TWI642730B - Dye compound and colored curable resin composition - Google Patents

Abstract

The present invention relates to a dye compound including a dye cation and an anion having two or more reactive groups.

Description

Dye compound and color-hardening resin composition

The present invention relates to a dye compound and a coloring curable resin composition.

A color-curable resin composition forming a color filter contained in a color filter included in a liquid crystal display device or the like or a solid-state imaging element, etc., describes a color-curable resin composition containing Formula (A -III-1) A compound, a binder resin, a solvent, a polymerization initiator, and a hardener shown in FIG.

An object of the present invention is to provide a dye compound that can be used in a color filter having excellent heat resistance.

The present invention provides the following [1] to [13].

[1] A dye compound comprising: A dye cation and an anion having two or more reactive groups.

[2] The dye compound according to [1], wherein the anion is an anion having a boron atom or an anion having an aluminum atom.

[3] The dye compound according to [1] or [2], wherein the dye cation is a cation represented by the formula (A-VI): [In the formula (A-VI), R ^1A to R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms (in An oxygen atom may be inserted between the carbon atoms constituting the alkyl group).

R ^9A to R ^12A each independently represent a hydrogen atom, and an alkyl group having 1 to 20 carbon atoms which may be substituted by an amine group, a dialkylamino group, or a halogen atom (an oxygen atom may be inserted between the carbon atoms constituting the alkyl group) , An alicyclic hydrocarbon group having 3 to 20 carbon atoms or an aryl group which may be substituted. R ^9A and R ^10A may be bonded to form a ring with the nitrogen atoms to which they are bonded, and R ^11A and R ^12A may be bonded to form a ring with the nitrogen atoms to which they are bonded.

A represents an aromatic hydrocarbon group which may have a substituent, or a heteroaromatic group which may have a substituent].

[4] The dye compound according to any one of [1] to [3], wherein the anion is an anion represented by the formula (A): (In the formula, M represents a boron atom or an aluminum atom. R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently represent a hydroxyl group, a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. Or a reactive group. However, at least one of R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ is a reactive group).

[5] The dye compound according to any one of [1] to [4], wherein the reactive group is a group having an ethylenically unsaturated bond.

[6] A coloring agent containing the dye compound according to any one of [1] to [5].

[7] The coloring agent according to [6], further comprising at least one dye selected from the group consisting of an anthraquinone dye and a tetraazaporphyrin dye.

[8] The coloring agent according to [6] or [7], which further contains a pigment.

[9] A coloring curable resin composition containing the coloring agent (A), the resin (B), the polymerizable compound (C) according to any one of [6] to [8], and a polymerization initiator Initiator (D), and solvent (E).

[10] The colored curable resin composition according to [9], which further contains a colorless metal complex (F).

[11] A coating film formed from the colored hardening resin composition according to [9] or [10].

[12] A color filter formed of the colored hardening resin composition according to [9] or [10].

[13] A display device comprising the color filter according to [12].

The dye compound of the present invention includes a dye cation and an anion having two or more reactive groups.

Dye cation means a cation of a conventional dye.

Specific examples of the dye cation include a cyanine dye shown below and a cation represented by the formula (A-VI).

In the formula (A-VI), R ^1A to R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms (in An oxygen atom may be inserted between the carbon atoms constituting the alkyl group), preferably each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 20 carbon atoms (at the carbon atom constituting the alkyl group) An oxygen atom can be inserted in between.

R ^9A to R ^12A each independently represent a hydrogen atom, and an alkyl group having 1 to 20 carbon atoms which may be substituted by an amine group, a dialkylamino group, or a halogen atom (an oxygen atom may be inserted between the carbon atoms constituting the alkyl group) , An alicyclic hydrocarbon group having 3 to 20 carbon atoms which may be substituted, or an aryl group which may be substituted, preferably each independently represents a hydrogen atom, an alkane having 1 to 20 carbon atoms which may be substituted by an amine group or a halogen atom Group (an oxygen atom may be inserted between the carbon atoms constituting the alkyl group), or an aryl group which may be substituted.

R ^9A and R ^10A may be bonded to form a ring with the nitrogen atoms to which they are bonded, and R ^11A and R ^12A may be bonded to form a ring with the nitrogen atoms to which they are bonded.

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

The cation represented by formula (A-VI) also includes its tautomer.

The cation represented by the formula (A-VI) is preferably a cation represented by the formula (A-I).

In the formula (A-I), X represents an oxygen atom or a sulfur atom.

R ⁴¹ to R ⁴⁶ each independently represent a hydrogen atom, and an alkyl group having 1 to 20 carbon atoms which may be substituted by an amine group, a dialkylamino group, or a halogen atom (an oxygen atom may be inserted between the carbon atoms constituting the alkyl group) , An alicyclic hydrocarbon group having 3 to 20 carbon atoms which may be substituted, or an aryl group which may be substituted, preferably independently represents a hydrogen atom, an alkane having 1 to 20 carbon atoms which may be substituted by an amine group or a halogen atom Group (an oxygen atom may be inserted between the carbon atoms constituting the alkyl group), or an aryl group which may be substituted.

R ⁴¹ and R ⁴² may be bonded and form a ring together with these bonded nitrogen atoms, R ⁴³ and R ⁴⁴ may be bonded and form a ring with these bonded nitrogen atoms, and R ⁴⁵ and R ⁴⁶ may be Bond and form a ring with these bonded nitrogen atoms.

R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms (an oxygen atom may be inserted between the carbon atoms constituting the alkyl group).

R ⁵⁵ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or an aryl group which may be substituted, and preferably represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, Or optionally substituted aryl].

The cation represented by the formula (A-I) also includes its tautomer.

In the formulae (A-VI) and (A-I), the alkyl group having 1 to 20 carbon atoms may be a straight chain or a branched chain. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl.

In the formulae (A-VI) and (AI), the alicyclic hydrocarbon group having 3 to 20 carbon atoms may be monocyclic or polycyclic. Examples of the alicyclic hydrocarbon group include cyclohexyl, cycloheptyl, and tricyclic [3.3.1.1. ^3,7 ] octyl.

Specific examples of the above-mentioned alkyl group and the above-mentioned alicyclic hydrocarbon group In other words, a base represented by the following formula is mentioned.

(In each formula, * represents a bond with a carbon atom or a nitrogen atom)

The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

In the formula (A-VI) and the formula (A-I), a group having an oxygen atom inserted between the carbon atoms constituting the alkyl group includes a group represented by the following formula.

(In each formula, * represents a bond with a carbon atom or a nitrogen atom)

Among them, a group having an oxygen atom inserted between carbon atoms constituting an alkyl group having 1 to 10 carbon atoms is more preferable, and a group having an oxygen atom inserted between carbon atoms constituting an alkyl group having 1 to 6 carbon atoms is more preferable.

In the formula (A-VI) and the formula (A-I), for the alkyl group having 1 to 20 carbon atoms substituted with an amine group, a dialkylamino group, or a halogen atom, the following formulas may be exemplified. The base shown.

(In each formula, * represents a bond with a nitrogen atom)

The above-mentioned alkyl group having 1 to 20 carbon atoms substituted with an amino group, a dialkylamino group or a halogen atom is preferably an alkyl group having 1 to 8 carbon atoms substituted with a dialkylamino group or a halogen atom.

In the formula (AI), the alkyl group having 1 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ may be a straight chain or a branched chain. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl.

Specific examples of the alkyl group having 1 to 8 carbons represented by R ⁴⁷ to R ⁵⁴ (an oxygen atom may be inserted between the carbon atoms constituting the alkyl group) include a group represented by the following formula.

(In each formula, * represents a bond with a carbon atom)

In the formula (A-VI) and the formula (A-I), examples of the aryl group include Aryl groups having 6 to 14 carbon atoms such as phenyl and naphthyl.

Examples of the substituent in the aryl group include halogen atoms such as fluorine atom, chlorine atom, and iodine; haloalkyl groups having 1 to 6 carbon atoms such as chloromethyl and trifluoromethyl; methoxy and ethoxy Alkoxy groups of 1 to 6 carbons; methyl, ethyl, etc. Alkyl groups of 1 to 6 carbons; hydroxyl; aminesulfonyl groups; methylsulfonyl groups of 1 to 6 carbon alkyl groups ;Wait.

Specific examples of the aryl group which may be substituted include a group represented by the following formula.

(In each formula, * represents a bond with a nitrogen atom)

In the formula (A-VI), as for the ring in which R ^9A and R ^10A , R ^11A and R ^12A are bonded together with the nitrogen atom to which they are bonded, a pyrrolidine ring, a morpholin ring, Piperidine ring, piperazine ring, etc.

In the formula (AI), as for the ring in which R ⁴¹ and R ⁴² , R ⁴³ and R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are bonded together with the nitrogen atom to which they are bonded, a pyrrolidine ring, Forint ring, piperidine ring, piperazine ring, etc.

From the standpoint of ease of synthesis, R ^1A to R ^8A in the formula (A-VI) are preferably independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, and more preferably, they are independent of each other. Ground is a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom.

From the standpoint of ease of synthesis, R ^9A to R ^12A in formula (A-VI), and R ⁴¹ to R ⁴⁶ and R ⁵⁵ in formula (AI) are each preferably independently 1 to 20 carbon atoms. Alkyl or substituted aryl is more preferably independently alkyl having 1 to 8 carbon atoms, or halogen atom, alkyl having 1 to 4 carbon atoms, or haloalkyl having 1 to 4 carbon atoms , A hydroxy group or an alkoxy-substituted aryl group having 1 to 4 carbon atoms, and still more preferably an alkyl group having 1 to 8 carbon atoms or an aryl group represented by the following formula, each independently.

(In each formula, * represents a bond with a nitrogen atom)

From the viewpoint of ease of synthesis, in formula (AI), R ⁴⁷ to R ^{54 are} preferably each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, and more preferably each independently are A hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom.

In the formula (A-VI), the aromatic hydrocarbon group which may have a substituent may be monocyclic or polycyclic. Examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group having 6 to 14 carbon atoms such as a phenyl group and a naphthyl group.

The aromatic hydrocarbon group may have a substituent. Examples of the substituent include an alkylamino group, a dialkylamino group, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, a phenylamino group, a halogen atom, a hydroxyl group, and SO ₃ ^- Wait. Examples of the alkyl group in the alkylamino group and the dialkylamino group include alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, and butyl. The phenyl group in the phenylamino group may have an alkyl group having 1 to 5 carbon atoms, a halogen atom, a halogen alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, methylsulfonyl group, SO ₃ ^- etc. substituents.

Examples of the aromatic hydrocarbon group which may have a substituent described above include a group represented by the following formula. Among them, a base represented by the formula (A1-2) and a base represented by the formula (A1-6) are preferred.

(In the above formula, * represents a bond with a carbon atom)

In formula (A-VI), the heteroaromatic group which may have a substituent may be monocyclic or polycyclic. Examples of the hetero atom in the heteroaromatic group include a nitrogen atom, a sulfur atom, and an oxygen atom. The heteroaromatic group may have two or more kinds of heteroatoms.

The heteroaromatic group is preferably a heteroaromatic group having 3 to 10 carbon atoms having at least one nitrogen atom, and examples thereof include imidazolyl, thiazolyl, and oxazolyl.

The heteroaromatic group may have a substituent. Examples of the substituent include an alkylamino group, a dialkylamino group, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, a phenylamino group, a halogen atom, a hydroxyl group, and SO ₃ ^- Wait. Examples of the alkyl group in the alkylamino group and the dialkylamino group include alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, and butyl. The phenyl group in the phenylamino group may have a substituent of an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a phenyl group, and the like.

Examples of the heteroaromatic group in the formula (A-VI) include a group represented by the following formula. Among them, a base represented by the formula (A1-12) and a base represented by the formula (A1-13) are preferred.

(In each formula, * represents a bond with a carbon atom)

In the formula (A-I), X represents an oxygen atom or a sulfur atom. From the viewpoint of ease of synthesis, a sulfur atom is preferred.

Specific examples of the cation represented by the formula (A-VI) include a cation represented by the following formula.

(In formula (AIa), R ⁴¹ to R ⁴⁶ and R ⁵⁵ are the same as defined above)

In the formula (AIa), R ⁴¹ to R ^{44 are} preferably each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group. R ⁴⁵ and R ^{46 are} preferably independently an alkyl group having 1 to 6 carbon atoms (an oxygen atom can be inserted between the carbon atoms constituting the alkyl group), and a phenyl group which can be substituted with an alkyl group having 1 to 4 carbon atoms. , Or together with these bonded nitrogen atoms to form a piperazine ring. R ^{55 is} preferably a phenyl group which may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or a sulfomethylmethyl group. Specific examples of the cation represented by the formula (AI) include a cation represented by the formula (AIa) and cations 1 to 12 having the substituents shown in Table 1.

The cations represented by formula (A-I) are preferably cations 1 to 6, cation 11, and cation 12, and more preferably cation 1, cation 2, and cation 12.

In the dye compound of the present invention, the reactive group generally has an ethylenically unsaturated bond.

In respect of the reactive group, examples thereof include ethynyl, CH allyl having 2-5 carbon atoms, a hydrocarbon group of the ₂ = CH-; and ^{_{CH 2 = CH-R X1 -}} (R X2) nx- (R X1 Represents a carbonyloxy group, an oxycarbonyl group, or a carbonyl group. R ^X2 represents an alkylene group having 1 to 4 carbon atoms. Nx represents a group represented by 0 or 1) and the like.

Specific examples of the reactive group include the groups shown below.

(In each formula, * indicates a bond key)

Among the dye compounds of the present invention, an anion having two or more reactive groups is preferably an anion having a boron atom and an anion having an aluminum atom, and more preferably an anion represented by formula (4).

In Formula (4), W ¹ and W ² each independently represent a group formed by releasing a proton from a proton donating group in a compound having a reactive group and a proton donating group.

M represents boron or aluminum.

The compound having a reactive group and a proton donating group is preferably an aromatic hydrocarbon compound having 6 to 10 carbon atoms having a hydroxyl group, a carboxyl group, and a reactive group, and more preferably a salicylic acid compound having a reactive group. Examples of the proton donating group in the aromatic hydrocarbon compound include H ^{+ which} constitutes a hydroxyl group and a carboxyl group.

Since the number of reactive groups represented by the formula (4) is two or more, there is a tendency that the heat resistance is excellent.

Examples of the compound having a reactive group and a proton donating group include the compounds shown below.

As for the anion represented by the formula (4), an anion represented by the formula (A) can be listed: (In the formula, M represents a boron atom or an aluminum atom. R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently represent a hydroxyl group, a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. Or a reactive group. However, at least one of R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ is a reactive group).

Examples of the anion represented by the formula (A) include Anions (BC-1) to anions (BC-43) and the like of the substituents shown in 2 and Table 3 (M represents a boron atom or an aluminum atom).

As for the anion represented by formula (4), anions (BC-4) to anions (BC-6), anions (BC-13) to anions (BC-15), and anions (BC-22) to Anions (BC-24), anions (BC-29), anions (BC-32) and anions (BC-39).

The dye compound of the present invention is preferably a compound including a cation represented by formula (A-VI) and an anion represented by formula (4), and more preferably a cation represented by formula (AI), and An anionic compound represented by formula (4).

The dye compound of the present invention can be prepared by mixing an alkali metal salt of an anion having two or more reactive groups with a dye in a solvent. Ion.

The dye cation is not particularly limited, and a commercially available product can be used.

Examples of the alkali metal in the alkali metal salt include lithium, sodium, and potassium.

When the alkali metal salt of the anion represented by the formula (A) is sodium, the compound represented by the formula (d1), sodium hydroxide, M (OH) can be made in the presence of an alcohol-based solvent such as methanol. ₃ (M represents a boron atom or an aluminum atom).

(In formula (d1), R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ have the above meanings, and M represents a boron atom or an aluminum atom)

For example, a dye compound including a cation represented by the formula (AI) and an anion represented by the formula (4) (hereinafter, also referred to as a dye (A1)) can be obtained by mixing the compound of the formula (A-II) in a solvent. The compound (hereinafter, also referred to as compound (A-II)) and an alkali metal salt of an anion represented by formula (4) are produced. Examples of the alkali metal include lithium, sodium, and potassium.

Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamidamine, N-methylpyrrolidone, dimethylsulfinium, acetonitrile, ethyl acetate, and toluene , Methanol, ethanol, isopropanol, acetone, tetrahydrofuran, dioxane, water and chloroform.

Among them, preferred are N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfine, methanol, ethanol, isopropanol, and water. . With these solvents, the solubility of the alkali metal salt of the anion represented by the compound (A-II) and the formula (4) tends to be high.

When the solvent is water, acids such as acetic acid and hydrochloric acid can be added.

The compound (A-II) and the alkali metal salt of the anion represented by the formula (4) may be mixed by dissolving both of them in the solvent described above or without dissolving them.

The mixing temperature of the compound (A-II) and the anionic alkali metal salt represented by formula (4) is preferably 0 ° C to 150 ° C, more preferably 10 ° C to 120 ° C, and even more preferably 20 ° C to 100 ° C. . The mixing time is preferably 1 hour to 72 hours, more preferably 2 hours to 24 hours, and even more preferably 3 hours to 12 hours.

When using a solvent that is miscible with water, The solution was further stirred for 1 to 3 hours as needed, and then the precipitate was filtered to obtain a dye (A1). The obtained dye (A1) can be washed with ion-exchanged water as needed.

When using a water-incompatible solvent, the reaction mixture and ion-exchanged water can be mixed, and further stirred for 1 to 3 hours as required, and then the organic layer can be separated to obtain a solution containing the dye (A1). This solution can be washed with ion-exchanged water as needed. The solvent is removed from the solution containing the dye (A1) to obtain the dye (A1).

The compound (A-II) can be produced by reacting a compound represented by the formula (B-I) with a compound represented by the formula (C-I). This reaction can be carried out in the presence of an organic solvent or without a solvent.

In formula (BI) and formula (CI), R ⁴¹ to R ⁵⁵ each have the same meaning as described above.

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). This reaction can be carried out in the presence of an organic solvent or without a solvent.

In the formula (B-II) and the formula (C-II), R ⁴¹ , R ⁴² , R ⁴⁵ to R ^50, and R ⁵⁵ have the same meanings as described above, respectively.

Relative to the compound represented by formula (BI), the amount of the compound represented by formula (CI) used is preferably 0.5 mole to 8 moles relative to 1 mole of the compound represented by formula (BI), More preferably, it is 1 mole or more and 3 moles or less.

The use amount of the compound represented by the formula (C-II) is preferably 0.5 mole relative to the compound represented by the formula (B-II). Above 8 mol and below, more preferably between 1 mol and 3 mol.

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

From the standpoint of yield, any reaction is preferably performed in an organic solvent. Examples of organic solvents 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 nitro hydrocarbons such as nitrobenzene Solvents; ketone solvents such as methyl isobutyl ketone; ammonium solvents such as 1-methyl-2-pyrrolidone; etc. The amount of the organic solvent used is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 2 parts by mass based on 1 part by mass of the compound represented by the formula (B-I) or formula (B-II). Above 10 parts by mass.

In terms of yield, the above 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 thionyl chloride.

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

The method for obtaining the compound (A-II) from the reaction mixture is not particularly limited, and various known methods can be used. Examples thereof include a method of mixing the reaction mixture with an alcohol (for example, methanol) and filtering the precipitated crystals. The reaction mixture is preferably added to the aforementioned alcohol. The temperature when the reaction mixture is added is preferably -100 ° C to 50 ° C, and more preferably -80 ° C to 0 ° C. After that, it is preferably stirred at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are preferably washed with water and then dried. Moreover, if necessary, it can be further refined by conventional methods such as recrystallization.

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

Examples of methods for producing the compound represented by the formula (C-I) and the compound represented by the formula (C-II) include conventional methods, such as those described in International Publication No. 2012/128318.

The alkali metal salt of the anion represented by the formula (4) can be a commercially available one, or it can be obtained from Japanese Patent No. 40977704 or Japanese Patent No. 4341251 and Journal of The Electrochemical Society, Vol. 148 No. 1 Period, 2001 and other methods.

Specific examples of the dye compound (dye (A1)) including a cation represented by the formula (A-VI) and an anion represented by the formula (4) include any cation selected from the cations 1 to 12 described above. A compound with any anion selected from the above anions (BC-1) to (BC-43), and a compound represented by the following formula.

<Colorant (A)>

The coloring agent of the present invention (hereinafter, also referred to as "colorant (A)") includes the dye compound of the present invention.

The colorant (A) may be a colorant including the colorant of the present invention, and may further contain at least one dye (A2) (hereinafter, also Called Dye (A2)).

Anthraquinone dyes can use conventional substances. Examples of the anthraquinone dye include: C.I. Solvent Yellow 117 (hereinafter, the description of C.I. Solvent Yellow is omitted, and only the number is described), 163, 167, 189; C.I. Solvent Orange 77, 86; CI Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247; CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79 , 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; CI Solvent Green 3, 28, 29, 32, 33; CI Acid Red 80 ; CI acid green 25, 27, 28, 41; CI acid violet 34; CI acid blue 25, 27, 40, 45, 78, 80, 112; CI disperse yellow 51; CI disperse violet 26, 27; CI disperse blue 1 , 14, 56, 60; CI Direct Blue 40; CI Mordant Red 3, 11; CI Mordant Blue 8; etc.

Anthraquinone dyes are preferably those dissolved in an organic solvent, and more preferably blue, purple or red anthraquinone dyes.

More preferable anthraquinone dyes include compounds represented by the formulae (3-1) to (3-11).

The anthraquinone dye is more preferably a compound represented by the formula (3-4) and a compound represented by the formula (3-11). If these anthraquinone dyes are used, not only high-contrast coating films and patterns can be formed, but also coating films and patterns with less foreign matter generation and excellent light resistance can be formed.

A tetraazaporphyrin dye is a compound having a tetraazaporphyrin skeleton in its molecule. When the tetraazaporphyrin dye is an acid dye or a basic dye, it can form any cation, anion and salt.

Tetraazaporphyrin dyes, preferably with Cu, Ni, Co, Pd, V or Mg is a complex of "central metal".

Specific examples of the tetraazaporphyrin dye include compounds represented by the formulae (2-1) to (2-38).

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

If it is a composition containing the tetraazaporphyrin dye, not only a high-contrast coating film and pattern can be formed, but also the generation of foreign matter is small.

The content ratio of the dye of the present invention is preferably 0.5% by mass or more and 80% by mass or less, more preferably 40% by mass or more and 80% by mass or less with respect to the total amount of the colorant (A).

The content of the dye (A2) is preferably 1 to 100 parts by mass, and more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the dye of the present invention.

In order to adjust the color, that is, to adjust the spectral characteristics, the colorant (A) may further contain other dyes, pigments (P), or a mixture thereof in addition to the dye and the dye (A2) of the present invention.

The dyes and dyes other than the dye (A2) of the present invention may be any of direct dyes and mordant dyes, and examples thereof include oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, and amines of acid dyes. Dyes such as salts and sulfonamide derivatives of acid dyes.

Examples of the dye include compounds classified as dyes in the color index (published by The Society of Dyers and Colourists), and conventional dyes described in Dyeing Notes (Seiransha). Examples of the dye include an azo dye, a cyanine dye, a triphenylmethane dye, a xanthene dye, a phthalocyanine dye, a naphthoquinone dye, a quinone imine dye, a methine dye, Azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, and the like. Among these, an organic solvent-soluble dye is preferably used.

Specific examples include: C.I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; CI Solvent Red 45, 49, 125, 130, 218; CI Solvent Orange 2, 7, 11, 15, 26, 56; CI Solvent Blue 4, 5, 37, 67, 70, 90; CI Solvent Green 1, 4, 5, 7, 34, 35 and other CI solvent dyes, CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73 , 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168 , 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238 , 240, 242, 243, 251; CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339 , 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Violet 6B, 7, 9, 9, 19, 30, 102; CI Acid Blue 1, 7, 9, 15, 18, 22, 29, 42, 59, 60, 62, 70, 72, 74, 82, 83, 86, 87, 90, 92, 93, 100, 102, 103, 104, 113, 117, 120, 126, 130, 131, 142, 147, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335; CI Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106 , 109 and other CI acid dyes, CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177 , 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; CI Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct Purple 47, 52, 54, 59, 60, 65, 66, 79, 80, 81 , 82, 84, 89, 90, 93, 95, 96, 103, 104; CI Direct Blue 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CI direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other CI direct dyes, CI disperse yellow 54, 76 and other CI disperse dyes, CI Basic Red 1, 10; CI Basic Blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68; CI basic green 1, etc. CI basic dyes, CI reactive yellow 2, 76, 116; CI reactive orange 16; CI reactive red 36; CI reactive dyes, CI mordant yellow 5, 8, 10, 16 , 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI mordant red 1, 2, 4, 9, 12, 12, 17, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; CI Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48 ; CI Mordant Purple 1, 2, 4, 5 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; CI mordant blue 1, 2, 3, 7, 9, 12, 13, 15 , 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 44, 49, 53, 61, 74, 77, 83, 84; CI mordant green 1, 3, 4, 5, 10, 15, 26 , 29, 33, 34, 35, 41, 43, 53, CI mordant dyes, CI reduced green 1 and other vat dyes, and so on.

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

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

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

As far as pigments are concerned: CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125 , 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55 , 59, 61, 64, 65, 71, 73 and other orange pigments; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216 , 224, 242, 254, 255, 264, 265 and other red pigments; CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 purple pigments; CI Pigment Green 7, 36, 58 green pigments; Brown pigments such as C.I. Pigment Brown 23, 25; black pigments such as C.I. Pigment Black 1, 7, etc.

The pigment (P) is preferably a phthalocyanine pigment and a dioxazine pigment, and more preferably at least one selected from the group consisting of C.I. Pigment Blue 15: 6 and Pigment Violet 23. By including the pigment, the transmission spectrum can be easily optimized, and the heat resistance, light resistance, and chemical resistance of the color filter are improved.

<Colored curable resin composition>

The colored curable resin composition of the present invention contains the above-mentioned colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D), and solvent (E).

The content of the colorant (A) is preferably 5 mass% or more and 70 mass% or less, more preferably 5 mass% or more and 60 mass% or less, and still more preferably 5 mass% or more and 50% relative to the total solid content. Mass% or less. When the content of the colorant (A) is within the aforementioned range, a desired spectroscopic and color density can be obtained.

In this specification, the "total amount of solid content" means the total amount after removing the component of the solvent (E) from the colored hardening resin composition of this invention. The total amount of the solid content and the content of each component relative to the total amount can be measured by conventional analytical means such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin (B). The alkali-soluble resin (B) (hereinafter referred to as "resin (B)") contains at least one monomer (a) derived from a group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. Copolymer of structural units.

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

The resin [K1] is at least one monomer (a) (hereinafter referred to as "(a)") selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and has a carbon number of 2 to Copolymer of cyclic ether structure and ethylenically unsaturated monomer (b) (hereinafter referred to as "(b)") in 4; resin [K2] is (a) and (b), and Copolymer of (a) copolymerizable monomer (c) (but different from (a) and (b)) (hereinafter referred to as "(c)"); resin [K3] is (a ) And (c); Resin [K4] is a copolymer obtained by reacting (b) with (a) and (c); Resin [K5] is based on the copolymerization of (b) and (c) The resin obtained by reacting (a); the resin [K6] is a copolymer obtained by copolymerizing (b) and (c), reacting (a), and then reacting carboxylic anhydride.

As for (a), specific examples include: unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, ortho-, meta-, and p-vinylbenzoic acid; maleic acid, fumaric acid, and citraconic acid Acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, Unsaturated dicarboxylic acids such as dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclic [2.2.1 ] Hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [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-ene, 5-carboxy- 6-ethylbicyclo [2.2.1] hept-2-ene and other bicyclic unsaturated compounds containing carboxyl groups; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride , 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2 -Unsaturated dicarboxylic anhydrides such as ene anhydrides; mono [2- (meth) acrylfluorenyloxyethyl] succinate, [2- (meth) acrylfluorenyloxyethyl] phthalic acid] Unsaturated mono [(meth) acrylfluorenyloxyalkyl] esters of polyvalent carboxylic acids with a valence of 2 or more; unsaturated acrylic esters containing hydroxyl and carboxyl groups in the same molecule such as α- (hydroxymethyl) acrylic acid Class, etc.

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

(b) means a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an ethylene oxide ring, an oxobutane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond Polymerizable compound.

(b) A monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acrylfluorenyloxy group is preferred.

Examples of (b) include a monomer having an ethylene oxide group and an ethylenically unsaturated bond, a monomer having an oxycyclobutane group and an ethylenically unsaturated bond, and a tetrahydrofuran group and an ethylenically unsaturated bond. Of monomers, etc.

As far as (b) is concerned, the resistance of the obtained color filter can be improved. From the viewpoint of further improving reliability such as heat resistance and chemical resistance, monomers having an ethylene oxide group and an ethylenically unsaturated bond are preferred.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, and (meth) acrylic acid. Third butyl ester, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic ring Amyl ester, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl ester (in this In the technical field, it is called "dicyclopentyl (meth) acrylate" as a common name. In some cases, it is called "tricyclodecyl (meth) acrylate"), and tricyclic (meth) acrylate [ 5.2.1.0 ^2,6 ] decene-8-yl ester (in this technical field, it is commonly called "dicyclopentenyl (meth) acrylate"), dicyclopentyl (meth) acrylate Ethoxyethyl ester, isoamyl (meth) acrylate, adamantane (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, ( (Meth) acrylates such as naphthyl (meth) acrylate, benzyl (meth) acrylate Type; (hydroxy) (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate; diethyl maleate, diethyl fumarate, Iran Dicarboxylic acid diesters such as diethyl taurate; bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] Hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [ 2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxy Bicyclo [2.2.1] hept-2-ene, 5,6-bis (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-tert-butoxycarbonyl bicyclic [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonyl bicyclic [2.2.1] hept-2-ene, 5-phenoxycarbonyl bicyclo [2.2.1] hept-2-ene, 5,6-bis (third butoxycarbonyl) bicyclo [2. 2.1] Bicyclic unsaturated compounds such as hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene; N-phenylmaleimide, N- Cyclohexylmaleimide, N-benzylmaleimide, 3-maleimide benzoate N-succinimide, 4-maleimide butyric acid N-succinimide Amine ester, 6-maleimide hexanoic acid N-succinimide, 3-maleimide propionic acid N-succinimide, N- (9-acridyl) maleimide Derivatives such as amines such as amines; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, Methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1, 3-butadiene and the like.

Among these, in terms of copolymerization reactivity and heat resistance, styrene, vinyltoluene, benzyl (meth) acrylate, and tricyclic (meth) acrylate are preferred [5.2.1.0 ^2,6 ] Decane-8-yl ester, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2- Ene.

In addition, in this specification, "(meth) acrylic acid" means at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid. Marks such as "(meth) acrylfluorenyl" and "(meth) acrylate" have the same meaning.

Specific examples of the resin (B) include 3,4-epoxycyclohexyl methyl (meth) acrylate / (meth) acrylic copolymer, and 3,4-epoxy (meth) acrylate. Tricyclic [5.2.1.0 ^2.6 ] resins such as decyl ester / (meth) acrylic copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer , Glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxy tricyclo (meth) acrylic acid [5.2.1.0 ^2.6 ] decyl ester / (meth) acrylic acid / N-cyclohexylmaleimide imide copolymer, 3,4-epoxy tricyclo (meth) acrylate [5.2.1.0 ^2.6 ] decyl / (meth) acrylic acid / vinyltoluene copolymer, 3- Resins such as methyl-3- (meth) propenyloxymethyloxycyclobutane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate / (meth) Acrylic copolymer, styrene / (meth) acrylic copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic copolymer and other resins [K3]; Base) resin obtained by adding benzyl acrylate / (meth) acrylic acid copolymer to glycidyl (meth) acrylate, and Tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer obtained by adding glycidyl (meth) acrylate to tricyclodecyl (meth) acrylate / (meth) acrylate Resin and other resins obtained by adding benzyl acrylate / (meth) acrylic acid copolymer to glycidyl (meth) acrylate [K4]; tricyclodecyl (meth) acrylate / (meth) acrylic acid epoxy A resin obtained by reacting a copolymer of propyl ester with (meth) acrylic acid, and a resin obtained by reacting a copolymer of trimethacrylate with (meth) acrylic acid / styrene / glycidyl (meth) acrylate by reacting (meth) acrylic acid Resin [K5]; resin obtained by reacting (meth) acrylic acid in a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate and then reacting tetrahydrophthalic anhydride Resin and other resins [K6] and so on.

The resin [K1] can be referred to, for example, the method described in the document "Experimental Method of Polymer Synthesis" (by Otsu Takayuki, Chemical Publishing House, First Edition, First Edition, March 1, 1972) and the method It is manufactured by citing documents described in the literature.

The resin (B) is preferably selected from the group consisting of the resin [K1], the resin [K2], and the resin [K3], and more preferably the resin (B) is selected from the group consisting of the resin [K2] and the resin [K3] One kind. With these resins, the developability of the colored curable resin composition is excellent. From the viewpoint of the adhesion between the colored pattern and the substrate, the resin [K2] is even 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 even more preferably 5,000 to 30,000. When the molecular weight is within the aforementioned range, there is a tendency that the hardness of the coating film increases, the residual film rate is high, the solubility of the unexposed portion to the developing solution is good, and the resolution of the colored pattern tends to increase.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

The acid value of the resin (B) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, and even more preferably 70 to 135 mg-KOH / g. Here, the acid value is the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B). The measured value can be obtained by, for example, 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, relative to the total amount of the solid content. When the content of the resin (B) is within the foregoing range, a colored pattern can be formed, and the resolution and the residual film rate of the colored pattern tend to increase.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and includes a compound having a polymerizable ethylenically unsaturated bond. (Meth) acrylate compounds.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethylhexylcarbitol acrylic acid. Esters, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the like, as well as (a), (b), and (c) above.

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 (Meth) acrylate, triethylene glycol di (meth) acrylate, bis (propenyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate Wait.

The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, and Neopentaerythritol penta (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, sanxin Pentaerythritol octa (meth) acrylate, trineopentaerythritol hepta (meth) acrylate, tetranepentaerythritol deca (meth) acrylate, tetranepentaerythritol nine (meth) acrylate, Tris (2- (meth) acrylfluorenyloxyethyl) isotricyanate, ethylene glycol modified neopentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol Hexa (meth) acrylate, propylene glycol modified neopentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified neopentaerythritol tetra ( Methacrylic acid esters and caprolactones modified dipentaerythritol hexa (meth) acrylate and the like, among them, dinepentaerythritol penta (meth) acrylate and dinepentaerythritol hexa (meth) acrylate are preferred. (Meth) acrylate.

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

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass with respect to the total amount of the solid content.

Content ratio of resin (B) to polymerizable compound (C) [resin (B): polymerizable compound (C)] On a mass basis, it is preferably 20:80 to 80:20, and more preferably 35:65 to 80:20.

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

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound that can start polymerization by the action of light or heat to generate living radicals, acids, and the like, and a conventional polymerization initiator can be used.

Examples of the polymerization initiator (D) include O-fluorenyl oxime compounds, alkylphenones compounds, biimidazole compounds, triazine compounds, and fluorenylphosphine oxide compounds.

Examples of the O-fluorenyl oxime compound include N-benzylideneoxy-1- (4-phenylmercaptophenyl) butane-1-one-2-imine, and N-benzylidene. Phenyloxy-1- (4-phenylmercaptophenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylmercaptophenyl) -3- Cyclopentylpropane-1-one-2-imine, N-ethoxyl-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl ] Ethane-1-imine, N-ethoxyl-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxa Cyclopentylmethyloxy) benzylidene} -9H-carbazol-3-yl] ethane-1-imine, N-acetamidooxy-1- [9-ethyl-6- (2 -Methylbenzylidene) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzylideneoxy-1- [9-ethyl-6- (2-methylbenzyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one-2-imine and the like. Commercially available products such as IRGACURE (registered trademark) OXE01, OXE02 (above, manufactured by BASF), and N-1919 (made by ADEKA) can be used. Among them, the O-fluorenyl oxime compound is preferably selected from the group consisting of N-benzyloxy-1- (4-phenylmercaptophenyl) butane-1-one-2-imine, and N-benzidine Oxy-1- (4-phenylmercaptophenyl) octane-1-one-2-imine and N-benzyloxy-1- (4-phenylmercaptophenyl) -3- At least one of the groups formed by cyclopentylpropane-1-one-2-imine, more preferably N-benzyloxy-1- (4-phenylmercaptophenyl) octane-1 -Keto-2-imine. If it is such an O-fluorenyl oxime compound, there is a tendency to obtain a color filter with high brightness.

Examples of the alkyl phenone compound include 2-methyl-2-morpholinyl-1- (4-methylmercaptophenyl) propane-1-one and 2-dimethylamine. 1- (4-morpholinylphenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl] butane-1-one, IRGACURE (registered trademark) 369, 907, 379 (above, manufactured by BASF), 2-hydroxy-2-formyl 1-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propane-1-one, 1-hydroxycyclohexylphenyl Ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one oligomer, α, α-diethoxyacetophenone, benzyldimethyl Acetal and so on.

Examples of the aforementioned biimidazole compounds include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3 -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (refer to Japanese Patent Application Laid-Open No. 6-75372, Japanese Patent Application Laid-Open No. 6-75373, etc.) (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra ( (Alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (dialkoxyphenyl) biimidazole, 2,2'- Bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole (see Japanese Patent Publication No. 48-38403 and Japanese Patent Publication No. 62-174204 Etc.), an imidazole compound in which a phenyl group at the 4,4 ', 5,5'-position is substituted with an alkoxycarbonyl group (see Japanese Patent Application Laid-Open No. 7-10913, etc.) and the like.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (tri (Chloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperyl-1,3,5-tri Azine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl ) Vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methyl) Phenyl) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl]- 1,3,5-triazine and the like.

Examples of the fluorenylphosphine oxide compound include 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide and the like.

Examples of the polymerization initiator (D) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Benzoin compounds; benzophenone, methyl o-benzylidene benzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenylsulfide, 3, 3 ', 4,4'-tetrakis (third butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, Quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, and the like.

The polymerization initiator (D) is preferably a polymerization containing at least one selected from the group consisting of an alkyl phenone compound, a triazine compound, a fluorenyl phosphine oxide compound, an O-fluorenyl oxime compound, and a biimidazole compound The initiator is more preferably a polymerization initiator containing an O-fluorenyl oxime compound.

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

<Solvent (E)>

The solvent (E) is not particularly limited, and solvents commonly used in this field can be used. Examples include ester solvents (solvents containing -COO- and -O- free), ether solvents (solvents containing -O- and -COO- free), and ether ester solvents (molecular- COO- and -O- solvents), ketone solvents (with -CO- in the molecule and no -COO- solvents), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amidine solvents, dimethyl sulfene, 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, pentyl formate, and isopentyl acetate. Ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, Cyclohexanol acetate, γ-butyrolactone and the like.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol. Ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butane Alcohol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropiperan, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl ether Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether, methyl anisole and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropyl Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionate Ethyl acetate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2 -Ethyl ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl acetate -3-methoxybutyl ester, 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, and 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 glycerol.

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

Examples of the amidine solvent include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

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

Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentyl Ketones, N, N-dimethylformamide, N-methylpyrrolidone, etc., more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol Methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, N-methylpyrrolidone.

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

<Colorless metal complex (F)>

The colored curable resin composition of the present invention may contain a colorless metal complex (F).

Examples of the colorless metal complex (F) include zinc complexes represented by 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.

Examples of the alkyl group having 1 to 4 carbon atoms in the formula (10) include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, and third butyl.

Specific examples of the zinc complex represented by the formula (10) include complexes having a substituent shown in Table 4. Among these, from the viewpoint of heat resistance, (10) -18 is preferred.

The content of the colorless metal complex with respect to the colorant (A) is preferably from 0.1% by mass to 30% by mass, and more preferably from 0.5% by mass to 15% by mass.

<Other ingredients>

The colored hardening resin composition of the present invention may contain a polymerization initiation aid, a leveling agent (H), an antioxidant, a filler, other polymer compounds, an adhesion promoter, a light stabilizer, and a chain transfer agent as required. Etc. Conventional additives in this technical field.

Examples of the leveling agent (H) include a polysiloxane-based surfactant, a fluorine-based surfactant, and a polysiloxane-based surfactant having a fluorine atom. These may have a polymerizable group in a side chain.

The antioxidant is not particularly limited as long as it is an antioxidant generally used in industry, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, or the like can be used.

<Manufacturing method of colored curable resin composition>

The colored curable resin composition of the present invention can be mixed with a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a colorless metal complex (F), And a solvent (E), a leveling agent (H), a polymerization initiation aid, an antioxidant, and other components used as required.

When the pigment (P) is contained, the pigment is preferably partially or completely mixed with the solvent (E) in advance, and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. In this case, a part or all of the pigment dispersant and the resin (B) may be blended as necessary. The intended coloring curable resin composition can be prepared by mixing the remaining components so as to have a predetermined concentration in the pigment dispersion liquid obtained as described above.

The dye of the colorant (A) is preferably prepared by dissolving a part or all of the solvent (E) in advance to prepare a solution. This solution is preferably filtered using a filter having a pore size of about 0.01 to 1 μm.

It is preferable to filter the mixed coloring curable resin composition with a filter having a pore size of about 0.01 to 10 μm.

<Coating film and color filter>

A coating film formed of the colored curable resin composition of the present invention and a color filter formed of the colored curable resin composition are also within the scope of the present invention.

The coating film may be composed of the coloring curable resin. The material is obtained by hardening. The coating film may have a colored pattern.

The film thickness of the coating film is not particularly limited and may be appropriately adjusted depending on the purpose, application, etc., and is usually 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photoetching method, an inkjet method, and a printing method. Among them, a photoetching method is preferred. The photoetching method is a method in which the colored curable resin composition is coated on a substrate and dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photoetching method, a colored coating film of a cured product of the coloring composition layer can be formed without using a mask and / or without developing during exposure. The colored pattern and colored coating film thus formed are the color filters of the present invention.

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

As for the substrate, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, and soda lime glass coated with silicon oxide can be used. Polycarbonate, polymethyl methacrylate, polyterephthalic acid Resin plates, such as ethylene glycol, and silicon, are formed on the substrate with aluminum, silver, silver / copper / palladium alloy films, or the like. On these substrates, additional color filter layers, resin layers, transistors, circuits, etc. can be formed.

The formation of each color pixel by the photo-etching method can be performed by a conventional or conventional device and conditions. It can be produced in the following manner.

First, a colored curable resin composition is applied to a substrate. On the board, a volatile component such as a solvent is removed by drying (pre-baking) and / or drying under reduced pressure and dried to obtain a smooth colored composition layer.

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

The temperature during heating and drying is preferably 30 to 120 ° C, and more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

When drying under reduced pressure, the drying is preferably performed under a pressure of 50 to 150 Pa and a temperature range of 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 color filter.

Then, the colored composition layer is exposed through a mask for forming a desired colored pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use can be used.

As for a light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferred. For example, a filter that blocks light below 350 nm can be used to block the wavelength region, or a band-pass filter that extracts light near 436 nm, 408 nm, and 365 nm can be used to selectively extract these wavelength regions. Specific examples of the light source include a mercury lamp, a light-emitting diode, a metal halide lamp, and a halogen lamp.

In order to illuminate parallel light uniformly on the entire exposure surface, or to correctly align the mask with the substrate on which the colored composition layer is formed, it is preferable to use an exposure device such as a mask alignment exposure machine and a stepper.

By exposing the coloring composition layer after exposure to the developer Development is performed to form a colored pattern on the substrate. The unexposed portion of the colored composition layer is dissolved in a developing solution and removed by development. The developing solution is preferably an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide. The concentration of the basic compound in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. Furthermore, the developing solution may contain a surfactant.

The developing method may be any of a puddle method, a dipping method, a spray method, and the like. Furthermore, the substrate can be tilted at an arbitrary angle during development.

After development, washing with water is preferred.

Furthermore, it is preferable 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 1 to 120 minutes, and more preferably 10 to 60 minutes.

By using the coloring curable resin composition of the present invention, a color filter excellent in heat resistance can be produced.

The color filter is a color filter that can be used as a display device (for example, a liquid crystal display device, an organic EL device, an electronic paper, and the like) and a solid-state imaging element. A display device containing the color filter is also one of the present invention.

(Example)

Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to these examples. In the examples, the percentages and parts representing the content or usage amount are used as the basis of quality when there is no special definition.

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

Synthesis Example 1

The following reactions were performed under a nitrogen atmosphere. After placing 32.2 parts of potassium thiocyanate and 160.0 parts of acetone in a flask equipped with a cooling tube and a stirring device, the mixture was stirred at room temperature for 30 minutes.

Then, 50.0 parts of 2-fluorobenzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. After the reaction mixture was ice-cooled, 40.5 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of the dropwise addition, the reaction mixture was further stirred at room temperature for 30 minutes.

Then, after the reaction mixture was ice-cooled, 34.2 parts of a 30% sodium hydroxide aqueous solution was added dropwise. After completion of the dropwise addition, the reaction mixture was further stirred at room temperature for 30 minutes. Then, 31.3 parts of chloroacetic acid was added dropwise at room temperature. After the dropwise addition was completed, the mixture was stirred under heating and refluxing for 7 hours. After cooling the reaction mixture to room temperature, the reaction solution was poured into 120.0 parts of tap water, and then 200 parts of toluene was added and stirred for 30 minutes. Then, the stirring was stopped, and the resulting mixture was allowed to stand for 30 minutes, and then separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then washed with 200 parts of tap water, and finally washed with 200 parts of saturated saline.

An appropriate amount of magnesium sulfate was added to the organic layer, and after stirring for 30 minutes, it was filtered to obtain a dehydrated organic layer. The solvent was distilled off from the obtained organic layer by an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60 ° C to obtain 49.9 parts of a compound represented by the formula (B-I-7). Yield: 51%

Synthesis Example 2

The following reactions were performed under a nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 9.9 parts of a compound represented by formula (BI-7) and 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) ) After 10.0 parts of toluene and 20.0 parts of toluene, 14.8 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 isopropanol. Then, the diluted reaction solution was poured into 300.0 parts of saturated saline, and then 100 parts of toluene was added and stirred for 30 minutes. Then, the stirring was stopped, and after standing for 30 minutes, it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of magnesium sulfate was added to the organic layer, and after stirring for 30 minutes, it was filtered to obtain a dehydrated organic layer. The solvent was distilled off from the obtained organic layer by an evaporator to obtain a blue-violet solid. The obtained blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried under reduced pressure at 60 ° C to obtain 17.2 parts of a compound represented by the formula (A-II-7). 85% yield

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

(Mass analysis) Ionization mode = ESI +: m / z = 619.3 [M-Cl] ⁺ Exact Mass: 654.3

Synthesis Example 3

10 parts of 5-allyl-3-methoxysalicylic acid methyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 200 parts of water and 100 parts of methanol, and then 1.8 parts of sodium hydroxide was added at 50 ° C. Heat for 2 hours. After cooling, the reaction solution was added to 200 parts of ice water, and after stirring for 1 hour, hydrochloric acid was added until the pH became 2. The resulting precipitate was filtered and washed with 200 parts of ion-exchanged water to obtain 8.5 parts of a compound represented by the formula (BC-14-A).

Synthesis Example 4

8.5 parts of the compound represented by the formula (BC-14-A) was added to 20 parts of methanol, 0.8 part of sodium hydroxide was added, and the mixture was stirred at 30 ° C for 1 hour. Then, 1.2 parts of boron was added to the reaction mixture, and it stirred at room temperature for 1 hour. After that, the mixture was stirred at 80 ° C for 2 hours. After cooling, the generated precipitate was filtered, and It was washed with 200 parts of ion-exchanged water, and the obtained white solid was dried at 60 ° C. for 24 hours to obtain 6.8 parts of an anion represented by the formula (BC-14-Na).

Example 1

The following reactions were performed under a nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 10.0 parts of a compound represented by formula (A-II-7), 6.7 parts of a compound represented by formula (BC-14-Na), and N, N-dimethyl After 100.0 parts of formamidine, it was stirred at 50 to 60 ° C for 3 hours.

Then, the reaction mixture was cooled to room temperature, and then dropped into 2000.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to obtain a turquoise solid. The cyan-green solid was further dried under reduced pressure at 60 ° C to obtain 12.0 parts of a compound represented by the formula (A-I-7). Yield: 83%

Synthesis Example 5

In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was flowed into a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was placed, and heated to 85 ° C while stirring. Then, 19 parts of methacrylic acid, 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, and 3,4-epoxy tricyclic acrylic [5.2.1.0] ^2,6] dec-9-yl ester of (content ratio in terms of molar ratio of 50:50) (trade name "E-DCPA", Daicel Co., Ltd.) were dissolved in 171 parts of propylene glycol monomethyl ether The solution of 40 parts of acetate was dripped into the flask using a drip pump for about 5 hours. On the other hand, a solution obtained by dissolving 26 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate was used. It took about 5 hours for another drip pump to drip into the flask. After the dripping of the polymerization initiator was completed, it was kept at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin (B-1)) having a solid content of 43.5%. The weight average molecular weight of the resin (B-1) is 8000, the molecular weight distribution is 1.98, and the acid value in terms of solid content is 53 mg-KOH / g.

The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.

Device: HLC-8120GPC (TOSOH (stock) system)

Column: TSK-GELG2000HXL

Column temperature: 40 ℃

Solvent: THF

Flow rate: 1.0mL / min

Tested liquid solid content concentration: 0.001 to 0.01% by mass

Injection volume: 50 μL

Detector: RI

Calibration Standards: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (made by TOSOH)

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

Synthesis Example 6

250.4 parts of propylene glycol monomethyl ether acetate was taken in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, and the temperature was increased to 120 ° C. while being replaced with nitrogen. Then add 6.13 parts of third butyl hydroperoxide (PERBUTYL O manufactured by Japan Oils and Fats Co., Ltd.) to 37.4 parts of methacrylic acid, 61.3 parts of benzyl methacrylate, 18.5 parts of glycidyl methacrylate, and having In a monomer mixture of 19.2 parts of tricyclodecane skeleton monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.). This was dropped into the flask from the dropping funnel over 2 hours, and further stirred at 120 ° C. for 2 hours for aging. Then, the inside of the flask was replaced with air. In 10.6 parts of acrylic acid, 0.9 parts of tris-dimethylaminomethylphenol (DMP-30) and 0.145 parts of hydroquinone were put into the matured ones, and continued at 120 ° C. After 6 hours of reaction, a solution of a copolymer (resin (B-2)) having a solid content of 38.4% by mass and an acid value of 122 mg-KOH / g was obtained. The weight average molecular weight Mw of the obtained resin (B-2) was 10,700, and the molecular weight distribution was 2.18. The weight average molecular weight and molecular weight distribution were measured by the same method as the resin (B-1).

[Preparation of colored curable resin composition]

Example 2

A coloring curable resin composition is obtained by mixing: a colorant (A): 20 parts of a dye represented by formula (AI-7); a colorant (A): 6 parts of a dye represented by formula (3-11) ; 53 parts of alkali-soluble resin (B): resin (B-2) (in terms of solid content conversion); polymerizable compound (C): dineopentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; Japanese chemical medicine ( 16); polymerization initiator (D): N-benzyloxy-1- (4-phenylmercaptophenyl) octane-1-one-2-imine (IRGACURE (registered Trademark) OXE-01; manufactured by BASF Corporation; O-fluorenyl oxime compound) 4.1 parts; solvent (E): propylene glycol monomethyl ether acetate 120 parts; solvent (E): 4-hydroxy-4-methyl- 380 parts of 2-pentanone; leveling agent (H): 0.12 parts of polyether modified polysiloxane (Toray Silicone SH8400; manufactured by DOW CORNING TORAY (shares)); antioxidant: 0.2 parts of SUMILIZER GP; and zinc complex (F): (10) -18 6.1 parts.

Comparative Example 1

A coloring curable resin composition is obtained by mixing: colorant (A): 26 parts of a dye represented by formula (A-III-1); alkali-soluble resin (B): resin (B-1) (solid matter) Content conversion) 53 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (Registered trademark) DPHA; 16 parts made by Nippon Kayaku Co., Ltd .; polymerization initiator (D): N-benzyloxy-1- (4-phenylmercaptophenyl) octane-1- Keto-2-imine (IRGACURE (registered trademark) OXE-01; manufactured by BASF Corporation; O-fluorenyl oxime 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): 0.15 parts of polyether modified polysiloxane (Toray Silicone SH8400; manufactured by DOW CORNING TORAY (stock)).

[Production of color filters]

This colored curable resin composition was spin-coated on a 2-inch square glass substrate (# 1737; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes to form a colored composition layer. After cooling, exposure was performed using an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) at an exposure amount (based on 365 nm) of 150 mJ / cm ² in an atmospheric environment. Furthermore, no photomask is used. The coloring composition layer after exposure was placed in an oven and post-baked at 180 ° C for 20 minutes to produce a color filter (film thickness 2.8 μm).

[Evaluation of heat resistance]

The coating film of the colored photosensitive resin composition was heated at 230 ° C. for 20 minutes, and the color difference (ΔEab *) of the coating film before and after heating was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS). The coating film obtained in Example 2 was subjected to the above-mentioned heat resistance evaluation. As a result, the color difference (ΔEab *) was 6.2. As a result of carrying out heat resistance evaluation in the same manner as Comparative Example 1, the color difference (ΔEab *) was 12.1, and it was found that the compound of the present case was excellent in heat resistance.

(Industrial availability)

Use of a color-setting curable resin composition containing the dye compound of the present invention can provide a color filter excellent in heat resistance. The color filter is a color filter that can be used as a display device (for example, a liquid crystal display device, an organic EL device, an electronic paper, and the like) and a solid-state imaging element.

Claims (11)

A dye compound comprising: a dye cation and an anion having two or more reactive groups, wherein the anion is the anion represented by formula (A):

M represents a boron atom or an aluminum atom; R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ independently represent a hydroxyl group, a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or reactivity However, at least one of R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ is a reactive group; and wherein the aforementioned reactive group is a group having an ethylenically unsaturated bond. The dye compound as described in item 1 of the patent application range, wherein the anion is an anion having a boron atom or an anion having an aluminum atom. The dye compound as described in item 1 or item 2 of the patent application scope, wherein the dye cation is a cation represented by formula (A-VI):

R ^1A to R ^8A independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms (between the carbon atoms constituting the alkyl group) Insert an oxygen atom); R ^9A to R ^12A each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (between the carbon atoms constituting the alkyl group) which may be substituted by an amine group, a dialkylamine group or a halogen atom (Oxygen atom can be inserted), an alicyclic hydrocarbon group having 3 to 20 carbon atoms or an aryl group which may be substituted; R ^9A and R ^10A may be bonded and form a ring together with these bonded nitrogen atoms, R ^11A and R ^12A may bond and form a ring together with the nitrogen atoms to which it is bonded; A represents an aromatic hydrocarbon group which may have a substituent, or a heteroaromatic group which may have a substituent. A coloring agent containing the dye compound as described in item 1 or 2 of the patent application. The coloring agent as described in item 4 of the patent application scope further contains at least one dye selected from the group consisting of anthraquinone dyes and porphyrazine dyes. The coloring agent as described in item 4 or 5 of the patent application scope further contains pigments. A coloring curable resin composition containing a coloring agent (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D ), And the solvent (E). The color-curing resin composition as described in item 7 of the patent application scope further contains a colorless metal complex (F). A coating film formed of the color-curing resin composition as described in item 7 or 8 of the patent application. A color filter formed from the color-curing resin composition as described in item 7 or 8 of the patent application. A display device containing the color filter as described in item 10 of the patent application scope.