TWI693216B - Compound, color-curing resin composition containing the compound, color filter and display device - Google Patents

Abstract

The object of the present invention is to provide a compound having excellent absorbance.

The present invention relates to a compound, which is represented by formula (AI):

[R ^1a ~ R ^8a are hydrogen atom, alkyl group, SO ₃ ^- group or SO ₃ M group; R ^9a , R ^10a are hydrogen atom, alkyl group, aromatic hydrocarbon group, or aralkyl group; R ^11a ~ R ^20a are Hydrogen atom, alkyl group, halogen atom, SO ₃ ^- group or SO ₃ M group; R ^45a and R ^46a are hydrogen atom, alkyl group, aromatic hydrocarbon group; R ^55a is hydrogen atom, alkyl group, aromatic hydrocarbon group]; this The invention also provides a color-curing resin composition, a color filter, and a display device including the compound.

Description

Compound, color-curing resin composition containing the compound, color filter and display device

The present invention relates to a compound useful as a pigment.

Patent Document 1 discloses C.I. Acid Blue 90 as a blue dye for color filters contained in a liquid crystal display device or the like or a solid-state imaging element. The acid blue 90 has the chemical structure shown below and is classified as a preferred dye in the above-mentioned Patent Document 1.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 4236559

The object of the present invention is to provide a compound with high absorbance, and to provide a color-curing resin composition containing such a compound.

The present invention includes the following inventions.

[1] A compound represented by formula (AI),

[In formula (AI), R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a and R ^8a each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and SO ₃ ^- group Or SO ₃ M group; R ^9a and R ^10a independently represent a hydrogen atom, an alkyl group having 1 to 10 carbons, an aromatic hydrocarbon group which may be substituted, or an aralkyl group which may be substituted; R ^11a to R ^20a respectively It independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogen atom, an SO ₃ ^- group or an SO ₃ M group; in the above R ^1a to R ^20a , the above alkyl group may also constitute a methylene group constituting the above An oxygen atom is inserted between; R ^45a and R ^46a independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group which may be substituted; R ^55a 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 ^45a , R ^46a , and R ^55a , for the above alkyl group, an oxygen atom may also be inserted between the methylene groups constituting it; M represents a hydrogen ion, a metal ion, or an ammonium ion ; Among them, R ^1a ~ R ^20a , R ^45a , R ^46a and R ^55a meet at least any of the requirements of (1), (2) and (3), and the requirements of (4): (1) R ^1a ~ R ^8a And at least one of R ^11a to R ^20a is an SO ₃ ^- group or SO ₃ M group; (2) at least one of R ^9a , R ^10a , R ^45a , R ^46a and R ^55a has an SO ₃ ^- group or SO ₃ M Aromatic hydrocarbon groups with substituents as substituents; (3) At least one of R ^9a and R ^10a is an aralkyl group having a SO ₃ ^- group or SO ₃ M group as a substituent on the ring; (4) Formula (AI) The number of SO ₃ ^- groups in the compound represented is 1, and the number of SO ₃ M groups is 0~6].

[2] A color-curing resin composition comprising the compound represented by the formula (A-I) in [1] above.

[3] A color filter formed by using the color-curable resin composition as described in [2] above.

[4] A display device comprising the color filter as described in [3] above.

The compounds of the present invention have higher absorbance. If a coloring curable resin composition containing such a compound is used, the amount of colorant used can be suppressed.

The compound of the present invention is a compound represented by formula (A-I) (hereinafter sometimes referred to as compound (A-I)). The compounds of the present invention also include tautomers or their equivalents.

[Chemical 3]

[In formula (AI), R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a and R ^8a each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and SO ₃ ^- group Or SO ₃ M group.

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

R ^11a to R ^20a independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogen atom, an SO ₃ ^- group or an SO ₃ M group.

In the above R ^1a to R ^20a , an oxygen atom may be inserted between the methylene groups constituting the above alkyl group.

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

R ^55a 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 ^45a , R ^46a , and R ^55a , an oxygen atom may be inserted between the methylene groups constituting the above alkyl group.

M represents hydrogen ion, metal ion or ammonium ion.

Among them, R ^1a ~ R ^20a , R ^45a , R ^46a and R ^55a meet at least any of the requirements of (1), (2) and (3), and the requirements of (4).

(1) At least one of R ^1a to R ^8a and R ^11a to R ^20a is an SO ₃ ^- group or an SO ₃ M group.

(2) At least one of R ^9a , R ^10a , R ^45a , R ^46a and R ^55a is an aromatic hydrocarbon group having a SO ₃ ^- group or SO ₃ M group as a substituent.

(3) At least one of R ^9a and R ^10a is an aralkyl group having an SO ₃ ^- group or an SO ₃ M group as a substituent on the ring.

(4) The number of SO ₃ ^- groups in the compound represented by formula (AI) is 1, and the number of SO ₃ M groups is 0~6]

The valence of the compound of formula (A-I) is 0.

The alkyl group represented by R ^1a to R ^20a may be any of linear, branched and cyclic. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, and decyl groups. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 6 carbon atoms.

The cyclic alkyl group represented by R ^1a to R ^20a may be monocyclic or polycyclic. Examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. The cyclic alkyl group preferably has 3 to 10 carbon atoms, more preferably 6 to 10 carbon atoms.

Specific examples of the alkyl group represented by R ^1a to R ^20a include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl; isopropyl, and Dibutyl, tertiary butyl, isopentyl, 1-methylpentyl, 2-ethylbutyl and other branched chain alkyl groups; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantane Examples of cyclic alkyl groups such as groups include groups represented by the following formulas. In the following formula, * represents a bonding key.

Among the groups represented by R ^1a to R ^20a , examples of the group having an oxygen atom inserted between the methylene groups constituting the alkyl group include, for example, groups represented by the following formulas. In the following formula, * represents a bonding key.

The group having an oxygen atom inserted 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 for inserting an oxygen atom is preferably a linear alkyl group. In addition, the number of carbons between oxygen atoms is preferably 1 to 4, more preferably 2 to 3.

In R ^9a to R ^10a , examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 10 carbon atoms such as phenyl and naphthyl.

In R ^9a to R ^10a , examples of the aromatic hydrocarbon group in the aralkyl group include phenyl and naphthyl. The carbon number of the aralkyl group is preferably 7-20.

Among the groups represented by R ^9a to R ^10a , examples of the substituents in the aromatic hydrocarbon group and the aralkyl group include halogen atoms such as fluorine atoms, chlorine atoms, and iodine; carbon numbers such as methoxy groups and ethoxy groups 1 to 6 alkoxy groups; hydroxyl groups; methyl, ethyl, propyl and other alkyl groups with 1 to 6 carbon atoms; sulfamoyl groups; mesylate and other carbon groups with 1 to 6 carbon atoms; methyl groups Oxycarbonyl, ethoxycarbonyl; -SO ₃ H group; -SO ₃ ^- group; alkoxycarbonyl group with the same carbon number of 1~6, etc.

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

Specific examples of the aralkyl group which may be substituted include a group in which methylene groups are bonded to the bonding bonds of the following specific examples of aromatic hydrocarbon groups.

[化6]

Among the groups represented by R ^11a to R ^20a , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and a fluorine atom is preferred.

In terms of ease of synthesis, R ^1a to R ^8a are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a methyl group.

In terms of ease of synthesis, R ^9a to R ^10a are each independently preferably 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. It is preferably an alkyl group having 1 to 8 carbons, a phenyl group, a naphthyl group, a phenyl group having a methyl group, a naphthyl group having a methyl group; unsubstituted or selected from halogen atoms, methoxy groups, ethoxy groups, amines One or more of sulfonyl, mesylate, methoxycarbonyl, and ethoxycarbonyl, especially a substituted aralkyl group, each independently and preferably a linear alkyl group having 1 to 4 carbon atoms base.

In terms of heat resistance, R ^11a to R ^{12a are} preferably at least one of a halogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably at least one of a halogen atom or an alkyl group having 1 to 8 carbon atoms. It is further preferred that at least any one is a fluorine atom or an alkyl group having 1 to 4 carbon atoms.

In terms of heat resistance, R ^13a to R ^{14a are} preferably at least any one of a halogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably at least any one is a halogen atom or an alkyl group having 1 to 8 carbon atoms. It is further preferred that at least any one is a fluorine atom or an alkyl group having 1 to 4 carbon atoms.

In terms of ease of synthesis, R ^15a to R ^20a are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Furthermore, a hydrogen atom or a methyl group is preferable.

Examples of the alkyl group in R ^45a and R ^46a include an alkyl group having 1 to 10 carbon atoms in R ^1a to R ^20a .

In R ^45a and R ^46a , specific examples of the alkyl group having 1 to 10 carbon atoms include groups represented by the following formulas. In the following formula, * represents a bonding key. Among them, the alkyl group having 1 to 8 carbon atoms is preferred, the alkyl group having 1 to 6 carbon atoms is more preferred, and the alkyl group having 1 to 4 carbon atoms is particularly preferred.

[Chem 8]

In R ^45a and R ^46a , as a group in which an oxygen atom is inserted between the methylene groups constituting the alkyl group, a group represented by the following formula may be mentioned. In the following formula, * represents a bonding key. The alkyl group for inserting an oxygen atom is preferably a linear alkyl group. In addition, the number of carbons between oxygen atoms is preferably 1 to 4, more preferably 2 to 3.

The group having an oxygen atom inserted 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 for inserting an oxygen atom is preferably a linear alkyl group. In addition, the number of carbons between oxygen atoms is preferably 1 to 4, more preferably 2 to 3.

Examples of the aromatic hydrocarbon group in R ^45a and R ^46a include aromatic hydrocarbon groups having 6 to 10 carbon atoms such as phenyl and naphthyl.

Examples of the aromatic hydrocarbon groups represented by R ^45a and R ^46a include halogen atoms such as fluorine atoms, chlorine atoms, and iodine as substituents; haloalkyl groups having 1 to 6 carbon atoms such as chloromethyl and trifluoromethyl; Alkoxy groups with 1 to 6 carbon atoms such as methoxy and ethoxy; hydroxyl; alkyl groups with 1 to 6 carbon atoms such as methyl, ethyl and propyl; sulfamoyl; carbon numbers such as mesylate Alkylsulfonyl groups of 1 to 6; alkoxycarbonyl groups of 1 to 6 carbon atoms such as methoxycarbonyl; -SO ₃ H group; -SO ₃ ^- group and so on.

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

In terms of ease of synthesis, R ^45a and R ^46a are each independently preferably a C 1-10 alkyl group or an aromatic hydrocarbon group that may be substituted, more preferably a halogen atom, a C 1 to 4 Haloalkyl, alkoxy having 1 to 4 carbons, hydroxyl, alkyl having 1 to 4 carbons, or aromatic hydrocarbon group which may be substituted with mesylate, or alkyl having 1 to 8 carbons It is 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 bonding key.

Examples of the alkyl group in R ^55a include the alkyl groups in R ^1a to R ^20a .

In R ^55a , specific examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, Straight chain alkyl groups such as n-decyl; isopropyl, second butyl, third butyl, isopentyl, 1-methylpentyl, 1-propylbutyl and other branched chain alkyl groups; cyclopropyl Examples of the cyclic alkyl group such as a group, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl group include groups represented by the following formulas. In the following formula, * represents a bonding key. Among them, the alkyl group having 1 to 8 carbon atoms is preferred, the alkyl group having 1 to 6 carbon atoms is more preferred, and the alkyl group having 1 to 4 carbon atoms is particularly preferred.

In R ^55a , as a group in which an oxygen atom is inserted between the methylene groups constituting the alkyl group, for example, a group represented by the following formula may be mentioned. In the following formula, * represents a bonding key. The alkyl group for inserting an oxygen atom is preferably a linear alkyl group. In addition, the number of carbons between oxygen atoms is preferably 1 to 4, more preferably 2 to 3.

In R ^55a , examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 10 carbon atoms, such as phenyl and naphthyl, preferably phenyl.

In R ^55a , as a substituent in the aromatic hydrocarbon group, a halogen atom such as a fluorine atom, a chlorine atom, and iodine; a halogen alkyl group having 1 to 6 carbon atoms such as chloromethyl and trifluoromethyl; methoxy , Ethoxy and other alkoxy groups having 1 to 6 carbon atoms; hydroxy; methyl and ethyl and other alkyl groups having 1 to 6 carbon atoms; sulfamoyl; mesylate and other alkyl groups with 1 to 6 carbon atoms Acyl; alkoxycarbonyl such as methoxycarbonyl with 1 to 6 carbon atoms; -SO ₃ H group; -SO ₃ ^- group and so on. Specific examples of the aromatic hydrocarbon group which may be substituted include groups represented by the following formulas. In the following formula, * represents a bonding key.

[化14]

In terms of ease of synthesis, R ^{55a is} preferably an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group which may be substituted, more preferably an alkyl group having 1 to 8 carbon atoms or a halogen atom, and having 1 carbon atom ~4 haloalkyl group, alkoxy group having 1 to 4 carbon atoms, hydroxyl group, alkyl group having 1 to 4 carbon atoms, or aromatic hydrocarbon group which may be substituted with mesylate group, preferably represented by the following formula Of aromatic hydrocarbon groups. In the following formula, * represents a bonding key.

[化15]

In M, examples of metal ions include alkali metal ions such as lithium ions, sodium ions, and potassium ions.

In M, the ammonium ion is preferably a quaternary ammonium ion such as a tetraalkylammonium ion. The quaternary ammonium ion is useful when it is contained in the colored curable resin composition.

In terms of absorbance, M is preferably a hydrogen ion or an alkali metal ion, more preferably a hydrogen ion.

The number of SO ₃ ^- groups possessed by the compound represented by formula (AI) is 1. In addition, the base number of SO ₃ M can be appropriately set within a range of 0 to 6, more preferably 1 to 3, and further preferably 1. In the compound (AI), the SO ₃ ^- group and the SO ₃ M group may also be provided as substituents represented by R ^1a to R ^8a and R ^11a to R ^20a , and may also be used as the following (1a) and (2a) With a substituent.

(1a) Substituents in the aromatic hydrocarbon groups represented by R ^9a , R ^10a , R ^45a , R ^46a and R ^55a

(2a) The substituent on the ring in the aralkyl group represented by R ^9a and R ^10a

The SO ₃ ^- group and the SO ₃ M group can also be bonded to the same aromatic ring, but in most cases they are bonded to different aromatic rings.

The valence of compound (A-I) is 0, which is an electrically neutral compound.

Examples of the compound represented by the formula (A-I) include compounds 1 to 90 represented by the formula (A-I-1).

[In formula (AI-1), R ^9a to R ^20a , R ^45a , R ^46a and R ^{55a are} shown in Table 1 to Table 6. Wherein, the compound of formula (AI-1) has at least one of SO ₃ ^- group and SO ₃ H group as any substituent of R ^1a to R ^8a , R ^11a to R ^20a , (1a) and (2a) ]

[Table 1]

In Table 1 to Table 6, Ph1 to Ph5 are as follows. In the following formula, * represents a bonding key.

Among them, the compound represented by formula (A-I-1) is preferably compound 31 to compound 90, more preferably compound 46 to compound 60.

Compound (AI) can be produced by sulfonation of a compound of formula (A-II) (hereinafter sometimes referred to as compound (A-II)). Examples of the compound (A-II) include hydrochloride, phosphate, perchlorate, BF ₄ salt, and PF ₆ salt.

[In the formula, 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 respectively Independently represents 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 to R ^20a independently represent a hydrogen atom and 1 to 10 carbon atoms An alkyl group or a halogen atom; in the above R ^1a to R ^20a , an oxygen atom may also be inserted between the methylene groups constituting the above alkyl group; R ^45a and R ^46a each independently represent a hydrogen atom and a carbon number 1 to 10 alkyl group, or an aromatic hydrocarbon group which may be substituted; R ^55a 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 ^45a , R ^46a , and R ^55a , for the alkyl group, may also be inserted to constitute the ethylene-methyl oxygen atom; M ¹ represents Cl ^-, phosphate ions, perchlorate, BF ₄ salt or a PF ₆ salt]

As the method of sulfonation, various known methods can be cited, for example, the methods described in Journal of Organic Chemistry, (1994), vol. 59, #11, p. 3232~3236.

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

[In formula (BI) and formula (CI), R ^1a to R ^20a , R ^45a , R ^46a and R ^55a represent the same meaning as above]

Moreover, the compound (A-II) can also be produced by reacting the compound represented by the formula (B-II) with the compounds represented by the formula (C-II) and the formula (C-III). This reaction can be carried out in the presence of an organic solvent or in the absence of a solvent.

[In formula (B-II), formula (C-II), and formula (C-III), R ^1a to R ^20a , R ^45a , R ^46a and R ^55a have the same meanings as above]

It is preferable that the compound represented by the formula (C-II) and the compound represented by the formula (C-III) are the same.

Relative to the compound represented by the formula (BI), the amount of the compound represented by the formula (CI) is preferably 0.5 mol or more and 8 mol or less with respect to the compound represented by 1 mol (BI), more Preferably, it is 1 mole or more and 3 mole or less.

Relative to the compound represented by the formula (B-II), the total usage amount of the compound represented by the formula (C-II) and the compound represented by the formula (C-III) is relative to that expressed by 1 mole formula (B-II) The compound represented is preferably 0.5 mol or more and 8 mol or less, more preferably 1 mol or more and 3 mol or less.

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

In terms of yield, any reaction is preferably carried out 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 groups such as nitrobenzene Hydrocarbon solvents; ketone solvents such as methyl isobutyl ketone; amide solvents such as 1-methyl-2-pyrrolidone. The amount of the organic solvent used is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 2 parts by mass or more, and 10 parts by mass relative to 1 part by mass of the compound represented by formula (BI) or formula (B-II). the following.

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 chloride, sulfuric acid, and sulfenyl 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 relative to 1 part by mass of the compound represented by formula (BI) or formula (B-II). the following.

The method for obtaining the compound (A-II) from the reaction mixture is not particularly limited, and various known methods can be used. For example, a method of mixing the reaction mixture with a solvent such as alcohol (for example, methanol) and the like, and filtering the precipitated crystals by filtration. Preferably, the reaction mixture is added to the above-mentioned solvent such as alcohol. The temperature at the time of adding the reaction mixture is preferably -100°C or higher and 50°C or lower, more preferably -80°C or higher and 0°C or lower. Moreover, it is preferable to perform stirring at the same temperature for about 0.5 to 2 hours thereafter. The crystals collected by filtration are preferably washed with water or the like and then dried. Furthermore, if necessary, purification may be further carried out by a known method such as recrystallization.

As methods for producing compound (B-I) and compound (B-II), various well-known methods can be cited, for example, the method described in West German Patent Application No. P3928243.0.

Examples of the method for producing the compound (C-II) and the compound (C-III) include various known methods such as the method described in International Publication No. 2012/053211.

When the compound (CI) is R ^9a and R ^10a being an alkyl group or an aralkyl group, the compound represented by formula (C-IV) (hereinafter referred to as compound (C-IV)) and an alkylating agent or The aralkylating agent is reacted to produce the compound (C-IV) by using a compound represented by formula (CV) (hereinafter referred to as compound (CV)) and a compound represented by formula (C-VI) ( Hereinafter referred to as compound (C-VI)) is produced by reacting. Furthermore, regardless of the type of R ^9a and R ^10a , the compound (CI) can be directly produced from the compound (CV) and the compound (C-VI).

(In the formula, R ^1a to R ^20a are the same as 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 R ^15a and R ^{18a is the} same, R ^{5B is the} same as R ^16a and R ^19a , R ^{6B is the} same as R ^17a and R ^20a ; R ^7B and R ^8B are halogen atoms).

As the alkylating agent, publicly known alkylating agents such as alkyl halogens and sulfates can be used, and in particular, the ease of obtaining is preferably an alkyl halogen, and the ease of synthesis is particularly preferably a first-class Alkyl iodide. As the aralkylating agent, benzyl halogen or the like can be used.

Examples of the alkylating agent specifically include methyl iodide, ethyl iodide, iodo-n-butane, bromoethane, bromo-n-butane, dimethyl sulfate, and diethyl sulfate. Specific examples of the aralkylating agent include benzyl iodide and benzyl bromide.

The amount of the alkylating agent or aralkylating agent used is preferably 2 moles or more, 6 moles or less, more preferably 2 moles or more, relative to the compound represented by 1 mole formula (C-IV) , Below 4 moles.

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

In terms of yield, any reaction is preferably carried out 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 hydrocarbon solvents such as nitrobenzene Ketone solvents such as methyl isobutyl ketone; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, 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, and more preferably 2 parts by mass or more and 10 parts by mass or less relative to 1 part by mass of the compound represented by the formula (C-IV).

In terms of yield, the above reaction is preferably carried out in the presence of an alkaline substance. Examples of the basic substance include sodium hydride, LDA (Lithium diisopropylamide, lithium diisopropylamide), DIBAL (Diisobutyl Aluminium), potassium tertiary butoxide, and the like.

The use amount of the alkaline substance is preferably 2 mol or more and 6 mol or less, more preferably 2 mol or more and 4 mol or less relative to the compound represented by 1 mol formula (C-IV).

The method for obtaining the compound (C-I) from the reaction mixture is not particularly limited, and various known methods can be used. For example, a method of mixing the reaction mixture with a solvent such as alcohol (for example, methanol) and the like, and filtering the precipitated crystals by filtration. The reaction mixture is preferably added to the above-mentioned solvent such as alcohol. The temperature at the time of adding the reaction mixture is preferably -100°C or higher and 50°C or lower, more preferably -80°C or higher and 0°C or lower. Further, thereafter, it is preferable to perform stirring at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are preferably washed with water or the like and then dried. Furthermore, if necessary, purification may be further carried out by a known method such as recrystallization.

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

In the formula (C-VI), examples of the halogen atom represented by R ^7B and R ^8B include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of ease of obtaining raw materials, it is preferably Fluorine atom, chlorine atom.

The amount of the compound (C-V) used is preferably 2 mol or more and 5 mol or less, more preferably 2 mol or more and 3 mol or less relative to 1 mol compound (C-VI).

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

In terms of yield, any reaction is preferably carried out 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 hydrocarbon solvents such as nitrobenzene Ketone solvents such as methyl isobutyl ketone; N,N-dimethylformamide, N,N-dimethyl Acetamide solvents such as acetamide and 1-methyl-2-pyrrolidone. The use amount of the organic solvent is preferably 1 part by mass or more and 20 parts by mass or less, and more preferably 2 parts by mass or more and 10 parts by mass or less relative to 1 part by mass of the compound represented by the formula (C-VI).

In terms of yield, the above reaction is preferably carried out in the presence of a palladium compound, a phosphine compound and a basic substance.

Examples of the palladium compound include palladium (II) acetate, palladium (II) chloride, palladium (II) bromide, bis (2,4-glutaric acid) palladium (II), and bis (dibenzylideneacetone) Palladium (0), tris (dibenzylideneacetone) dipalladium (0), etc.

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

Examples of phosphine compounds include: dppf (Bis (diphenylphosphino) ferrocene, bis (diphenylphosphino) ferrocene), Xantphos (4,5-bis (diphenylphosphine)-9,9-dimethyloxa Anthracene), BINAP((±)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthalene, (±)-2,2'-bis-(diphenylphosphino)-1,1'-linked Naphthalene), Xphos (2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl), Sphos (2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl ), MePhos (2-dicyclohexylphosphine-2'-methylbiphenyl), etc.

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

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

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

The method for obtaining the compound (C-IV) from the reaction mixture is not particularly limited, and various known methods can be used. For example, a method of mixing the reaction mixture with a solvent such as alcohol (for example, methanol) and the like, and filtering the precipitated crystals by filtration. The reaction mixture is preferably added to the above Alcohol and other solvents. The temperature at the time of adding the reaction mixture is preferably -100°C or higher and 50°C or lower, more preferably -80°C or higher and 0°C or lower. Further, thereafter, it is preferable to perform stirring at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are preferably washed with water or the like and then dried. Moreover, if necessary, it can be further purified by a known method such as recrystallization.

The compound (A-I) of the present invention can be applied to fiber products. For example, the fiber material can be colored by kneading into the fiber material, impregnation, adhesion, etc. In addition, the compound (A-I) of the present invention can be included in the colored curable resin composition as a dye of a colorant (hereinafter sometimes referred to as "colorant (A)"). The colored curable resin composition preferably further contains a resin (B), and more preferably contains a polymerizable compound (C), a polymerization initiator (D), and a solvent (E). Moreover, it is also preferable to further contain a polymerization initiation aid (D1), a leveling agent (F), and the like.

In this specification, the compounds exemplified as each component can be used alone or in combination of plural types unless otherwise specified.

<Colorant (A)>

As the colorant (A), a dye using the compound (AI) of the present invention as an active ingredient may be used alone, but other dyes (A1), pigments (P), or Wait for the mixture.

染料、酞菁染料、萘醌染料、醌亞胺染料、次甲基染料、次甲基偶氮染料、方酸鎓染料、吖啶染料、苯乙烯基染料、香豆素染料、喹啉染料及硝基染料等。該等中，較佳為使用有機溶劑可溶性染 料。 Examples of the dye (A1) include oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes. For example, according to the color index (The Published by Society of Dyers and Colourists) and classified as a dye compound, or a well-known dye described in Dyeing Notes (Dyeing Society). Moreover, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes,

Dyes, phthalocyanine dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, methine azo dyes, squarium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and Nitro dyes, etc. Among these, organic solvent-soluble dyes are preferably used.

Specifically, CI solvent yellow 4 (hereinafter, CI solvent yellow is omitted, only the number is described), 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; CI Solvent Red 24, 45, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150 , 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; CI Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99; CI Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97 , 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 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, 17, 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 Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75 , 94, 95, 107, 108, 149, 162, 169, 173; CI Acid Red 73, 80, 91, 92, 97, 138, 151, 211, 274, 289; CI Acid Green 3, 5, 9, 25 , 27, 28, 41; CI Acid Violet 34, 120; CI Acid Blue 25, 27, 40, 45, 78, 80, 112 and other CI acid dyes, CI Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141; CI direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct Violet 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 51, 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 dyes such as CI basic green 1, CI reactive yellow 2, 76, 116; CI reactive orange 16, CI reactive dyes such as CI reactive red 36, 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, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32, 33, 36, 37, 38, 39, 41, 43 , 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; 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 violet 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, 49, 53, 61, 74, 77, 83, 84; CI mordant green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34 , CI mordant dyes such as CI, 35, 41, 43, 53 and CI vat dyes such as CI Vat Green 1, etc.

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

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

染料。作為

染料，可使用公知之物質。例如，較佳為式(1)所表示之化合物。 Also, regarding the classification according to the chemical structure, it is preferably

dye. As

As the dye, known substances can be used. For example, the compound represented by formula (1) is preferred.

[In formula (1), R ¹ and R ² each independently represent a phenyl group which may have a substituent; R ³ and R ⁴ each independently represent a monovalent saturated hydrocarbyl group having 1 to 10 carbon atoms. The hydrogen atom contained may also be substituted with a halogen atom, and -CH ₂ -contained in the saturated hydrocarbon group may also be substituted with -O-, -CO- or -NR ¹¹ -; R ¹ and R ³ may also be bonded to each other Junction, together with these bonded nitrogen atoms to form a ring containing nitrogen atoms, R ² and R ⁴ can also be bonded to each other, together with these bonded nitrogen atoms to form a ring containing nitrogen atoms; 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 independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m represents an integer of 0 to 4; when m is an integer of 2 or more, plural R ⁵ may be the same or different; R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may also be replaced by a halogen atom; Z ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ ; R ⁹ and R ¹⁰ independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. R ⁹ and R ¹⁰ may also be bonded to each other to form a 3- to 10-membered nitrogen-containing heterocyclic ring together with a nitrogen atom; R ^{11 is} independently Represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms]

Examples of monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms representing R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl Straight-chain alkyl groups with 1 to 20 carbon atoms, such as yl, nonyl, decyl, dodecyl, hexadecyl, and eicosyl; isopropyl, isobutyl, second butyl, third Branched alkyl groups with 3 to 20 carbon atoms, such as butyl, isopentyl, neopentyl and 2-ethylhexyl; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and tricyclic C3-20 alicyclic saturated hydrocarbon groups such as decyl.

Examples of -CO ₂ R ⁸ include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, third butoxycarbonyl, hexoxycarbonyl, and eicosyloxycarbonyl.

Examples of -SO ₃ R ⁸ include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, third butoxysulfonyl, hexyloxysulfonyl, and bis Alkoxy sulfonyl and so on.

Examples of -SO ₂ NR ⁹ R ¹⁰ include: sulfamoyl; N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropyl Sulfasalamide, N-butylsulfaminyl, N-isobutylsulfaminyl, N-second butylsulfaminyl, N-third butylsulfaminyl, N-pentyl Sulfamoyl, N-(1-ethylpropyl) sulfamoyl, N-(1,1-dimethylpropyl) sulfamoyl, N-(1,2-dimethylpropyl ) Sulfamoyl, N-(2,2-dimethylpropyl) sulfamoyl, N-(1-methylbutyl) sulfamoyl, N-(2-methylbutyl)amine Sulfonyl, N-(3-methylbutyl) sulfonamide, N-cyclopentyl sulfonamide, N-hexyl sulfonamide, N-(1,3-dimethylbutyl) Sulfamoyl, N-(3,3-dimethylbutyl) sulfamoyl, N-heptyl sulfamoyl, N-(1-methylhexyl) sulfamoyl, N-(1 ,4-dimethylpentyl) sulfamoyl, N-octyl sulfamoyl, N-(2-ethylhexyl) sulfamoyl, N-(1,5-dimethylhexyl)amine Sulfonyl, N-(1,1,2,2-tetramethylbutyl) sulfonamide and other N-mono-substituted sulfamoyl; N,N-dimethylamine sulfonamide, N,N -Ethylmethylsulfamoyl, N,N-diethylaminesulfamoyl, N,N-propylmethylsulfamoyl, N,N-isopropylmethylsulfamoyl, N ,N-T-Butylmethylsulamide, N,N-Butylethylsulamide, N,N-bis(1-methylpropyl)sulamide, N,N-heptylmethyl N,N-disubstituted sulfamoyl, etc.

R ⁹ and R ¹⁰ may also be bonded to each other to form a 3- to 10-membered nitrogen-containing heterocyclic ring together with the nitrogen atom. Examples of the heterocyclic ring include the following.

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

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

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

Examples of the C 1-6 alkyl groups representing R ⁶ and R ⁷ include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and second butyl groups. , Third butyl, isopentyl and neopentyl.

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

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

The above ⁺ N(R ¹¹ ) _{4 is} preferably at least two of the four R ¹¹ are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. In addition, the total carbon number of the four R ¹¹ is preferably 20 to 80, and more preferably 20 to 60.

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

Examples of -OR ⁸ include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and dioxy Decaalkoxy and so on.

Examples of -SR ⁸ include methylthio, ethylthio, butylthio, hexylthio, decylthio, and eicosylthio.

As -SO ₂ R ⁸ , for example, mesylate, ethanesulfonyl, butylsulfonyl, hexylsulfonyl, decanesulfonyl, eicosanesulfonyl and the like can be mentioned.

R ³ and R ^{4 are} preferably unsubstituted monovalent saturated hydrocarbon groups having 1 to 10 carbon atoms, more preferably monovalent saturated hydrocarbon groups having 1 to 4 carbon atoms, and more preferably methyl and ethyl groups.

R ¹ and R ³ can also be bonded to each other to form a nitrogen atom-containing ring together with these bonded nitrogen atoms, R ² and R ⁴ can also be bonded to each other, and these bonded nitrogen atoms to one And form a ring containing nitrogen atoms. Examples of the nitrogen atom-containing ring include the following.

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

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

m is preferably an integer of 0~2, more preferably 0 or 1.

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

[In formula (2), R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent an alkyl group having 1 to 4 carbon atoms; p and q each independently represent an integer of 0 to 5; where p is 2 or more In the case, the plural R ²³ may be the same or different, and in the case where q is 2 or more, the plural R ²⁴ may be the same or different]

Examples of the C 1-4 alkyl groups representing R ²¹ , R ²² , R ²³ and R ²⁴ include methyl, ethyl, propyl, butyl, isopropyl, isobutyl and second butyl , Third butyl, etc.

Preferably, R ²¹ and R ²² are independently methyl and ethyl. R ²³ and R ^{24 are} preferably methyl.

p and q are preferably integers from 0 to 2, more preferably 0 or 1.

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

[Chem 28]

[In formula (3), R ³¹ and R ³² each independently represent a C 1-4 alkyl group; R ³³ and R ³⁴ each independently represent a hydrogen atom or a C 1-4 alkyl group]

Examples of the C 1-4 alkyl groups representing R ³¹ , R ³² , R ³³ and R ³⁴ include the same as described above. Preferably, R ³¹ and R ³² are each independently methyl or ethyl. Preferably, R ³³ and R ³⁴ are each independently a hydrogen atom or a methyl group.

As the compound (1), for example, compounds represented by each of formula (1-1) to formula (1-7) may be mentioned. Among them, the compound represented by formula (1-1) is preferable in terms of excellent solubility in an organic solvent.

The pigment (P) is not particularly limited, and known pigments can be used, and examples include Pigments classified as pigments according to colorimetric index (published by The Society of Dyers and Colourists).

Examples of pigments include CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 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 and other purple pigments; CI Pigment Green 7, 36, 58 and other green pigments; CI Pigment Brown 23, 25 and other brown pigments; CI Pigment Black 1, 7 and other black pigments.

顏料，更佳為選自由C.I.顏料藍15：6及顏料紫23所組成之群中之至少一種。藉由含有上述顏料，容易進行透射光譜之最佳化，彩色濾光片之耐光性及耐化學品性變得良好。 The pigment (P) is preferably a phthalocyanine pigment and two

The pigment is more preferably at least one selected from the group consisting of CI Pigment Blue 15:6 and Pigment Violet 23. By containing the above pigment, it is easy to optimize the transmission spectrum, and the light resistance and chemical resistance of the color filter become good.

Pigments may also be subjected to rosin treatment, surface treatment using pigment derivatives with an acidic or basic group introduced, grafting treatment of the pigment surface with a polymer compound, etc., and sulfuric acid micronization. Micronization treatment, cleaning treatment using an organic solvent or water to remove impurities, removal treatment of ionic impurities by ion exchange method, etc. The pigment preferably has a uniform particle size.

The pigment can be dispersed by containing a pigment dispersant to make the pigment A pigment dispersion liquid in a state of being uniformly dispersed in a solution. The pigments can be separately dispersed, or a plurality of kinds can be mixed and then dispersed.

Examples of the pigment dispersant include surfactants, and any of cationic, anionic, nonionic, and amphoteric surfactants may be used. Specific examples include pigment dispersants such as polyester, polyamine, and acrylic. These pigment dispersants may be used alone or in combination of two or more. Examples of pigment dispersants include trade names KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOWLEN (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Corporation), and EFKA (registered trademark) (Manufactured by BASF), Ajisper (registered trademark) (manufactured by Ajinomoto Fine Chemical Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK-Chemie), etc.

In the case of using a pigment dispersant, the amount used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of pigment. If the use amount of the pigment dispersant is within the above range, there is a tendency to obtain a uniformly dispersed pigment dispersion.

The content of the compound (A-I) relative to the total amount of the colorant (A) is preferably 1% by mass or more and 100% by mass or less, and more preferably 10% by mass or more and 100% by mass or less.

When the dye (A1) is included, the content rate is preferably 0.5% by mass or more and 80% by mass or less, and more preferably 40% by mass or more and 90% by mass relative to the total amount of the colorant (A). When the pigment (P) is included, its content is preferably 35% by mass or more and 99% by mass or less, more preferably 1% by mass or more, and 70% by mass or less relative to the total amount of the colorant (A). Furthermore, it is preferably 1% by mass or more and 50% by mass or less.

The content of the coloring agent (A) is preferably 5% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and still more preferably 5% by mass relative to the total amount of solid content. Above, 50% by mass or less. If the content of the colorant (A) is within the above range, the desired spectrophotometry can be obtained.

In this specification, the "total amount of solid content" refers to the total amount of components from which the solvent (E) is removed from the colored curable resin composition. The total amount of solid content and the content of each component relative to the total amount can be measured by a known analysis method such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) is preferably an alkali-soluble resin (B). The alkali-soluble resin (B) (hereinafter sometimes referred to as "resin (B)") contains a structural unit derived from at least one monomer (Ba) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride Of copolymers.

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

The resin [K1] is selected from at least one monomer (Ba) (hereinafter sometimes referred to as "(Ba)") selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride and a cyclic ring having 2 to 4 carbon atoms Copolymer of ether structure and ethylenically unsaturated monomer (Bb) (hereinafter sometimes referred to as "(Bb)"); resin [K2] (Ba), (Bb), copolymerizable with (Ba) Copolymer of monomer (Bc) (which is different from (Ba) and (Bb)) (hereinafter sometimes referred to as "(Bc)"); copolymer of resin [K3] (Ba) and (Bc); Resin [K4] is a resin obtained by reacting a copolymer of (Ba) and (Bc) with (Bb); resin [K5] is performed by making a copolymer of (Bb) and (Bc) with (Ba) The resin obtained by the reaction; the resin [K6] is a resin obtained by reacting a copolymer of (Bb) and (Bc) with (Ba) and then reacting with a carboxylic acid anhydride.

烯-2,3-二羧酸、5-羧基雙環[2.2.1]庚-2-烯、5,6-二羧基雙環[2.2.1]庚-2-烯、5-羧基-5-甲基雙環[2.2.1]庚-2-烯、5-羧基-5-乙基雙環[2.2.1]庚-2-烯、5-羧基-6-甲基雙環[2.2.1]庚-2-烯、5-羧基-6-乙基雙環[2.2.1]庚-2-烯等含有羧基之雙環不飽和化合物類；順丁烯二酸酐、檸康酸酐、伊康酸酐、3-乙烯基鄰苯二甲酸酐、4-乙烯基鄰苯二甲酸酐、3,4,5,6-四氫鄰苯二甲酸酐、1,2,3,6-四氫鄰苯二甲酸酐、二甲基四氫鄰苯二甲酸酐、雙環[2.2.1]庚-2-烯-5,6-二羧酸酐等不飽和二羧酸類之酸酐；琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、鄰苯二甲酸單[2-(甲基)丙烯醯氧基乙基]酯等2元以上之多元羧酸之不飽和單[(甲基)丙烯醯氧基烷基]酯類；α-(羥基甲基)丙烯酸之類的同一分子中含有羥基及羧基之不飽和丙烯酸酯類等。 Examples of (Ba) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; maleic acid; Acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid Unsaturated dicarboxylic acids such as dicarboxylic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5- drop

Ene-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 -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-vinyl Phthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyl Tetrahydrophthalic anhydride, bicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic anhydride and other unsaturated dicarboxylic acid anhydrides; succinic acid mono[2-(meth)acryloyloxy Unsaturated mono[(meth)acryloyloxyalkyl] with 2 or more polyvalent carboxylic acids, such as ethyl ethyl]ester, mono[2-(meth)acryloyloxyethyl]phthalate, etc. Esters; unsaturated acrylic esters containing hydroxyl and carboxyl groups in the same molecule as α-(hydroxymethyl) acrylic acid.

In terms of the reactivity of the copolymerization or the solubility of the obtained resin in the alkaline aqueous solution, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable among these.

(Bb) For example, it means a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of oxirane ring, oxetane ring, and tetrahydrofuran ring) and ethylenic unsaturation The polymerizable compound of the bond.

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

In addition, in this specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth)acryloyl" and "(meth)acrylate" have the same meaning.

Examples of (Bb) include monomers having an oxetanyl group and an ethylenically unsaturated bond (Bb1) (hereinafter sometimes referred to as "(Bb1)"), monomer (Bb2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(Bb2)"), having a tetrahydrofuranyl group Monomer (Bb3) with ethylenic unsaturated bond (hereinafter sometimes referred to as "(Bb3)"), etc.

Examples of (Bb1) include monomers (Bb1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(Bb1-1)"), A monomer (Bb1-2) having an epoxidized structure of an alicyclic unsaturated hydrocarbon (hereinafter sometimes referred to as "(Bb1-2)").

Examples of (Bb1-1) include: glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and glycidylvinyl Ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl -M-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidoxymethyl) styrene, 2,4-bis (glycidyl) Glyceryloxymethyl) styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris Glyceryloxymethyl) styrene, 2,3,5-tris (glycidoxymethyl) styrene, 2,3,6-tris (glycidoxymethyl) styrene, 3,4,5 -Tris (glycidoxymethyl) styrene, 2,4,6-tris (glycidoxymethyl) styrene, etc.

Examples of (Bb1-2) include vinyl cyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000; manufactured by Daicel Corporation), ( 3,4-epoxycyclohexyl methyl methacrylate (eg Cyclomer (registered trademark) A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexyl methyl (meth)acrylate (eg Cyclomer M100; Daicel Co., Ltd.), compound represented by formula (BI), compound represented by formula (BII), etc.

[化30]

[In formula (BI) and formula (BII), R ^a and R ^b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may also be substituted with a hydroxyl group; X ^a and X ^b represent a single bond, * -R ^c -, * -R ^c -O-, * -R ^c -S- or * -R ^c -NH-; R ^c represents a C1-C6 alkane Base; * indicates a bond with O]

Examples of the C 1 to C 4 alkyl groups for R ^a and R ^b include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, and third butyl groups.

Examples of the alkyl group in which the hydrogen atom of R ^a and R ^b is substituted with hydroxy include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3- Hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc. .

R ^a and R ^{b are} preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically In particular, a hydrogen atom, a methyl group, an ethyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are preferably mentioned, and a hydrogen atom and a methyl group are more preferably mentioned.

Examples of the alkanediyl group of R ^c include linear or branched alkanediyl groups, and specific examples thereof include methylene, ethylidene, propane-1,3-diyl and butane-1. Straight-chain alkanediyls such as 4-diyl, pentane-1,5-diyl, hexane-1,6-diyl; branched-chain alkanediyls such as propane-1,2-diyl.

X ^a and X ^b preferably include single bonds, * -R ^c -, or * -R ^c -O-, more preferably single bonds, or * -R ^c -O-, particularly preferably single bonds , Methylene, ethylidene, * -CH ₂ -O- and * -CH ₂ CH ₂ -O-, can better enumerate single bonds, * -CH ₂ CH ₂ -O- (* represents the same as O Bond key).

As the compound represented by formula (BI), any of formula (BI-1) to formula (BI-15) may be mentioned The compounds represented by the above. Among them, formula (BI-1), formula (BI-3), formula (BI-5), formula (BI-7), formula (BI-9) or formula (BI-11) to formula (BI) are preferred The compound represented by -15) is more preferably a compound represented by formula (BI-1), formula (BI-7), formula (BI-9) or formula (BI-15).

Examples of the compound represented by formula (BII) include compounds represented by any of formula (BII-1) to formula (BII-15). Among them, formula (BII-1), formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9) or formula (BII-11) to formula (BII) are preferred The compound represented by -15) is more preferably a compound represented by formula (BII-1), formula (BII-7), formula (BII-9) or formula (BII-15).

[化33]

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

As (Bb2), a monomer having oxetanyl group and (meth)acryloyloxy group is more preferable. Examples of (Bb2) include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, 3- Ethyl-3-methacryloxymethyl oxetane, 3-ethyl-3-propenyl oxymethyl oxetane, 3-methyl-3-methacryl oxetane Ethylethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methacryloxyethyloxetane, 3 -Ethyl-3-propylene Oxyethyl oxetane, etc.

As (Bb3), a monomer having a tetrahydrofuran group and (meth)acryloyloxy group is more preferable. Specific examples of (Bb3) include tetrahydrofurfuryl acrylate (for example, Viscoat V# 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (Bb), in terms of further improving the reliability of the obtained color filter, such as heat resistance and chemical resistance, (Bb1) is preferable. Furthermore, in terms of excellent storage stability of the colored curable resin composition, (Bb1-2) is more preferable.

酯、(甲基)丙烯酸金剛烷基酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸炔丙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸苄酯等(甲基)丙烯酸酯類；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯等含羥基之(甲基)丙烯酸酯類；順丁烯二酸二乙酯、反丁烯二酸二乙酯、伊康酸二乙酯等二羧酸二酯；雙環[2.2.1]庚-2-烯、5-甲基雙環[2.2.1]庚-2-烯、5-乙基雙環[2.2.1]庚-2-烯、5-羥基雙環[2.2.1]庚-2-烯、5-羥基甲基雙環[2.2.1]庚- 2-烯、5-(2'-羥基乙基)雙環[2.2.1]庚-2-烯、5-甲氧基雙環[2.2.1]庚-2-烯、5-乙氧基雙環[2.2.1]庚-2-烯、5,6-二羥基雙環[2.2.1]庚-2-烯、5,6-二(羥基甲基)雙環[2.2.1]庚-2-烯、5,6-二(2'-羥基乙基)雙環[2.2.1]庚-2-烯、5,6-二甲氧基雙環[2.2.1]庚-2-烯、5,6-二乙氧基雙環[2.2.1]庚-2-烯、5-羥基-5-甲基雙環[2.2.1]庚-2-烯、5-羥基-5-乙基雙環[2.2.1]庚-2-烯、5-羥基甲基-5-甲基雙環[2.2.1]庚-2-烯、5-第三丁氧基羰基雙環[2.2.1]庚-2-烯、5-環己氧基羰基雙環[2.2.1]庚-2-烯、5-苯氧基羰基雙環[2.2.1]庚-2-烯、5,6-雙(第三丁氧基羰基)雙環[2.2.1]庚-2-烯、5,6-雙(環己氧基羰基)雙環[2.2.1]庚-2-烯等雙環不飽和化合物類；N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苄基順丁烯二醯亞胺、N-琥珀醯亞胺基-3-順丁烯二醯亞胺苯甲酸酯、N-琥珀醯亞胺基-4-順丁烯二醯亞胺丁酸酯、N-琥珀醯亞胺基-6-順丁烯二醯亞胺己酸酯、N-琥珀醯亞胺基-3-順丁烯二醯亞胺丙酸酯、N-(9-吖啶基)順丁烯二醯亞胺等二羰基醯亞胺衍生物類；苯乙烯、α-甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、乙烯基甲苯、對甲氧基苯乙烯等含乙烯基之芳香族化合物；丙烯腈、甲基丙烯腈等含乙烯基之腈；氯乙烯、偏二氯乙烯等鹵化烴；丙烯醯胺、甲基丙烯醯胺等含乙烯基之醯胺；乙酸乙烯酯等酯；1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯等二烯等。 Examples of (Bc) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and (meth)acrylic acid. Tributyl ester, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid ring Amylester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl ester (method) In the technical field, it is commonly known as "dicyclopentyl (meth)acrylate"; sometimes referred to as "tricyclodecyl (meth)acrylate"), tricyclo (meth)acrylate [5.2.1.0 ^2,6 ]decene-8-yl ester (in this technical field, it is commonly known as "dicyclopentenyl (meth)acrylate"), dicyclopentoxyethyl (meth)acrylate, ( Meth)acrylic acid

Ester, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, (meth) (Meth)acrylates such as benzyl acrylate; hydroxyl-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; maleic acid Dicarboxylic acid diesters such as diethyl ester, fumaric acid diethyl ester, and itaconic acid diethyl ester; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]heptan 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-diethoxy Bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hepta-2 -Ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-third butoxycarbonyl bicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxy Carboxycarbonyl bicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonyl bicyclo[2.2.1]hept-2-ene, 5,6-bis(third butoxycarbonyl)bicyclo[2.2.1 ] Hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl) bicyclo[2.2.1] bicyclic unsaturated compounds such as hept-2-ene; N-phenyl maleimide, N -Cyclohexyl maleimide diimide, N-benzyl maleimide diimide, N-succinimide-3-maleimide benzoate, N-succinimide Amino-4-maleimide diimidyl butyrate, N-succinimide-6-maleimide diimide caproate, N-succinimide-3-maleimide Dicarbonylimine derivatives such as diimide propionate, N-(9-acridinyl) maleimide diimide; styrene, α-methylstyrene, m-methylstyrene, Vinyl-containing aromatic compounds such as p-methylstyrene, vinyltoluene and p-methoxystyrene; vinyl-containing nitriles such as acrylonitrile and methacrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; Vinyl-containing amides such as acrylic amide and methacrylamide; esters such as vinyl acetate; 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butane Diene, etc.

Among these, in terms of copolymerization reactivity and heat resistance, (Bc) is preferably a vinyl-containing aromatic compound, a dicarbonyl amide imine derivative, or a bicyclic unsaturated compound. Specifically, styrene, vinyl toluene, N-phenyl maleimide diimide, N-cyclohexyl maleimide diimide, N-benzyl maleimide diimide, bicyclic [2.2.1] Hept-2-ene and so on.

In the resin [K1], regarding the ratio of the structural units derived from each monomer, among all the structural units constituting the resin [K1], it is preferable that the structural unit derived from (Ba) is 2 to 60 mol %, The structural unit derived from (Bb) is 40-98 mol%, more preferably the structural unit derived from (Ba) is 10-50 mol%, and the structural unit derived from (Bb) is 50-90 mol% .

If the ratio of the structural unit of the resin [K1] is within the above range, there is a tendency for the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the obtained color filter to be excellent .

The resin [K1] can be disclosed in, for example, the document "Experimental Method of Polymer Synthesis" (by Otsu Takayuki, published by Dojin Chemical Co., Ltd., first edition, first print, published on March 1, 1972) The method and the cited documents disclosed in this document are manufactured.

Specifically, a specific amount of (Ba) and (Bb), a polymerization initiator, a solvent, etc. are put into a reaction vessel, for example, by replacing oxygen with nitrogen to form a deoxygenated environment, heating while stirring And heat preservation method. In addition, the polymerization initiator and the solvent used here are not particularly limited, and can be used by ordinary users in this field. Examples of the polymerization initiator include azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxides The solvent (benzoyl peroxide, etc.) may be any solvent as long as it dissolves each monomer, and examples thereof include the solvent (E) described below as the solvent (E) of the color-curable resin composition of the present invention.

Furthermore, the obtained copolymer may be used as it is after the reaction, or it may be a concentrated or diluted solution, or it may be taken out in the form of solid (powder) by reprecipitation or the like. Especially during the polymerization, by using the solvent contained in the color-curing resin composition of the present invention as a solvent, the solution after the reaction can be directly used for the preparation of the color-curing resin composition of the present invention, so that The manufacturing process of the color-curable resin composition of the present invention is simplified.

In the resin [K2], regarding the ratio of the structural units derived from each monomer, among all the structural units constituting the resin [K2], it is preferable that the structural unit derived from (Ba) is 2 to 45 mol %, The structural unit derived from (Bb) is 2 to 95 mol%, the structural unit derived from (Bc) is 1 to 65 mol%, more preferably the structural unit derived from (Ba) is 5 to 40 mol% The structural unit derived from (Bb) is 5 to 80 mol%, and the structural unit derived from (Bc) is 5 to 60 mol%.

If the ratio of the structural unit of the resin [K2] is within the above range, there are storage stability of the colored curable resin composition, developability when forming a colored pattern, and solvent resistance and heat resistance of the obtained color filter And excellent mechanical strength.

The resin [K2] can be produced in the same manner as the method described as the production method of the resin [K1], for example.

In the resin [K3], regarding the ratio of the structural units derived from each monomer, among all the structural units constituting the resin [K3], it is preferable that the structural unit derived from (Ba) is 2 to 60 mol %, The structural unit derived from (Bc) is 40-98 mol%, more preferably the structural unit derived from (Ba) is 10-50 mol%, and the structural unit derived from (Bc) is 50-90 mol%.

The resin [K3] can be produced in the same manner as the method described as the production method of the resin [K1], for example.

The resin [K4] can be produced by obtaining a copolymer of (Ba) and (Bc) and adding a cyclic ether having 2 to 4 carbon atoms of (Bb) to the carboxylic acid of (Ba) And/or carboxylic anhydride.

First, the copolymer of (Ba) and (Bc) is produced in the same manner as the method described as the production method of the resin [K1]. In this case, the ratio of structural units derived from each monomer is preferably The same ratio as listed in Resin [K3].

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

After the production of the copolymer of (Ba) and (Bc), the atmosphere in the flask is replaced with nitrogen to the air, and the reaction catalyst of (Bb), carboxylic acid or carboxylic anhydride and cyclic ether (such as tris(dimethyl) Aminomethyl)phenol, etc.) and polymerization inhibitors (for example, hydroquinone, etc.) are put into a flask, and the reaction is performed at 60 to 130° C. for 1 to 10 hours, for example, to produce resin [K4].

The amount of (Bb) used is preferably 5 to 80 moles, more preferably 10 to 75 moles relative to (Ba) 100 moles. By adjusting the amount of (Bb) used in this range, there are the storage stability of the colored curable resin composition, the developability during pattern formation, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern The tendency of the balance to become good. Since cyclic ethers have high reactivity and it is difficult to retain unreacted (Bb), the (Bb) used as the resin [K4] is preferably (Bb1), and more preferably (Bb1-1).

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

The reaction conditions such as the loading method of each reagent, reaction temperature and reaction time can be appropriately adjusted in consideration of the manufacturing equipment or the calorific value of polymerization and the like. Furthermore, the manufacturing method and the calorific value of the polymerization can be considered in the same manner as the polymerization conditions, and the charging method or reaction temperature can be adjusted as appropriate.

In the production of the resin [K5], as the first step, the copolymer of (Bb) and (Bc) is obtained in the same manner as the production method of the resin [K1]. In the same manner as above, the obtained copolymer may be used as it is after the reaction, or it may be a concentrated or diluted solution, or it may be taken out as a solid (powder) by a method such as reprecipitation.

The ratio of the structural units derived from (Bb) and (Bc) to the total number of moles of all the structural units constituting the copolymers of (Bb) and (Bc) above

Preferably, the structural unit derived from (Bb) is 5 to 95 mol%, The structural unit derived from (Bc) is 5 to 95 mol%, more preferably the structural unit derived from (Bb) is 10 to 90 mol%, and the structural unit derived from (Bc) is 10 to 90 mol% .

Furthermore, as the second step, the carboxylic acid or carboxylic anhydride possessed by (Ba) and the copolymer possessed by (Bb) and (Bc) are derived under the same conditions as the manufacturing method of resin [K4]. The cyclic ether of (Bb) reacts to obtain resin [K5].

In the second stage, the use amount of (Ba) reacted with the copolymer of (Bb) and (Bc) is preferably 5 to 80 moles relative to 100 moles (Bb). Since the cyclic ether has high reactivity, it is difficult to retain unreacted (Bb), so (Bb) used for the resin [K5] is preferably (Bb1), and more preferably (Bb1-1).

Resin [K6] is a resin obtained by further reacting carboxylic anhydride and resin [K5]. Carboxylic anhydride is reacted with the hydroxyl group produced by the reaction of cyclic ether with carboxylic acid or carboxylic anhydride.

The resin [K6] is a resin obtained by further reacting a carboxylic acid anhydride with a resin [K5]. Specifically, it can be produced by making the carboxylic acid anhydride and the cyclic ether derived from (Bb) and ( The hydroxyl group produced by the reaction of carboxylic acid or carboxylic anhydride of Ba) reacts.

Examples of carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetra Hydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, bicyclo[2.2.1]hept-2-ene-5,6- Dicarboxylic anhydride, etc. The use amount of carboxylic anhydride is preferably 0.5 to 1 mole relative to the use amount of (Ba) 1 mole.

Specific examples of the resin (B) include: (meth)acrylic acid 3,4-epoxycyclohexyl methyl ester/(meth)acrylic acid copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[ 5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid copolymer and other resins [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, (A Base) glycidyl acrylate/styrene/(meth)acrylic acid copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/N- Cyclohexyl maleic diimide copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/vinyltoluene copolymer, 3- Resins such as methyl-3-(meth)acryloxymethyloxetane/(meth)acrylic acid/styrene copolymer [K2]; benzyl (meth)acrylate/(meth)acrylic acid Resins such as copolymers, styrene/(meth)acrylic copolymers, benzyl (meth)acrylate/tricyclodecyl (meth)acrylate/(meth)acrylic copolymers, etc. [K3]; in (meth) Resin with glycidyl (meth)acrylate added to benzyl acrylate/(meth)acrylic acid copolymer, added to tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer Resin with glycidyl (meth)acrylate, and glycidyl (meth)acrylate added to tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer Resin and other resins [K4]; a resin obtained by reacting a copolymer of (meth)acrylic acid and tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate, and (meth)acrylic acid and Resin and other resins obtained by reacting a copolymer of tricyclodecyl (meth) acrylate/styrene/glycidyl (meth) acrylate [K5]; tricyclic (meth) acrylic acid and (meth) acrylic acid A resin such as a resin obtained by reacting a copolymer of decyl ester/glycidyl (meth)acrylate and further reacting the obtained resin with tetrahydrophthalic anhydride [K6], etc.

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

The weight average molecular weight in terms of polystyrene 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. If the molecular weight is in the above range, the hardness of the coating film will increase, the residual film rate will also be high, the solubility of the unexposed portion in the developing solution will be good, and the resolution of the colored pattern will tend 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, 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 is more preferably 70 to 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be obtained by titration using an aqueous potassium hydroxide solution, for example.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass relative to the total amount of solid content. If the content of the resin (B) is within the above 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 using the active radicals and/or acids generated from the polymerization initiator (D), for example, a polymerizable compound having an ethylenic unsaturated bond, etc., preferably It is a (meth)acrylate compound.

Examples of the polymerizable compound having an ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethylhexyl carbitol acrylate. , 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc., and (Ba), (Bb) and (Bc) 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. Methacrylate, triethylene glycol di(meth)acrylate, bis(acryloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc.

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)acrylic acid. Ester, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hexa(meth)acrylate, four pentaerythritol deca(meth)acrylate, four pentaerythritol hexa(meth)acrylate Ester, tris(2-(meth)acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra(methyl)propionate Acrylic acid ester, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol Tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc., among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

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

The content of the polymerizable compound (C) relative to the total amount of solid content is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass. If the content of the polymerizable compound (C) is within the above range, the residual film rate when forming a colored pattern and the chemical resistance of the color filter tend to increase.

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

If the content of the polymerizable compound (C) is within the above range, the residual film rate when forming a colored pattern and the chemical resistance of the color filter tend to increase.

<polymerization initiator (D)>

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

化合物、及醯基氧化膦化合物等。 Examples of the polymerization initiator (D) include O-acyl oxime compounds, phenalkone compounds, biimidazole compounds,

Compounds, and acylphosphine oxide compounds, etc.

The O-acyl oxime compound is a compound having a partial structure represented by formula (Dd1). In the following, * indicates a bonding key.

[化35]

Examples of the O-acyloxime compounds include N-benzyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine and N-benzyloxy Yl-1-(4-phenylthiophenyl)octan-1-one-2-imine, N-benzyloxy-1-(4-phenylthiophenyl)-3-cyclopentyl Propane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]ethane -1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolyl (Methoxy)benzyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzene (Methyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyloxy-1-[9-ethyl-6-(2-methyl Benzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (made by BASF) and N-1919 (made by ADEKA) can also be used. Among them, the O-acyl oxime compound is preferably selected from the group consisting of N-benzyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzyloxy Yl-1-(4-phenylthiophenyl)octan-1-one-2-imine and N-benzyloxy-1-(4-phenylthiophenyl)-3-cyclopentyl At least one of the groups consisting of propane-1-one-2-imine, more preferably N-benzyloxy-1-(4-phenylthiophenyl)octan-1-one-2- Imine.

The phenalkyl ketone compound is, for example, a compound having a partial structure represented by formula (Dd2) or a partial structure represented by formula (Dd3). In these partial structures, the benzene ring may also have a substituent.

As the compound having a partial structure represented by the formula (Dd2), for example, 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propane-1-one, 2-dimethyl Amino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl ]-1- [4-(4-morpholinyl)phenyl]butane-1-one and the like. Commercial products such as Irgacure 369, 907, and 379 (above are manufactured by BASF Corporation) can also be used.

As the compound having a partial structure represented by formula (Dd3), for example, 2-hydroxy-2-methyl-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 -Oligomer of ketone, α,α-diethoxyacetophenone, benzoyl dimethyl ketal, etc.

In terms of sensitivity, the phenalkyl ketone compound is preferably a compound having a partial structure represented by formula (Dd2).

Examples of the biimidazole compound include compounds represented by formula (Dd4).

[In formula (Dd4), R ^d1 to R ^d6 represent an aryl group having 6 to 10 carbon atoms which may have a substituent]

Examples of the C 6-10 aryl groups for R ^d1 to R ^d6 include phenyl, tolyl, xylyl, ethylphenyl, and naphthyl, and phenyl is preferred.

Examples of the substituent that can be substituted on the aryl group of R ^d1 to R ^d6 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. A chlorine atom is preferred. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, butoxy, etc., preferably methoxy.

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 (for example, refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5 ,5'-Tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-Tetra(dialkoxyphenyl)biimidazole , 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japan Japanese Patent Laid-Open No. 62-174204, etc.), an imidazole compound in which a phenyl group in 4,4', 5,5'-position is substituted with an alkoxycarbonyl group (for example, refer to Japanese Patent Laid-Open No. 7-10913, etc.), etc. Among them, compounds represented by the following formula and mixtures of these are preferred.

化合物，例如可列舉：2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三

、2,4-雙(三氯甲基)-6-向日葵基-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三

等。 As the above three

Compounds, for example: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tris

, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-sunflower group-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tris

, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-tri

, 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.

Examples of the above-mentioned acylphosphine oxide compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide and the like.

Furthermore, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl phthalate, 4-phenylbenzophenone, 4-benzyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis (third butylperoxycarbonyl) dibenzoyl Ketone, 2,4,6-trimethyl bis Benzophenone compounds such as benzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone; 10-butyl-2-chloroacridone, benzophenone, phenylacetaldehyde Methyl acid ester, titanocene compound, etc.

These are preferably used in combination with the following polymerization initiation aid (D1) (especially amines).

Examples of acid-generating polymerization initiators include 4-hydroxyphenyldimethylammonium p-toluenesulfonate, 4-hydroxyphenyldimethylammonium hexafluoroantimonate, and 4-ethoxybenzene Dimethyl benzoic acid p-toluenesulfonate, 4-acetoxyphenylmethylbenzyl benzoic acid hexafluoroantimonate, triphenylacrylic acid p-toluenesulfonic acid salt, triphenylacrylic acid hexafluoroantimonate, Onium salts such as diphenyliodonium p-toluenesulfonate, diphenylphosphonium hexafluoroantimonate, or nitrobenzyl tosylate, benzoin tosylate, etc.

化合物、醯基氧化膦化合物、O-醯基肟化合物及聯咪唑化合物所組成之群中之至少一種的聚合起始劑，更佳為包含O-醯基肟化合物之聚合起始劑。 As the polymerization initiator (D), a polymerization initiator that generates active radicals is preferred. Specifically, it includes a compound selected from

The polymerization initiator of at least one of the group consisting of a compound, an acyl phosphine oxide compound, an O-acyl oxime compound and a biimidazole compound is more preferably a polymerization initiator containing an O-acyl oxime compound.

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

<Polymerization Initiator (D1)>

The polymerization start aid (D1) is a compound or sensitizer for promoting the polymerization of the polymerizable compound that initiates polymerization by the polymerization initiator. When the polymerization initiator (D1) is included, it is usually used in combination with the polymerization initiator (D).

化合物及羧酸化合物等。 Examples of the polymerization start aid (D1) include amine compounds, alkoxyanthracene compounds, and 9-oxosulfur

Compounds and carboxylic acid compounds.

Examples of the amine compound include alkanolamines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, Isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4-dimethyl Aminobenzoates such as 2-ethylhexylaminobenzoate; N,N-dimethyl-p-toluidine; 4,4'-bis(dimethylamino)benzophenone (commonly known as rice) Ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone and other alkylaminobenzophenones Among others, alkylaminobenzophenone is preferred, and 4,4'-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (Hodogaya Chemical Industry Co., Ltd.) can also be used.

Examples of the alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl -9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

化合物，可列舉：2-異丙基-9-氧硫

、4-異丙基-9-氧硫

、2,4-二乙基-9-氧硫

、2,4-二氯-9-氧硫

、1-氯-4-丙氧基-9-氧硫

等。 As the above 9-oxygen sulfur

Compounds include: 2-isopropyl-9-oxysulfur

, 4-isopropyl-9-oxysulfur

, 2,4-Diethyl-9-oxysulfur

, 2,4-Dichloro-9-oxysulfur

, 1-chloro-4-propoxy-9-oxysulfur

Wait.

Examples of the above-mentioned carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, and methoxyphenylthio Acetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine , Naphthoxyacetic acid, etc.

In the case of using the polymerization initiation aid (D1), the content is preferably 0.1 to 30 parts by mass relative to the total amount of 100 parts by mass of the resin (B) and the polymerizable compound (C), more preferably 1~20 parts by mass. If the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent generally used in this field can be used. Examples include ester solvents (solvents containing -COO- in the molecule and no -O-), ether solvents (solvents containing -O- in the molecule and -COO- free), and ether ester solvents (containing -COO in the molecule) -Solvent with -O-), ketone solvent (with -CO- in the molecule, solvent without -COO-), alcohol solvent (with OH in the molecule, without -O-, -CO- and -COO- Solvent), aromatic hydrocarbon solvent, acetamide solution Agents, dimethyl sulfoxide, etc.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, 2-hydroxyisobutyric acid methyl ester, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. , Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclic Hexanol acetate, γ-butyrolactone, etc.

烷、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇甲基乙基醚、二乙二醇二丙醚、二乙二醇二丁醚、苯甲醚、苯基乙基醚、甲基苯甲醚等。 Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monoethyl ether. Ethylene 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-di

Alkanes, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ethyl Ether, methyl anisole, etc.

Examples of ether ester solvents include: methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl acetate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethoxy-2-methylpropionic acid ethyl ester, 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, di Propylene glycol methyl ether acetate, etc.

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

Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, and cyclohexane Alcohol, ethylene glycol, propylene glycol, glycerin, etc.

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

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

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

Among them, preferred are ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether Ether acetate, 3-methoxy-1-butanol, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl lactate, N-methylpyrrolidone, 4-hydroxyl -4-Methyl-2-pentanone, N,N-dimethylformamide, etc., more preferably ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether Acetate, 3-methoxy-1-butanol, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl lactate, N-methylpyrrolidone.

The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass relative to the total amount of the colored curable resin composition. In other words, the total amount of 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 during coating becomes good, and when the color filter is formed, the absorbance is insufficient, so the display characteristics tend to be good.

<Leveling agent (F)>

Examples of the leveling agent (F) include polysiloxane-based surfactants, fluorine-based surfactants, and polysiloxane-based surfactants having fluorine atoms. These may also have a polymerizable group on the side chain.

Examples of polysiloxane-based surfactants include surfactants having a siloxane bond 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 (manufactured by Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401 , TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan Co., Ltd.), etc.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, Fluorad FC431 (made 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 (manufactured by DIC Corporation), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Precision Chemical Research Institute Co., Ltd.), etc.

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

When the leveling agent (F) is contained, the content is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more, and 0.1% by mass relative to the total amount of the colored curable resin composition. The following is more preferably 0.005 mass% or more and 0.07 mass% or less. If the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<other ingredients>

The colored curable resin composition may also contain additives known in the technical field such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., if necessary.

<Manufacturing method of colored curable resin composition>

The coloring curable resin composition can be, for example, a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and a leveling agent if necessary (F), polymerization initiation aid (D1) and other components are mixed and prepared.

When the pigment (P) is included, the pigment is preferably mixed with part or all of the solvent (E) in advance, and dispersed using a bead mill or the like so that the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, part or all of the above pigment dispersant and resin (B) may be blended as needed. In the pigment dispersion liquid thus obtained, the remaining components are mixed so as to become a specific concentration, whereby the target colored curable resin composition can be prepared.

In addition, it is preferable to prepare the solution by dissolving the compound (A-I) in part or all of the solvent (E) in advance. Furthermore, it is preferable to filter the solution using a filter with a pore diameter of about 0.01 to 1 μm.

Preferably, the color-curable resin composition after mixing is filtered by a filter with a pore diameter of about 0.01 to 10 μm.

<Manufacturing method of color filter>

Examples of the method for producing a colored pattern from the color-curable resin composition of the present invention include photolithography, inkjet method, and printing method. Among them, the photolithography method is preferred. The photolithography method is a method of applying the above-mentioned colored curable resin composition on a substrate, drying it to form a coloring composition layer, exposing the colored composition layer via a photomask, and developing it. In the photolithography method, by not using a photomask during exposure and/or not performing development, a colored coating film can be formed as a cured product of the coloring composition layer. The colored pattern or colored coating film thus formed is the color filter of the present invention.

The thickness of the manufactured color filter is not particularly limited, and can be based on the purpose or use It can be adjusted appropriately, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass coated with silicon oxide on the surface, or polycarbonate, polymethyl methacrylate, and poly terephthalate are used A board of resin such as ethylene formate, silicon, and a board on which aluminum, silver, silver/copper/palladium alloy film, etc. are formed on the above substrate. Other color filter layers, resin layers, transistors, circuits, etc. can also be formed on these substrates.

The formation of pixels of various colors by photolithography can be carried out using well-known or conventional devices or conditions. For example, it can be produced in the following manner.

First, the colored curable resin composition is applied on a substrate, and then heat-dried (pre-baked) and/or dried under reduced pressure, thereby drying and removing volatile components such as a solvent to obtain a smooth coloring composition layer.

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

In the case of heating and drying, the temperature is preferably 30 to 120°C, more preferably 50 to 110°C. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

In the case of reduced-pressure drying, it 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 it may be appropriately selected according to the target film thickness of the color filter.

Next, the coloring composition layer is exposed through a photomask used to form a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the intended use can be used.

The light source used for exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. For example, a filter that cuts off this wavelength region is used to cut off light that does not reach 350 nm, or a bandpass filter that extracts these wavelength regions is used to selectively extract near 436 nm, Light near 408nm and 365nm. Specifically, examples of the light source include mercury lamps, light-emitting diodes, metal halogen lamps, and halogen lamps.

In order to be able to uniformly irradiate parallel light to the entire exposure surface, or to accurately align the photomask with the substrate on which the colored composition layer is formed, it is preferable to use a photomask to align the exposure device such as an exposure machine and a stepper.

The coloring composition layer after exposure is brought into contact with a developing solution to perform development, thereby forming a coloring pattern on the substrate. By development, the unexposed portion of the coloring composition layer is dissolved in the developer and removed. As the developing solution, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide is preferable. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Furthermore, the developer may contain a surfactant.

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

Preferably, it is washed with water after development.

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

Since the compound of the present invention has high absorbance, the color-curing resin composition using the same can be used to produce high-brightness color filters. The color filter can be used as a color filter for display devices (such as liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

This application claims the benefit of priority based on Japanese Patent Application No. 2014-223768 filed on October 31, 2014. The entire contents of the specification of Japanese Patent Application No. 2014-223768 filed on October 31, 2014 are incorporated herein by reference.

[Example]

Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited by these examples. In the examples, the% and parts indicating the content or the used amount are quality standards unless otherwise specified.

Hereinafter, the structure of the compound is confirmed by mass analysis (LC: Model 1200 manufactured by Agilent, MASS: LC/MSD model manufactured by Agilent), and UV-VIS (V-650 manufactured by Japan Spectroscopy Corporation).

[Example 1]

The following reaction is carried out under a nitrogen atmosphere. 32.2 parts of potassium thiocyanate and 160.0 parts of acetone were put in the flask equipped with a cooling tube and a stirring device, and it stirred at room temperature for 30 minutes. Then, 50.0 parts of 2-fluorobenzyl chloride (made by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Then, after cooling the reaction mixture in an ice bath, 40.5 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After the dropwise addition was completed, the mixture was further stirred at room temperature for 30 minutes. Then, after cooling the reaction mixture in an ice bath, 34.2 parts of a 30% sodium hydroxide aqueous solution was added dropwise. After the dropwise addition was completed, the mixture was further stirred at room temperature for 30 minutes. Then, 31.3 parts of chloroacetic acid was added dropwise at room temperature. After the dropwise addition, the mixture was stirred under heating and reflux for 7 hours. Then, 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 it was allowed to stand for 30 minutes. As a result, it was separated into an organic layer and an aqueous layer. After the water layer was discarded by the liquid separation operation, the organic layer was washed with 200 parts of 1 equivalent hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of thenardite was added to the organic layer and stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was distilled to remove the solvent in an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified light yellow liquid was dried under reduced pressure at 60°C to obtain 49.9 parts of the compound represented by formula (B-I-2). The yield was 51%.

The following reaction is carried out under a nitrogen atmosphere. After putting 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N,N-dimethylformamide in a flask equipped with a cooling tube and a stirring device, the mixed solution was cooled in an ice bath. Under ice-cooling, 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in small portions over 30 minutes, and the mixture was stirred for 1 hour while warming to room temperature. A small amount of 10.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the reaction solution in small portions, and the mixture was stirred at room temperature for 24 hours. A small amount of the reaction solution was added to 200 parts of ice water one by one, and then allowed to stand at room temperature for 15 hours. The water was removed by decantation to obtain a viscous solid in the form of residue. After adding 60 parts of methanol to this viscous solid, the mixture was stirred at room temperature for 15 hours. After the precipitated solid was separated by filtration, it was purified by column chromatography. The purified light yellow solid was dried under reduced pressure at 60° C. to obtain 9.8 parts of the compound represented by formula (C-I-2). The yield is 53%.

The following reaction is carried out under a nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 8.2 parts of the compound represented by formula (BI-2), 10.0 parts of the compound represented by formula (CI-2) and 20.0 parts of toluene were added, and then 12.2 parts of phosphoryl chloride were added, And stir at 95~100℃ for 3 hours. Then, after cooling the reaction mixture to room temperature, it was diluted with 170.0 parts of isopropyl alcohol. Then, the diluted reaction solution was poured into 300.0 parts of saturated saline , Then add 100 parts of toluene and stir for 30 minutes. Then, the stirring was stopped, and it was allowed to stand for 30 minutes. As a result, it was separated into an organic layer and an aqueous layer. After discarding the water layer by liquid separation operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of thenardite was added to the organic layer and stirred for 30 minutes, and then filtered to obtain an organic layer. The obtained organic layer was distilled to remove the solvent in an evaporator to obtain a blue-purple solid. Further, the blue-purple solid was dried under reduced pressure at 60°C to obtain 18.4 parts of the compound represented by formula (A-II-2). The yield is 100%.

Identification of the compound represented by formula (A-II-2)

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

Accurate quality: 722.3

The following reaction is carried out under a nitrogen atmosphere. After 2.0 parts of the compound represented by formula (A-II-2) and 7.3 parts of dichloromethane were put in a flask equipped with a cooling tube and a stirring device, the reaction solution was cooled in an ice bath. Then, 1.6 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred overnight while warming to room temperature. Then, while cooling the reaction solution in an ice bath, it was diluted with 34.0 parts of N,N-dimethylformamide. Then, after the diluted reaction solution was poured into 140.0 parts of toluene, stirring was performed for 30 minutes. Then, the stirring was stopped and decantation was performed to obtain a blue-violet viscous solid. Furthermore, the blue-purple viscous solid was dried under reduced pressure at 60° C. to obtain 2.3 parts of the compound represented by formula (A-I-2). The yield is 100%.

In the formula (AI-2), "-SO ₃ ^- " and "-SO ₃ H" mean that they are bonded to carbon atoms on at least one of the six phenyl rings, respectively.

Identification of the compound represented by formula (A-I-2)

(Mass analysis) ionization mode=ESI+: m/z=847.3[M+H] ⁺

ESI-: m/z=845.5[MH] ^-

Accurate quality: 846.2

0.35g compound of formula (AI-2) represented dissolved in ethyl lactate to become the volume of 250cm ^3, in which the use of ethyl lactate 2cm ³ was diluted to become the volume of 100cm ³ (at a concentration of 0.028g / L ), the absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length 1 cm). This compound showed an absorbance of 2.5 (arbitrary units) at λmax=627 nm.

[Comparative Example 1]

The CI Acid Blue 90 (trade name of Daiwa BLUE 300, Daiwa Kasei) was dissolved in 0.35 g of ethyl lactate became the volume of 250cm ^3, in which the use of ethyl lactate 2cm ³ was diluted to become the volume of 100cm ³ (Concentration: 0.028 g/L), the absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). The compound showed an absorbance of 2.2 (arbitrary unit) at λmax=615 nm.

The absorbance of the compound of Example 1 (A-I-2) and the absorption of C.I. Acid Blue 90 of Comparative Example 1 Compared with the luminosity, it is 0.3 (the concentration is 0.028g/L).

[Example 2]

The following reaction is carried out under a nitrogen atmosphere. After putting 24.2 parts of N-ethylaniline (made by Tokyo Chemical Industry Co., Ltd.) and 240 parts of N,N-dimethylformamide in a flask equipped with a cooling tube and a stirring device, the mixed solution was cooled in an ice bath. Under ice cooling, 8.0 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in small portions over 30 minutes, and 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.) was added to the reaction liquid in small amounts one by one, and stirred at room temperature for 72 hours. Water was added to the reaction solution, extraction was performed with dichloromethane, and washing was performed three times with saturated saline. It was dried with magnesium sulfate, concentrated after filtration. The obtained crude body was purified by column chromatography. The purified light yellow solid was dried under reduced pressure at 60° C. to obtain 7.4 parts of the compound represented by formula (C-I-3). The yield is 27%.

The following reaction is carried out under a nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 7.6 parts of the compound represented by the formula (BI-2), 10.0 parts of the compound represented by the formula (CI-3) and 20.0 parts of toluene were added, followed by 11.4 parts of phosphoryl chloride, And stir at 95~100℃ for 3 hours. Then, after cooling the reaction mixture to room temperature, it was diluted with 170.0 parts of isopropyl alcohol. Then, the diluted reaction solution was poured into 300.0 parts of saturated brine, 100 parts of toluene was added, and stirred for 30 minutes. Then, the stirring was stopped and it was allowed to stand for 30 minutes. As a result, it was separated into an organic layer and an aqueous layer. After discarding the water layer by liquid separation operation, the organic layer was washed with 300 parts of saturated saline. Add an appropriate amount of awn to the organic layer After stirring for 30 minutes, it was filtered to obtain a dried organic layer. The obtained organic layer was distilled to remove the solvent in an evaporator to obtain a blue-purple solid. The obtained blue-violet solid was purified by column chromatography. The purified blue-purple solid was dried under reduced pressure at 60°C to obtain 17.8 parts of the compound represented by formula (A-II-3). The yield is 100%.

Identification of the compound represented by formula (A-II-3)

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

Accurate quality: 750.3

When the compound represented by formula (A-II-3) is sulfonated in the same manner as in Example 1, the compound represented by formula (A-I-3) is obtained.

In the formula (AI-3), "-SO ₃ ^- " and "-SO ₃ H" mean that they are bonded to carbon atoms on at least one of the six phenyl rings, respectively.

[Example 3]

The following reaction is carried out under a nitrogen atmosphere. After putting 28.9 parts of potassium thiocyanate and 160.0 parts of acetone in the flask equipped with a cooling tube and a stirring device, it stirred at room temperature for 30 minutes. Then, 50.0 parts of 2,6-difluorobenzyl chloride (made by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Then, after cooling the reaction mixture in an ice bath, 36.4 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After the dropwise addition was completed, the mixture was further stirred at room temperature for 30 minutes. Then, after cooling the reaction mixture in an ice bath, 34.2 parts of a 30% sodium hydroxide aqueous solution was added dropwise. After the dropwise addition was completed, the mixture was further stirred at room temperature for 30 minutes. Then, 28.1 parts of chloroacetic acid was added dropwise at room temperature. After the dropwise addition, the mixture was stirred under heating and reflux for 7 hours. Then, 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 it was allowed to stand for 30 minutes. As a result, it was separated into an organic layer and an aqueous layer. After the water layer was discarded by the liquid separation operation, the organic layer was washed with 200 parts of 1 equivalent hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of thenardite was added to the organic layer, and after stirring for 30 minutes, it was filtered to obtain a dried organic layer. The obtained organic layer was distilled to remove the solvent in an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified light yellow liquid was dried under reduced pressure at 60°C to obtain 25.2 parts of the compound represented by formula (B-I-3). The yield is 27%.

The following reaction is carried out under a nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 8.1 parts of the compound represented by the formula (BI-3), 10.0 parts of the compound represented by the formula (CI-3) and 20.0 parts of toluene were added, followed by the addition of 11.4 parts of phosphoryl chloride, And stir at 95~100℃ for 3 hours. Then, after cooling the reaction mixture to room temperature, it was diluted with 170.0 parts of isopropyl alcohol. Then, the diluted reaction solution was poured into 300.0 parts of saturated brine, 100 parts of toluene was added, and stirred for 30 minutes. Then, the stirring was stopped, and it was allowed to stand for 30 minutes. As a result, it was separated into an organic layer and an aqueous layer. After discarding the water layer by liquid separation operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of thenardite was added to the organic layer, and after stirring for 30 minutes, it was filtered to obtain a dried organic layer. The obtained organic layer was distilled to remove the solvent in an evaporator to obtain a blue-purple solid. The obtained blue-violet solid was purified by column chromatography. The purified blue-purple solid was dried under reduced pressure at 60°C to obtain 18.3 parts of the compound represented by formula (A-II-4). The yield is 100%.

Identification of the compound represented by formula (A-II-4)

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

Accurate quality: 768.3

When the compound represented by formula (A-II-4) is sulfonated in the same manner as in Example 1, the compound represented by formula (A-I-4) is obtained.

In the formula (AI-4), "-SO ₃ ^- " and "-SO ₃ H" mean that they are bonded to carbon atoms on at least one of the six phenyl rings, respectively.

[Industry availability]

The compounds of the present invention have higher absorbance. When the color-curable resin composition used for manufacturing the liquid crystal display part contains the compound of the present invention, the amount used may be small.

Claims (4)

A compound, which is represented by the formula (AI):

[In formula (AI), R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a and R ^8a each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and SO ₃ ^- group Or SO ₃ M group; R ^9a and R ^10a independently represent a hydrogen atom, an alkyl group having 1 to 10 carbons, an aromatic hydrocarbon group which may be substituted, or an aralkyl group which may be substituted; R ^11a to R ^20a respectively It independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogen atom, an SO ₃ ^- group or an SO ₃ M group; in the above R ^1a to R ^20a , the above alkyl group may also constitute a methylene group constituting the above An oxygen atom is inserted between; R ^45a and R ^46a independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group which may be substituted; R ^55a 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 ^45a , R ^46a , and R ^55a , for the above alkyl group, an oxygen atom may also be inserted between the methylene groups constituting it; M represents a hydrogen ion, a metal ion, or an ammonium ion ; Among them, R ^1a ~ R ^20a , R ^45a , R ^46a and R ^55a meet at least any of the requirements of (1), (2) and (3), and the requirements of (4): (1) R ^1a ~ R ^8a And at least one of R ^11a to R ^20a is an SO ₃ ^- group or a SO ₃ M group; (2) at least one of R ^9a , R ^10a , R ^45a , R ^46a and R ^55a has an SO ₃ ^- group or SO ₃ M Aromatic hydrocarbon groups with substituents as substituents; (3) At least one of R ^9a and R ^10a is an aralkyl group having a SO ₃ ^- group or SO ₃ M group as a substituent on the ring; (4) Formula (AI) The number of SO ₃ ^- groups in the compound represented is 1, and the number of SO ₃ M groups is 0~6]. A color-curing resin composition comprising the compound represented by the formula (A-I) of claim 1. A color filter formed by using the color-curing resin composition according to claim 2. A display device including the color filter according to claim 3.