, and then diluted with 170.0 parts of isopropyl alcohol. 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. Then, the stirring was stopped, and after standing for 30 minutes, the organic layer and the aqueous layer were separated. After the water layer was discarded by liquid separation operation, the organic layer was washed with 300 parts of saturated brine. After adding an appropriate amount of Glauber's salt to the organic layer and stirring for 30 minutes, it was filtered to obtain a dried organic layer. The obtained organic layer was subjected to solvent distillation with an evaporator to give a blue-purple solid. The blue-violet solid was dried under reduced pressure at 60 ° C to obtain 15.9 parts of a compound represented by formula (A-II-5) (yield 100%).

Identification of compounds represented by formula (A-II-5)

( ¹⁹ F NMR; 380 MHz; δ value (ppm, based on hexafluorobenzene); DMSO); -109.1 (1F, br.s)

The following reaction was carried out under a nitrogen atmosphere. 10.0 parts of the compound represented by the formula (A-II-5), lithium bis(trifluoromethanesulfonyl) phthalimide (east) 4.2 parts of Nippon Chemical Industry Co., Ltd. and 100.0 parts of N,N-dimethylformamide were placed in a flask equipped with a cooling tube and a stirring device, and then stirred at 50 to 60 ° C for 3 hours. Next, the reaction mixture was cooled to room temperature, and the mixture was stirred for 1 hour while stirring 2000.0 parts of tap water to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. The resulting blue-green solid was purified by column chromatography. The purified blue-green solid was dried under reduced pressure at 60 ° C to give 3.6 parts (yield 28%) of the compound of formula (A-I-5).

Identification of compounds represented by formula (A-I-5)

( ¹⁹ F NMR; 380 MHz; δ value (ppm, based on hexafluorobenzene); DMSO); -74.7 (6F, s), -109.1 (1F, br.s)

(UV-VIS)

0.10 g of the compound represented by the formula (AI-5) was dissolved in chloroform to have a volume of 100 cm ³ , and 2 cm ³ of the compound was diluted with chloroform to have a volume of 250 cm ³ (concentration: 0.008 g/L), and spectrophotometry was used. The absorption spectrum was measured by a quartz cell (length of light; 1 cm). This compound showed an absorbance of 0.7 (arbitrary unit) at λ max = 624 nm.

Reference Synthesis Example 3

The following reaction was carried out under a nitrogen atmosphere. 0.03 parts of ginseng (diphenylideneacetone) dipalladium (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.06 parts of XPhos (manufactured by Aldrich Co., Ltd.), and 1.5 parts of sodium tributoxide (manufactured by Tokyo Chemical Industry Co., Ltd.), 4, 4' -1 parts of dichlorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.9 parts of 2,6-difluoroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), and 9.3 parts of toluene (manufactured by Nacalai Tesque Co., Ltd.) were placed in a cooling tube and stirred. After the flask was placed in the apparatus, the reaction solution was adjusted by stirring at room temperature for 30 minutes. Next, the reaction solution was heated at 80 ° C and stirred for 2 hours. After the reaction solution was ice-cooled, the precipitated solid was filtered to give a yellow solid. After 123.9 parts of toluene was added to the filtrate to adjust the organic layer, the organic layer was repeatedly subjected to a liquid separation operation by 123.9 parts of tap water. After the washed organic layer was dehydrated with magnesium sulfate, the solvent was evaporated to give a yellow solid. The obtained yellow solid 1 and yellow solid 2 were purified by column chromatography, respectively. The purified yellow solid was dried under reduced pressure at 60 ° C to give 3.1 parts of the compound of formula (C-IV-6).

Yield 98%

Identification of compounds represented by formula (C-IV-6)

( ¹ H NMR; 400 MHz; δ value (ppm, TMS basis); DMSO); 6.74 (4H, br.d, J = 8.6 Hz), 7.15-7.35 (6H, m), 7.61 (4H, br.d, J=8.6Hz), 8.53 (2H, br.s)

( ¹⁹ F NMR; 380 MHz; δ value (ppm, based on hexafluorobenzene); DMSO); 114.3 (4F, br.t, J = 6.8 Hz)

(mass spectrometry) ionization mode = ESI +: m / z = 437.5 [M + H] ⁺

Exact Mass: 436.1

The following reaction was carried out under a nitrogen atmosphere. After 2.5 parts of the compound represented by the formula (C-IV-6) and 18.3 parts of N,N-dimethylformamide were placed in a flask equipped with a cooling tube and a stirring device, the mixed solution was ice-cooled. After 1.9 parts of potassium tributoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in small portions for 30 minutes under ice cooling, the mixture was stirred under ice cooling for 1 hour. 2.7 parts of ethyl iodide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise in small portions, and the mixture was stirred at room temperature for 2 hours. After 86 parts of tap water and 76 parts of ethyl acetate were added to the reaction solution, a liquid separation operation was carried out to obtain an organic layer. After the obtained organic layer was dried over magnesium sulfate, the solvent was evaporated to give a yellow solid. The obtained yellow solid was purified by column chromatography. The purified yellow solid was dried under reduced pressure at 60 ° C to give 2.0 parts of the compound of formula (C-I-6). Yield 71%

Identification of compounds represented by formula (C-I-6)

( ¹ H NMR; 400 MHz; δ value (ppm, TMS basis); DMSO); 1.37 (6H, t, J = 7.0 Hz), 3.69 (4H, q, J = 7.0 Hz), 6.64 (4H, br.d) , J=9.0Hz), 7.28 (4H, br.dd, J=8.0, 7.5Hz), 7.44-7.53 (2H, m), 7.58 (4H, br.d, J=9.0Hz)

( ¹⁹ F NMR; 380 MHz; δ value (ppm, based on hexafluorobenzene); DMSO); 113.9 (4F, br.t, J = 7.5 Hz)

(mass spectrometry) ionization mode = ESI +: m / z = 493.5 [M + H] ⁺

Exact Mass: 492.2

The following reaction was carried out under a nitrogen atmosphere. 6.5 parts of the compound represented by the formula (BI-2), 10.0 parts of the compound represented by the formula (CI-6), and 50.0 parts of toluene were placed in a flask having a cooling tube and a stirring device, followed by addition of phosphorus oxychloride 24.7 parts and stirred at 95 to 100 ° C for 3 hours. Then, the reaction mixture was cooled to room temperature, and then diluted with 170.0 parts of isopropyl alcohol. 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. Then, the stirring was stopped, and after standing for 30 minutes, the organic layer and the aqueous layer were separated. After the water layer was discarded by liquid separation operation, the organic layer was washed with 300 parts of saturated brine. After adding an appropriate amount of Glauber's salt to the organic layer and stirring for 30 minutes, it was filtered to obtain a dried organic layer. The obtained organic layer was subjected to solvent distillation with an evaporator to give a blue-purple solid. Further, the blue-violet solid was dried under reduced pressure at 60 ° C to give 16.7 parts of the compound of formula (A-II-6). Yield 100%

Identification of compounds represented by formula (A-II-6)

( ¹⁹ F NMR; 380 MHz; δ value (ppm, based on hexafluorobenzene); DMSO); 109.1 (1F, br.s), 114.2 (4F, br.s)

The following reaction was carried out under a nitrogen atmosphere. 10.0 parts of the compound represented by the formula (A-II-6), lithium bis(trifluoromethanesulfonyl) phthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.5 parts, and N,N-dimethylformamidine After 100.0 parts of the amine was placed in a flask having a cooling tube and a stirring device, the mixture was stirred at 50 to 60 ° C for 3 hours. Next, the reaction mixture was cooled to room temperature, and the mixture was stirred for 1 hour while stirring 2000.0 parts of tap water to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. The resulting blue-green solid was purified by column chromatography. The purified blue-green solid was dried under reduced pressure at 60 ° C to give 10.2 parts of the compound of formula (A-I-6). Yield 79%

Identification of compounds represented by formula (A-I-6)

( ¹⁹ F NMR; 380 MHz; δ value (ppm, based on hexafluorobenzene); DMSO); 74.7 (6F, s) 109.1 (1F, br.s), 114.2 (4F, br.s)

(UV-VIS)

0.10 g of the compound represented by the formula (AI-6) was dissolved in chloroform to have a volume of 100 cm ³ , and 2 cm ³ of the compound was diluted with chloroform to have a volume of 250 cm ³ (concentration: 0.008 g/L), and spectrophotometry was used. The absorption spectrum was measured by a quartz cell (length of light; 1 cm). This compound showed an absorbance of 0.7 (arbitrary unit) at λ max = 601 nm.

Comparative Synthesis Example 1

The following reaction was carried out under a nitrogen atmosphere. After 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N,N-dimethylformamide were placed in a flask equipped with a cooling tube and a stirring device, the mixed solution was ice-cooled. After 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in small portions for 30 minutes under ice cooling, the mixture was stirred for 1 hour while warming to room temperature. 4.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) It was added to the reaction solution and stirred at room temperature for 24 hours. After a small amount of the reaction liquid was successively added to 200 parts of ice water, it was allowed to stand at room temperature for 15 hours, and water was removed by decantation to obtain a viscous solid in the form of a residue. After 60 parts of methanol was added to the thus-adhered solid, it was stirred at room temperature for 15 hours. After the precipitated solid was filtered, it was purified by column chromatography. The purified pale yellow solid was dried under reduced pressure at 60 ° C to give 9.8 part of the compound of formula (C-I-7). Yield 53%

Identification of compounds represented by formula (C-I-7)

( ¹ H NMR; 400 MHz; δ value (ppm, TMS basis); DMSO); 3.34 (6H, s), 6.83 (4H, br.d, J = 9.0 Hz), 7.20-7.28 (6H, m), 7.43 (4H, br.dd, J=8.5, 7.5Hz), 7.58 (4H, br.d, J=9.0Hz)

The following reaction was carried out under a nitrogen atmosphere. 8.2 parts of the compound represented by the formula (BI-2), 10.0 parts of the compound represented by the formula (CI-7), and 20.0 parts of toluene were placed in a flask having a cooling tube and a stirring device, followed by addition of phosphorus oxychloride. 12.2 parts and stirred at 95 to 100 ° C for 3 hours. Then, the reaction mixture was cooled to room temperature, and then diluted with 170.0 parts of isopropyl alcohol. 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. Then, the stirring was stopped, and after standing for 30 minutes, the organic layer and the aqueous layer were separated. After abandoning the water layer by liquid separation operation, Wash the organic layer with 300 parts of brine. An appropriate amount of Glauber's salt was added to the organic layer and stirred for 30 minutes, and then filtered to obtain an organic layer. The obtained organic layer was subjected to solvent distillation with an evaporator to give a blue-purple solid. Further, the blue-violet solid was dried under reduced pressure at 60 ° C to give 18.4 parts of the compound of formula (A-II-7). Yield 100%

Identification of compounds represented by formula (A-II-7)

( ¹⁹ F NMR; 380 MHz; δ value (ppm, based on hexafluorobenzene); DMSO); 109.0 (1F, br.s)

(mass spectrometry) ionization mode = ESI +: m / z = 687.3 [M-Cl] ⁺

Exact Mass: 722.3

The following reaction was carried out under a nitrogen atmosphere. 10.0 parts of the compound represented by the formula (A-II-7), lithium bis(trifluoromethanesulfonyl) phthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.), 5.9 parts, and N,N-dimethylformamidine After 100.0 parts of the amine was placed in a flask having a cooling tube and a stirring apparatus, the mixture was stirred at 50 to 60 ° C for 3 hours. Next, the reaction mixture was cooled to room temperature, and the mixture was stirred for 1 hour while stirring 2000.0 parts of tap water to obtain a dark blue suspension. filter The resulting suspension gave a blue-green solid. The blue-green solid was dried under reduced pressure at 60 ° C to give 13.2 parts of the compound of formula (A-I-7). Yield 86%

Identification of compounds represented by formula (A-I-7)

( ¹⁹ F NMR; 380 MHz; δ value (ppm, based on hexafluorobenzene); DMSO); 74.7 (6F, s) 109.0 (1F, br.s)

(UV-VIS)

0.35g compound of formula (AI-7) was dissolved in chloroform represented by the volume becomes 250cm ^3, and 2cm ³ wherein the volume to be diluted with chloroform 100cm ³ (concentration: 0.028g / L), spectrophotometric The absorption spectrum was measured by a quartz cell (length of light; 1 cm). This compound showed an absorbance of 2.8 (arbitrary unit) at λ max = 620 nm.

Preparation of colored curable resin composition]

Example 1

Mixing: coloring agent (A): 26 parts of the dye represented by the formula (A-I-2); Alkali-soluble resin (B): resin (B-1) (converted in solid form) 53 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; Nippon Chemical Co., Ltd. 16 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (IRGACURE (registered trademark) OXE-01; manufactured by BASF Corporation; O-mercaptopurine compound) 4 parts; solvent (E): propylene glycol monomethyl ether acetate 120 parts; solvent (E): 4-hydroxy-4-methyl-2- 480 parts of pentanone; and leveling agent (H): 0.15 parts of polyether modified fluorenone oil (Toray Silicone SH8400; manufactured by Toray Dow-Corning Co., Ltd.); and a colored curable resin composition was obtained.

Comparative example 1

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

Alkali-soluble resin (B): resin (B-1) (converted in solid form) 53 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; Nippon Chemical Co., Ltd. 16 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl) octane Alkan-1-one-2-imine (IRGACURE (registered trademark) OXE-01; manufactured by BASF Corporation; O-mercaptopurine compound) 4 parts; solvent (E): propylene glycol monomethyl ether acetate 120 parts; Solvent (E): 480 parts of 4-hydroxy-4-methyl-2-pentanone; and leveling agent (H): polyether modified fluorenone oil (Toray Silicone SH8400; manufactured by Toray Dow-Corning Co., Ltd.) 0.15 parts

Thus, a colored curable resin composition was obtained.

Production of color filters]

The colored curable resin composition was applied by a spin coating method on a 2 square inch glass substrate (#1737; manufactured by Corning), and then prebaked at 100 ° C for 3 minutes to form a colored composition layer. After cooling, exposure was carried out using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) under an atmospheric atmosphere at an exposure amount of 150 mJ/cm ² (365 nm basis). Furthermore, no reticle is used. The colored composition layer after the exposure was post-baked in an oven at 180 ° C for 20 minutes to prepare a color filter (film thickness: 2.8 μm).

Heat resistance rating]

The coating film of the coloring photosensitive resin composition was heated at 230 ° C for 20 minutes, and the color difference (ΔEab*) before and after heating of the coating film was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS). The coating film obtained in Example 1 was subjected to the above heat resistance evaluation, and as a result, the color difference (ΔEab*) was 3.5. Further, in the same manner as in Comparative Example 1, the heat resistance evaluation was carried out, and as a result, the color difference (ΔEab*) was 12.1, and it was found that the compound of the present invention was excellent in heat resistance.

Example 2

mixing: Coloring agent (A): 20 parts of the compound represented by the formula (AI-2); alkali-soluble resin (B): resin (B-2) (in terms of solid content) 34.3 parts; polymerizable compound (C): dioxane Tetraol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 34.3 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiobenzene) Octyl-1-keto-2-imine (IRGACURE (registered trademark) OXE-01; manufactured by BASF Corporation; O-mercaptopurine compound) 6.9 parts; solvent (E): propylene glycol monomethyl ether acetate 365 parts; solvent (E): 4-hydroxy-4-methyl-2-pentanone 250 parts; solvent (E): propylene glycol monomethyl ether 23 parts; solvent (E): ethyl lactate 4 parts; solvent ( E): methyl 3-methoxypropionate 16 parts; and leveling agent (H): polyether modified fluorenone oil (Toray Silicone SH8400; manufactured by Toray Dow-Corning Co., Ltd.) 0.06 parts; leveling agent (H): a fluorine-based surfactant (MEGAFAC F554; manufactured by DIC Co., Ltd.) 0.08 parts; an antioxidant (J): a phosphorus-based antioxidant (Sumilizer GP; manufactured by Sumitomo Chemical Co., Ltd.) 3.4 parts; Resin composition.

The coating film of the coloring composition was produced in the same manner as in Example 1, and the heat resistance was evaluated. As a result, the color difference (ΔEab*) of the coating film of the coloring composition was 2.7.

Comparative example 2

mixing: Coloring agent (A): 20 parts of the compound represented by the formula (AI-7); alkali-soluble resin (B): resin (B-2) (in terms of solid content) 34.3 parts; polymerizable compound (C): dioxane Tetraol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 34.3 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiobenzene) Octyl-1-keto-2-imine (IRGACURE (registered trademark) OXE-01; manufactured by BASF Corporation; O-mercaptopurine compound) 6.9 parts; solvent (E): propylene glycol monomethyl ether acetate 365 parts; solvent (E): 4-hydroxy-4-methyl-2-pentanone 250 parts; solvent (E): propylene glycol monomethyl ether 23 parts; solvent (E): ethyl lactate 4 parts; solvent ( E): methyl 3-methoxypropionate 16 parts; and leveling agent (H): polyether modified fluorenone oil (Toray Silicone SH8400; manufactured by Toray Dow-Corning Co., Ltd.) 0.06 parts; leveling agent (H): a fluorine-based surfactant (MEGAFAC F554; manufactured by DIC Co., Ltd.) 0.08 parts; an antioxidant (J): a phosphorus-based antioxidant (Sumilizer GP; manufactured by Sumitomo Chemical Co., Ltd.) 3.4 parts; Resin composition.

The coating film of the coloring composition was formed in the same manner as in Example 1, and the heat resistance was evaluated. As a result, the color difference (ΔEab*) of the coating film of the coloring composition was 3.8.

Additional heat resistance rating]

The coating film of the colored photosensitive resin composition after the heat resistance evaluation was heated at 230 ° C for 60 minutes, and the color difference (ΔEab*) before and after heating of the coating film was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS). When the coating film obtained in Example 2 was subjected to the above evaluation of the additional heat resistance, the color difference (ΔEab*) was 0.7. In addition, the evaluation of the additional heat resistance was carried out in the same manner as in Comparative Example 2. As a result, the color difference (ΔEab*) was 1.5, and it was found that the compound of the present invention was excellent in heat resistance.

Example 3

Mixing: coloring agent (A): 20 parts of the compound represented by the formula (AI-3); alkali-soluble resin (B): resin (B-2) (in terms of solid content) 34.3 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (IRGACURE (registered trademark) OXE-01; manufactured by BASF Corporation; O-mercaptopurine Compound) 6.9 parts; solvent (E): 365 parts of propylene glycol monomethyl ether acetate; solvent (E): 4-hydroxy-4-methyl-2-pentanone 250 parts; solvent (E): propylene glycol monomethyl 23 parts of the ether; solvent (E): ethyl lactate 4 parts; solvent (E): methyl 3-methoxypropionate 16 parts; and leveling agent (H): polyether modified fluorenone oil (Toray Silicone SH8400; made by Toray Dow-Corning Co., Ltd.) 0.06 parts; leveling agent (H): fluorine-based surfactant (MEGAFAC F554; manufactured by DIC) 0.08 parts; antioxidant (J): phosphorus-based antioxidant (Sumilizer GP; Sumitomo Chemical Co., Ltd.) 3.4 parts; and a colored curable resin composition was obtained.

The coating film of the coloring composition was produced in the same manner as in Example 1, and the heat resistance was evaluated. As a result, the color difference (ΔEab*) of the coating film of the coloring composition was 1.6. Then, the evaluation of the additional heat resistance was carried out, and as a result, the color difference (ΔEab*) of the coating film of the colored composition was 0.8.

Example 4

Mixing: coloring agent (A): 16 parts of the compound represented by the formula (AI-2); coloring agent (A): 4 parts of the compound represented by the formula (3-11); alkali-soluble resin (B): resin (B) -2) (solid content conversion) 34.3 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemical Co., Ltd.) 34.3 parts; polymerization initiator ( D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (IRGACURE (registered trademark) OXE-01; manufactured by BASF; O-醯 肟 compound 6.9 parts; solvent (E): 365 parts of propylene glycol monomethyl ether acetate; solvent (E): 4-hydroxy-4-methyl-2-pentanone 250 parts; solvent (E): 23 parts of propylene glycol monomethyl ether; solvent (E): ethyl lactate 4 parts; solvent (E): methyl 3-methoxypropionate 16 parts; and leveling agent (H): polyether modified fluorenone Oil (Toray Silicone SH8400; manufactured by Toray Dow-Corning Co., Ltd.) 0.06 parts; Leveling agent (H): fluorine-based surfactant (MEGAFAC F554; manufactured by DIC) 0.08 parts; antioxidant (J): phosphorus-based antioxidant (Sumilizer GP; Sumitomo Chemical Co., Ltd.) 3.4 parts; A colored curable resin composition was obtained.

The coating film of the coloring composition was formed in the same manner as in Example 1, and the heat resistance was evaluated. As a result, the color difference (ΔEab*) of the coating film of the coloring composition was 2.0. Then, the evaluation of the additional heat resistance was carried out, and as a result, the color difference (ΔEab*) of the coating film of the colored composition was 0.8.

Example 5

Mixing: coloring agent (A): 16 parts of the compound represented by the formula (AI-3); coloring agent (A): 4 parts of the compound represented by the formula (3-11); alkali-soluble resin (B): resin (B) -2) (solid content conversion) 34.3 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemical Co., Ltd.) 34.3 parts; polymerization initiator ( D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (IRGACURE (registered trademark) OXE-01; manufactured by BASF; O-醯 肟 compound 6.9 parts; solvent (E): 365 parts of propylene glycol monomethyl ether acetate; solvent (E): 4-hydroxy-4-methyl-2-pentanone 250 parts; solvent (E): 23 parts of propylene glycol monomethyl ether; solvent (E): 4 parts of ethyl lactate; Solvent (E): methyl 3-methoxypropionate 16 parts; and leveling agent (H): polyether modified fluorenone oil (Toray Silicone SH8400; manufactured by Toray Dow-Corning Co., Ltd.) 0.06 parts; Flat agent (H): fluorine-based surfactant (MEGAFAC F554; manufactured by DIC) 0.08 parts; antioxidant (J): phosphorus-based antioxidant (Sumilizer GP; Sumitomo Chemical Co., Ltd.) 3.4 parts; A colored curable resin composition.

The coating film of the coloring composition was prepared in the same manner as in Example 1, and the heat resistance was evaluated. As a result, the color difference (ΔEab*) of the coating film of the coloring composition was 1.5. Then, the evaluation of the additional heat resistance was carried out, and as a result, the color difference (ΔEab*) of the coating film of the colored composition was 0.8.

Reference example 1

Mixing: coloring agent (A): 20 parts of the compound represented by the formula (AI-4); alkali-soluble resin (B): resin (B-2) (in terms of solid content) 34.3 parts; polymerizable compound (C): two Neopentyl alcohol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 34.3 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylsulfide) Phenylphenyl)octane-1-one-2-imine (IRGACURE (registered trademark) OXE-01; manufactured by BASF Corporation; O-mercaptopurine compound) 6.9 parts; solvent (E): propylene glycol monomethyl ether B 365 parts of acid ester; solvent (E): 250 parts of 4-hydroxy-4-methyl-2-pentanone; Solvent (E): 23 parts of propylene glycol monomethyl ether; solvent (E): ethyl lactate 4 parts; solvent (E): methyl 3-methoxypropionate 16 parts; and leveling agent (H): poly Ether-modified ketone oil (Toray Silicone SH8400; manufactured by Toray Dow-Corning Co., Ltd.) 0.06 parts; leveling agent (H): fluorine-based surfactant (MEGAFAC F554; manufactured by DIC) 0.08 parts; antioxidant (J): 3.4 parts of a phosphorus-based antioxidant (Sumilizer GP; manufactured by Sumitomo Chemical Co., Ltd.); and a colored curable resin composition was obtained.

Reference example 2

Mixing: coloring agent (A): 20 parts of the compound represented by the formula (AI-5); alkali-soluble resin (B): resin (B-2) (in terms of solid content) 34.3 parts; polymerizable compound (C): two Neopentyl alcohol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 34.3 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylsulfide) Phenylphenyl)octane-1-one-2-imine (IRGACURE (registered trademark) OXE-01; manufactured by BASF Corporation; O-mercaptopurine compound) 6.9 parts; solvent (E): propylene glycol monomethyl ether B 365 parts acid ester; solvent (E): 4-hydroxy-4-methyl-2-pentanone 250 parts; solvent (E): propylene glycol monomethyl ether 23 parts; solvent (E): ethyl lactate 4 parts; Solvent (E): methyl 3-methoxypropionate 16 parts; and leveling agent (H): polyether modified fluorenone oil (Toray Silicone SH8400; manufactured by Toray Dow-Corning Co., Ltd.) 0.06 parts; Flat agent (H): fluorine-based surfactant (MEGAFAC F554; manufactured by DIC) 0.08 parts; antioxidant (J): phosphorus-based antioxidant (Sumilizer GP; Sumitomo Chemical Co., Ltd.) 3.4 parts; A colored curable resin composition.

Reference example 3

Mixing: coloring agent (A): 20 parts of the compound represented by the formula (AI-6); alkali-soluble resin (B): resin (B-2) (in terms of solid content) 34.3 parts; polymerizable compound (C): two Neopentyl alcohol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 34.3 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylsulfide) Phenylphenyl)octane-1-one-2-imine (IRGACURE (registered trademark) OXE-01; manufactured by BASF Corporation; O-mercaptopurine compound) 6.9 parts; solvent (E): propylene glycol monomethyl ether B 365 parts acid ester; solvent (E): 4-hydroxy-4-methyl-2-pentanone 250 parts; solvent (E): propylene glycol monomethyl ether 23 parts; solvent (E): ethyl lactate 4 parts; Solvent (E): methyl 3-methoxypropionate 16 parts; and leveling agent (H): polyether modified fluorenone oil (Toray Silicone SH8400; Toray Dow-Corning Co., Ltd.) 0.06 parts; leveling agent (H): fluorine-based surfactant (MEGAFAC F554; manufactured by DIC) 0.08 parts; antioxidant (J): phosphorus-based antioxidant (Sumilizer GP) ; Sumitomo Chemical Co., Ltd.) 3.4 parts; and a colored curable resin composition was obtained.

Reference example 4

Mixing: coloring agent (A): 16 parts of the compound represented by the formula (AI-4); coloring agent (A): 4 parts of the compound represented by the formula (3-11); alkali-soluble resin (B): resin (B) -2) (solid content conversion) 34.3 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemical Co., Ltd.) 34.3 parts; polymerization initiator ( D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (IRGACURE (registered trademark) OXE-01; manufactured by BASF; O-醯 肟 compound 6.9 parts; solvent (E): 365 parts of propylene glycol monomethyl ether acetate; solvent (E): 4-hydroxy-4-methyl-2-pentanone 250 parts; solvent (E): 23 parts of propylene glycol monomethyl ether; solvent (E): ethyl lactate 4 parts; solvent (E): methyl 3-methoxypropionate 16 parts; and leveling agent (H): polyether modified fluorenone Oil (Toray Silicone SH8400; manufactured by Toray Dow-Corning Co., Ltd.) 0.06 parts; Leveling agent (H): fluorine-based surfactant (MEGAFAC F554; manufactured by DIC) 0.08 parts; antioxidant (J): phosphorus-based antioxidant (Sumilizer GP; Sumitomo Chemical Co., Ltd.) 3.4 parts; A colored curable resin composition was obtained.

Reference example 5

Mixing: coloring agent (A): 16 parts of the compound represented by the formula (AI-5); coloring agent (A): 4 parts of the compound represented by the formula (3-11); alkali-soluble resin (B): resin (B) -2) (solid content conversion) 34.3 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemical Co., Ltd.) 34.3 parts; polymerization initiator ( D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (IRGACURE (registered trademark) OXE-01; manufactured by BASF; O-醯 肟 compound 6.9 parts; solvent (E): 365 parts of propylene glycol monomethyl ether acetate; solvent (E): 4-hydroxy-4-methyl-2-pentanone 250 parts; solvent (E): 23 parts of propylene glycol monomethyl ether; solvent (E): ethyl lactate 4 parts; solvent (E): methyl 3-methoxypropionate 16 parts; and leveling agent (H): polyether modified fluorenone Oil (Toray Silicone SH8400; manufactured by Toray Dow-Corning Co., Ltd.) 0.06 parts; leveling agent (H): fluorine-based surfactant (MEGAFAC F554; DIC) 0.08 parts; antioxidant (J): 3.4 parts of a phosphorus-based antioxidant (Sumilizer GP; manufactured by Sumitomo Chemical Co., Ltd.); and a colored curable resin composition was obtained.

Reference example 6

Mixing: coloring agent (A): 16 parts of the compound represented by the formula (AI-6); coloring agent (A): 4 parts of the compound represented by the formula (3-11); alkali-soluble resin (B): resin (B) -2) (solid content conversion) 34.3 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemical Co., Ltd.) 34.3 parts; polymerization initiator ( D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (IRGACURE (registered trademark) OXE-01; manufactured by BASF; O-醯 肟 compound 6.9 parts; solvent (E): 365 parts of propylene glycol monomethyl ether acetate; solvent (E): 4-hydroxy-4-methyl-2-pentanone 250 parts; solvent (E): 23 parts of propylene glycol monomethyl ether; solvent (E): ethyl lactate 4 parts; solvent (E): methyl 3-methoxypropionate 16 parts; and leveling agent (H): polyether modified fluorenone Oil (Toray Silicone SH8400; manufactured by Toray Dow-Corning Co., Ltd.) 0.06 parts; leveling agent (H): fluorine-based surfactant (MEGAFAC F554; manufactured by DIC) 0.08 parts; Antioxidant (J): 3.4 parts of a phosphorus-based antioxidant (Sumilizer GP; manufactured by Sumitomo Chemical Co., Ltd.); and a colored curable resin composition was obtained.

Industrial availability

According to the compound of the present invention, a color filter excellent in heat resistance can be provided. This color filter is useful as a color filter system used for display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

Claims (11)

A compound represented by the formula (A-VI): [In the formula (A-VI), the ion Y represents an anion of m-valent; R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A each independently represent a hydrogen atom or a carbon number; 1 to 10 alkyl; R ^9A and R ^10A each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an optionally substituted aromatic hydrocarbon group, or an optionally substituted aralkyl group; R ^11A and R ^12A each independently represents a halogen atom and an alkyl group having 1 to 10 carbon atoms, but at least one of R ^11A and R ^12A is an alkyl group having 1 to 10 carbon atoms; and R ^13A and R ^14A each independently represent a halogen atom; An alkyl group having 1 to 10 carbon atoms, wherein at least one of R ^13A and R ^14A is an alkyl group having 1 to 10 carbon atoms; and R ^15A , R ^16A , R ^17A , R ^18A , R ^19A and R ^20A are each independently The hydrogen atom and the alkyl group having 1 to 10 carbon atoms; in the above R ^1A to R ^20A , the alkyl group may have an oxygen atom interposed between the methylene groups constituting the same; and A represents an aromatic hydrocarbon group or a hetero group which may have a substituent; Aromatic group; m represents an integer from 1 to 14]. A compound represented by the formula (AI): [In the formula (AI), the ion Y represents an anion of m-valent; R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A each independently represent a hydrogen atom or a carbon number of 1~. 10 alkyl; R ^9A and R ^10A each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an optionally substituted aromatic hydrocarbon group, or an optionally substituted aralkyl group; R ^11A and R ^12A respectively The halogen atom and the alkyl group having 1 to 10 carbon atoms are independently represented, but at least one of R ^11A and R ^12A is an alkyl group having 1 to 10 carbon atoms; and R ^13A and R ^14A each independently represent a halogen atom and a carbon number; An alkyl group of 1 to 10, wherein at least one of R ^13A and R ^14A is an alkyl group having 1 to 10 carbon atoms; and R ^15A , R ^16A , R ^17A , R ^18A , R ^19A and R ^20A each independently represent hydrogen. An atom or an alkyl group having 1 to 10 carbon atoms; in the above R ^1A to R ^20A , the alkyl group may have an oxygen atom interposed between the methylene groups constituting the same; and R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom and carbon. a number of 1 to 10 alkyl groups, or a substituted aromatic hydrocarbon group; R ⁵⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an optionally substituted aromatic hydrocarbon group; and the above R ⁴⁵ , R ⁴⁶ and R ⁵⁵ The alkyl group may also constitute a sub Between group interrupted by oxygen atoms; m represents an integer of 1 to 14]. The compound of claim 1 or 2, wherein the counter ion is a fluorine-containing anion having a fluorine atom. The compound according to claim 1 or 2, wherein the counter ion is an anion containing the following elements as an essential element: oxygen, and at least one element selected from the group consisting of tungsten, molybdenum, rhenium and phosphorus. A colored curable resin composition comprising a compound (A1), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), wherein the compound (A1) is as requested Any one of items 1 to 4 is composed of an ion represented by the formula (A-VI) and a counter ion. The colored curable resin composition of claim 5, wherein the composition comprises a dye (A2) selected from at least one of the group consisting of an anthraquinone dye and a porphyrazine dye. The colored curable resin composition of claim 5 or 6, comprising a colorless metal complex (F). The colored curable resin composition according to any one of claims 5 to 7, which It also contains blue pigments. A coating film formed by the color hardening resin composition according to any one of claims 5 to 8. A color filter formed of the colored curable resin composition according to any one of claims 5 to 8. A display device comprising a color filter as claimed in claim 10.