TW201823225A - Compound and coloring curable resin composition - Google Patents

Abstract

The present invention provides a compound represent by the formula (Ia) which can be used as dye (R<SP>1a</SP>, R<SP>2a</SP>, R<SP>3a</SP> and R<SP>4a</SP> are each independently represents an alkyl group with a carbon number of 1 to 20, and a cycloalkyl group with a carbon number of 5 to 10. provided that the case that R<SP>1a</SP>, R<SP>2a</SP>, R<SP>3a</SP> and R<SP>4a</SP> all represents the same group is excluded.).

Description

   Compound and colored hardening resin composition   

The present invention relates to a compound that can be used as a dye and a coloring curable resin composition.

Dyes are used, for example, in the field of fiber materials, liquid crystal display devices, inkjet, and the like that use reflected light or transmitted light to display colors. As such a dye, for example, a sulfodibenzopiperan-based dye represented by the following formula (a) having a dibenzopiperan skeleton is known (Patent Document 1). In addition, a rhodamine (also referred to as rhodamine) B represented by the following formula (b) is also known (Non-Patent Document 1).

    [Prior technical literature]         [Patent Literature]    

Patent Document 1: Japanese Patent Application Laid-Open No. 3-107489

    [Non-patent literature]    

Non-Patent Document 1: Hosoda Toyotomi, "New Dye Chemistry", Gibakudo Co., Ltd .; 1st edition, May 1973, p. 274

The solubility of the above-mentioned compounds in organic solvents has not always been satisfactory.

The present invention includes the following inventions.

[1] a compound represented by formula (Ia), [R ^1a , R ^2a , R ^3a and R ^4a each independently represent an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms; furthermore, R ^1a and R ^2a can be combined with each other and with each other The bonded nitrogen atoms form a ring together, and R ^3a and R ^4a can be combined with each other and form a ring with these bonded nitrogen atoms, except that the cases where R ^1a , R ^2a , R ^3a and R ^{4a are} all the same base; The -CH ₂ -contained in the alkyl group may be substituted with -O-, -NR ^b -or -CO-, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or- OH substitution, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 8 carbon atoms, and R ^b represents an alkyl group having 1 to 3 carbon atoms].

[2] The compound according to [1], wherein R ^1a , R ^2a , R ^3a, and R ^4a each independently represent an alkyl group having 1 to 20 carbon atoms, and -CH ₂ -contained in the alkyl group may be -O- or -CO- is substituted, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom or an aromatic hydrocarbon group having 6 to 10 carbon atoms.

[3] The compound according to [1] or [2], wherein at least two of R ^1a , R ^2a , R ^3a, and R ^4a are alkyl groups having 2 to 20 carbon atoms, and the above-mentioned alkyl group contains -CH ₂ -may be substituted with -O- or -CO-, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom or an aromatic hydrocarbon group having 6 to 10 carbon atoms.

[4] The compound according to any one of [1] to [3], wherein R ^1a , R ^2a , R ^3a, and R ^4a are each independently an alkyl group having 2 to 20 carbon atoms, and the alkyl group contains -CH ₂ -may be substituted by -O-.

[5] The compound according to any one of [1] to [4], wherein one of R ^1a , R ^2a , R ^3a, and R ^4a is contained in an alkyl group having 2 to 20 carbon atoms- CH ₂ -substituted by -O-.

[6] The compound according to [1], wherein R ^1a and R ^2a are each independently an alkyl group having 2 to 6 carbon atoms, and R ^3a and R ^4a are each independently an alkyl group having 1 to 6 carbon atoms.

[7] The compound according to [1], wherein R ^1a and R ^2a are each ethyl, and R ^3a and R ^4a are each independently methyl, propyl, or butyl.

[8] The compound according to [1], wherein each of R ^1a and R ^2a is an ethyl group, and R ^3a is a -CH ₂ -substituted by -O- group contained in an alkyl group having 4 to 15 carbon atoms.

[9] a compound represented by formula (Ib), [R ^1b , R ^2b and R ^3b each independently represent an alkyl group having 1 to 8 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atom may be substituted with an alkoxy group having 1 to 3 carbon atoms; Ar represents a group represented by formula (i), (R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a halogen atom; m represents an integer of 1 to 5, and when m is 2 or more, a plurality of R may be each the same Or different; * represents a bonding bond with a nitrogen atom)]].

[10] The compound according to [9], wherein R ^1b , R ^2b and R ^3b are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl or 2-ethylhexyl.

[11] The compound according to [9] or [10], wherein R is a methyl group.

[12] The compound according to any one of [9] to [11], wherein m is 1 or 2.

[13] The compound according to any one of [9] to [12], wherein Ar is a group represented by formula (C-0), a group represented by formula (C-1), or formula (C- 2) the base shown, (* Indicates a bonding bond with a nitrogen atom).

[14] a compound represented by formula (Ic), [X ¹ and X ² are different from each other and each represents an alkyl group having 1 to 8 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms. A hydrogen atom may be substituted with an alkoxy group having 1 to 3 carbon atoms; Ar ¹ and Ar ² each independently represent a group represented by formula (i), (R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a halogen atom; m represents an integer of 1 to 5, and when m is 2 or more, a plurality of R may be the same Or different; * represents a bonding bond with a nitrogen atom)]].

[15] The compound according to [14], wherein X ¹ and X ² are each methyl, ethyl, n-propyl, isopropyl, n-butyl, or 2-ethylhexyl.

[16] The compound according to [14] or [15], wherein R is a methyl group.

[17] The compound according to any one of [14] to [16], wherein m is 1 or 2.

[18] The compound according to any one of [14] to [17], wherein Ar ¹ and Ar ² are each independently a group represented by formula (C-0) and a group represented by formula (C-1) Base or base represented by formula (C-2), (* Indicates a bonding bond with a nitrogen atom).

[19] A coloring agent comprising the compound described in any one of [1] to [18].

[20] The coloring agent according to [19], further comprising a pigment.

[21] A coloring curable resin composition comprising the coloring agent according to [19] or [20], a resin, a polymerizable compound, a polymerization initiator, and a solvent.

[22] A coating film formed from the colored curable resin composition according to [21].

[23] A color filter formed of the coloring curable resin composition according to [21].

[24] A display device including the color filter according to [23].

The compound of the present invention is excellent in solubility in an organic solvent, and it is expected that the color filter formed of the color-curing resin composition containing the compound of the present invention has higher brightness.

The first compound of the present invention is a compound represented by formula (Ia) (hereinafter also referred to as "compound (Ia)"). The compounds of the present invention also include their tautomers and stereoisomers (Stereoisomer).

[R ^1a , R ^2a , R ^3a and R ^4a each independently represent an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms; furthermore, R ^1a and R ^2a can be combined with each other and with each other The combined nitrogen atoms form a ring together, and R ^3a and R ^4a can be combined with each other and form a ring with the combined nitrogen atoms, except that the cases where R ^1a , R ^2a , R ^3a and R ^{4a are} all the same base; The -CH ₂ -contained in the alkyl group may be substituted with -O-, -NR ^b -or -CO-, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or- OH substitution, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by an alkoxy group having 1 to 8 carbon atoms, and R ^b represents an alkyl group having 1 to 3 carbon atoms].

In the formula (Ia), there is no case where all of R ^1a , R ^2a , R ^3a , and R ^4a are the same base.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl , Tridecyl, tetradecyl, pentadecyl, hexadecyl, hexadecyl, octadecyl, undecyl, eicosyl, etc. Alkyl; isopropyl, isobutyl, secondary butyl, isopentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1- Ethylbutyl, 2-ethylbutyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2 -Ethylpentyl, 3-ethylpentyl, 1-propylbutyl, 1- (1-methylethyl) butyl, 1- (1-methylethyl) -2-methylpropyl , 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 1-ethylhexyl, 2 -Ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 1-n-propylpentyl, 2-propylpentyl, 1- (1-methylethyl) pentyl, 1-butylbutyl Base, tertiary butyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,2-dimethyl Butyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1-ethyl-2-methylpropyl, 1,1-dimethylpentyl, 1,2-di Methylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethyl Methylpentyl, 3,3-dimethylpentyl, 3,4-dimethylpentyl, 1-ethyl-1-methylbutyl, 1-ethyl-2-methylbutyl, 1 -Ethyl-3-methylbutyl, 2-ethyl-1-methylbutyl, 2-ethyl-3-methylbutyl, 1,1-dimethylhexyl, 1,2-dimethyl Hexyl, 1,3-dimethylhexyl, 1,4-dimethylhexyl, 1,5-dimethylhexyl, 2,2-dimethylhexyl, 2,3-dimethylhexyl, 2, 4-dimethylhexyl, 2,5-dimethylhexyl, 3,3-dimethylhexyl, 3,4-dimethylhexyl, 3,5-dimethylhexyl, 4,4-dimethyl Hexyl, 4,5-dimethylhexyl, 1-ethyl-2-methylpentyl, 1-ethyl-3-methylpentyl, 1-ethyl-4-methylpentyl, 2-ethyl Methyl-1-methylpentyl, 2-ethyl-2-methylpentyl, 2-ethyl-3-methylpentyl, 2-ethyl-4-methylpentyl, 3-ethyl- 1-methylpentyl, 3-ethyl-2-methylpentyl, 3-ethyl-3-methylpentyl, 3-ethyl-4-methylpentyl , 1-propyl-1-methylbutyl, 1-propyl-2-methylbutyl, 1-propyl-3-methylbutyl, 1- (1-methylethyl) -1- Methylbutyl, 1- (1-methylethyl) -2-methylbutyl, 1- (1-methylethyl) -3-methylbutyl, 1,1-diethylbutyl And branched chain alkyl groups having 3 to 20 carbon atoms such as 1,2-diethylbutyl.

The -CH ₂ -contained in the above alkyl group may be substituted with -O-, -NR ^b -or -CO-, R ^b represents an alkyl group having 1 to 3 carbon atoms, and an alkyl group having 1 to 3 carbon atoms may be listed as: Methyl, ethyl, propyl, isopropyl and the like. The -CH ₂ -substituted by -O-, -NR ^b -or -CO- contained in the alkyl group is preferably the -CH ₂ -substituted by -O- or -CO- contained group in the alkyl group. The -CH ₂ -substituted by -O- group contained in the alkyl group is more preferred.

The hydrogen atom contained in the alkyl group may be substituted with a halogen atom, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or -OH, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 8 carbon atoms. A hydrogen atom contained in an alkyl group is substituted with a halogen atom, an aromatic hydrocarbon group having 6 to 20 carbon atoms or -OH, and a hydrogen atom contained in the alkyl group is substituted with a halogen atom or an aromatic hydrocarbon group with 6 to 20 carbon atoms. The base is better.

Examples of the halogen atom include a fluorine atom, and examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, a biphenyl group, a tolyl group, an ethylphenyl group, a propylphenyl group, and a butylphenyl group. , Pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl and the like. Examples of the alkoxy group having 1 to 8 carbon atoms include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, secondary butoxy, pentoxy, iso Pentyloxy, hexyloxy, heptyloxy, octyloxy and the like.

Specific examples of the group in which the hydrogen atom contained in the alkyl group is substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms are as follows. In the following formula, * represents a bonding bond with a nitrogen atom.

Regarding the -CH ₂ -substituted by -O-, -NR ^b -or -CO- contained in the alkyl group, the hydrogen atom contained in the alkyl group is substituted by a halogen atom, an aromatic hydrocarbon group having 6 to 20 carbon atoms or -OH Substituted groups, and -CH ₂ -substituted by -O-, -NR ^b -or -CO- contained in alkyl groups and hydrogen atoms contained in alkyl groups by halogen atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms, or Examples of the -OH substituted group include the following formulae (D-1) to (D-18), (D-31) to (D-45), and (D-50) to (D-57) Show the base. In the following formula, * represents a bonding bond with a nitrogen atom.

Among them, from the viewpoint of ease of production and better solubility in organic solvents, the formulas (D-2), (D-8), (D-14), (D-17), The formula (D-42), formula (D-43), formula (D-45), or formula (D-56) are preferred. The formula (D-8), formula (D-14), formula The base represented by (D-17), formula (D-42) or formula (D-45) is more preferable.

Examples of the cycloalkyl group having 5 to 10 carbon atoms include: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 2-methylpentyl, 2-methylhexyl, 2,5-dimethylpentyl , 2,6-dimethylhexyl, etc.

Examples of the ring that R ^1a and R ^{2a are} bonded to each other and formed with these bonded nitrogen atoms include, for example, a pyrrolidine ring, a morpholin ring, a piperidine ring, and piperidine. Ring etc.

Examples of the ring in which R ^3a and R ^{4a are} bonded to each other and formed with these bonded nitrogen atoms include, for example, a pyrrolidine ring, a morpholin ring, a piperidine ring, and piperidine. Ring etc.

Preferably, R ^1a , R ^2a , R ^3a and R ^4a are each independently an alkyl group having 1 to 20 carbon atoms, and -CH ₂ -contained in the alkyl group may be substituted with -O- or -CO-, and the above The compound (Ia) in which a hydrogen atom contained in the alkyl group may be substituted with a halogen atom or an aromatic hydrocarbon group having 6 to 10 carbon atoms.

Preferably, at least two of R ^1a , R ^2a , R ^3a and R ^4a are alkyl groups having 2 to 20 carbon atoms, and -CH ₂ -contained in the alkyl group may be substituted by -O- or -CO- The compound (Ia) in which a hydrogen atom contained in the alkyl group may be substituted with a halogen atom or an aromatic hydrocarbon group having 6 to 10 carbon atoms.

Preferred are compounds (Ia) in which R ^1a , R ^2a , R ^3a and R ^4a are each independently an alkyl group having 2 to 20 carbon atoms and the -CH ₂ -which may be substituted with -O- contained in the alkyl group.

Preferred is a compound (Ia) in which at least one of R ^1a , R ^2a , R ^3a and R ^4a is a -CH ₂ -O-substituted group contained in an alkyl group having 2 to 20 carbon atoms.

Preferred are compounds (Ia) in which R ^1a and R ^2a are each independently an alkyl group having 2 to 6 carbon atoms, and R ^3a and R ^4a are each independently an alkyl group having 1 to 6 carbon atoms.

Preferred are compounds (Ia) in which R ^1a and R ^2a are each an ethyl group, and R ^3a and R ^4a are each independently a methyl group, a propyl group, or a butyl group.

Preferred are compounds (Ia) in which each of R ^1a and R ^2a is an ethyl group, and R ^3a is a -CH ₂ -O-substituted group contained in an alkyl group having 4 to 15 carbon atoms.

Specific examples of the compound (Ia) include the compounds shown in Table 1. In Table 1, Me represents -CH ₃ , Et represents -CH ₂ CH ₃ , Pr represents -CH ₂ CH ₂ CH ₃ , i-Pr represents -CH (CH ₃ ) ₂ , and Bu represents -CH ₂ CH ₂ CH ₂ CH ₃ , i-Bu means -CH ₂ CH (CH ₃ ) ₂ , Pen means -CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ , Hex means -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ , EtHex means -CH ₂ CH (C ₂ H ₅ ) (CH ₂ ) ₃ CH ₃ .

Among them, from the viewpoints of ease of production and particularly excellent solubility in organic solvents, compounds (Ia-2), compounds (Ia-3), compounds (Ia-4), compounds (Ia-5), and compounds (Ia-6), compound (Ia-7), compound (Ia-8), compound (Ia-9), compound (Ia-13), compound (Ia-14), compound (Ia-15), compound ( Ia-16), compound (Ia-51), compound (Ia-55), compound (Ia-59), compound (Ia-63), compound (Ia-66), compound (Ia-67), compound (Ia -68), compound (Ia-69), compound (Ia-70), compound (Ia-71), compound (Ia-73), compound (Ia-75), or compound (Ia-77), preferably compound (Ia-7), compound (Ia-16), compound (Ia-67), compound (Ia-68) or compound (Ia-69) is more preferable.

Compound (Ia) can be obtained by reacting a compound represented by formula (IIIa) (hereinafter also referred to as "compound (IIIa)") with a compound represented by formula (IVa) (hereinafter also referred to as "compound (IVa)"), A compound represented by formula (Va) (hereinafter also referred to as "compound (Va)") is obtained, and the obtained compound (Va) is reacted with a compound represented by formula (VIa) (hereinafter also referred to as "compound (VIa)") While manufacturing.

[In formula (IVa), R ^1a and R ^2a each have the same meaning as described above]

[In formula (IVa), R ^3a and R ^4a each have the same meaning as described above].

Further, a compound represented by formula (VIIa) (hereinafter also referred to as "compound (VIIa)") can be obtained by reacting compound (IIIa) with compound (VIa), and the obtained compound (VIIa) and compound ( IVa) to produce compound (Ia).

This reaction can be carried out in the presence of a solvent. Examples of the above solvents include: hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; methanol, ethanol, propanol, isopropanol, and butanol Alcohol solvents such as ethylene glycol; nitro hydrocarbon solvents such as nitrobenzene; ketone solvents such as methyl isobutyl ketone; 1-methyl-2-pyrrolidone, N, N-dimethylformamide, N , N-dimethylacetamide, and other amine solvents; water and so on.

The reaction temperature is preferably -10 ° C to 180 ° C, and more preferably 0 ° C to 100 ° C. The reaction time is preferably from 1 hour to 12 hours, and more preferably from 1 hour to 8 hours.

The amount of the compound (IVa) or the compound (VIa) used is preferably 1 mol or more and 30 mol or less, more preferably 2 mol or more and 4 mol or less, relative to 1 mol of the compound (IIIa).

The method for obtaining the target compound (Ia) from the reaction mixture is not particularly limited, and various known methods can be used. For example, the reaction mixture may be mixed with an acid (for example, acetic acid, hydrochloric acid, etc.), and then the precipitated crystals may be filtered. The acid is preferably prepared by preparing an acid aqueous solution and adding a reaction mixture to the aqueous solution. The temperature when the reaction mixture is added is preferably 0 ° C to 50 ° C, and more preferably 10 to 40 ° C. After adding the reaction mixture to the acidic aqueous solution, it is preferable to stir at about 0.5 to 2 hours at the same temperature. The crystals collected by filtration are washed with water or the like and then dried. Furthermore, if necessary, it can be further purified by conventional methods such as recrystallization.

The second compound of the present invention is a compound represented by formula (Ib) (hereinafter also referred to as "compound (Ib)"). The compounds of the present invention also include their tautomers.

[R ^1b , R ^2b, and R ^3b each independently represent an alkyl group having 1 to 8 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atom may be substituted with an alkoxy group having 1 to 3 carbon atoms. Ar represents a base represented by formula (i).

(R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a halogen atom; m represents an integer of 1 to 5, and when m is 2 or more, a plurality of R may be the same Or different; * represents a bonding bond with a nitrogen atom)]].

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ^1b , R ^2b and R ^3b include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl. Linear alkyl such as n-octyl; isopropyl, isobutyl, secondary butyl, isopentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4 -Methylpentyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 1-propylbutyl, 1- (1-methylethyl) butyl, 1- (1-methylethyl ) -2-methylpropyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl , 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 1-n-propylpentyl, 2-propylpentyl, 1- (1-methylethyl) Amyl, 1-butylbutyl, tertiary butyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethyl Methylbutyl, 2,3-dimethylbutyl, 1-ethyl-2-methylpropyl, 1,1-dimethylpentyl, 1,2-dimethylpentyl, 1,3 - Methylpentyl, 1,4-dimethylpentyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethyl Methylpentyl, 3,4-dimethylpentyl, 1-ethyl-1-methylbutyl, 1-ethyl-2-methylbutyl, 1-ethyl-3-methylbutyl , 2-ethyl-1-methylbutyl, 2-ethyl-3-methylbutyl, 1,1-dimethylhexyl, 1,2-dimethylhexyl, 1,3-dimethyl Hexyl, 1,4-dimethylhexyl, 1,5-dimethylhexyl, 2,2-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5 -Dimethylhexyl, 3,3-dimethylhexyl, 3,4-dimethylhexyl, 3,5-dimethylhexyl, 4,4-dimethylhexyl, 4,5-dimethylhexyl , 1-ethyl-2-methylpentyl, 1-ethyl-3-methylpentyl, 1-ethyl-4-methylpentyl, 2-ethyl-1-methylpentyl, 2 -Ethyl-2-methylpentyl, 2-ethyl-3-methylpentyl, 2-ethyl-4-methylpentyl, 3-ethyl-1-methylpentyl, 3-ethyl 2-methylpentyl, 3-ethyl-3-methylpentyl, 3-ethyl-4-methylpentyl, 1-propyl-1-methylbutyl, 1-propyl- 2-methylbutyl, 1-propyl-3-methylbutyl, 1- (1-methylethyl) -1-methylbutyl, 1- (1-methyl Methyl) 2-methylbutyl, 1- (1-methylethyl) -3-methylbutyl, 1,1-diethylbutyl, 1,2-diethylbutyl and other branches Chain alkyl; etc.

The hydrogen atom contained in the alkyl group having 1 to 8 carbon atoms may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the aromatic hydrocarbon group having 6 to 10 carbon atoms may be exemplified by phenyl, naphthyl, and tolyl , Ethylphenyl, n-propylphenyl, isopropylphenyl and the like. The hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted by an alkoxy group having 1 to 3 carbon atoms. Examples of the alkoxy group having 1 to 3 carbon atoms include methoxy, ethoxy, N-propoxy, isopropoxy.

Examples of the group in which a hydrogen atom contained in the alkyl group is substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms include the following groups.

(* Indicates a bond with a nitrogen atom)

Examples of the alkyl group having 1 to 3 carbon atoms represented by R include methyl, ethyl, n-propyl, isopropyl, and the like, and a hydrogen atom contained in the alkyl group having 1 to 3 carbon atoms is substituted with a halogen atom. Examples include the following.

-CF ₃ -CH ₂ Cl -CH ₂ Br -CH ₂ F

-C ₂ H ₄ Cl -C ₂ H ₄ Br -C ₂ H ₄ F

-C ₂ H ₄ -CH ₂ Cl -C ₂ H ₄ -CH ₂ Br -C ₂ H ₄ -CH ₂ F

m represents an integer of 1 to 5, and from the viewpoint of obtaining raw materials, 1 or 2 is preferred.

Examples of the group represented by formula (i) include the following groups. Among them, a base represented by formula (C-0), a base represented by formula (C-1), or a base represented by formula (C-2) is preferred.

(* Indicates a bond with a nitrogen atom)

Examples of the compound (Ib) include the compounds shown in Table 2. In Table 2, Me represents -CH ₃ , Et represents -CH ₂ CH ₃ , Pr represents -CH ₂ CH ₂ CH ₃ , i-Pr represents -CH (CH ₃ ) ₂ , and Bu represents -CH ₂ CH ₂ CH ₂ CH ₃ , t-Bu represents -C (CH ₃ ) ₃ , and EtHex represents -CH ₂ CH (C ₂ H ₅ ) (CH ₂ ) ₃ CH ₃ . In the Ar column of Table 2, the numbers starting with C represent the numbers of the above formula exemplified as the base represented by formula (i).

Among them, from the viewpoint of particularly excellent solubility in organic solvents, the compound (Ib-8), the compound (Ib-36), the compound (Ib-37), the compound (Ib-38), and the compound (Ib-101) are good.

Next, the manufacturing method of a compound (Ib) is demonstrated.

Examples of the method for producing the compound (Ib) include a compound represented by formula (IIb) (hereinafter also referred to as "compound (IIb)") and a compound represented by formula (IIIb) (hereinafter also referred to as "compound (IIIb)" ) In an organic solvent to obtain a compound represented by the formula (IVb) (hereinafter also referred to as "compound (IVb)"), and the compound (IVb) and a compound represented by the formula (Vb) (hereinafter also referred to as "compound" (Vb) ") A method for producing a reaction in an organic solvent.

[In formula (IIIb), R ^1b and R ^2b each have the same meaning as described above]

[In formula (IVb), R ^1b and R ^2b each have the same meaning as described above]

[In formula (Vb), R ^3b , R and m each have the same meaning as described above]

Examples of the organic solvent in the reaction between the compound (IIb) and the compound (IIIb) include: hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, and butanol; Nitrocarbon solvents such as nitrobenzene; ketone solvents such as methyl isobutyl ketone; amine solvents such as 1-methyl-2-pyrrolidone; etc.

In the reaction between the compound (IIb) and the compound (IIIb), the reaction temperature is preferably 0 ° C to 100 ° C, and more preferably 20 ° C to 80 ° C. The reaction time is preferably from 1 hour to 12 hours, and more preferably from 1 hour to 8 hours.

The amount of the compound (IIIb) used is preferably 1 mol or more and 30 mol or less, and more preferably 2 mol or more and 20 mol or less relative to 1 mol of the compound (IIb).

Examples of the organic solvent in the reaction between the compound (IVb) and the compound (Vb) include: hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, and butanol; Nitrocarbon solvents such as nitrobenzene; ketone solvents such as methyl isobutyl ketone; amine solvents such as 1-methyl-2-pyrrolidone; etc.

In the reaction between the compound (IVb) and the compound (Vb), the reaction temperature is preferably 30 ° C to 180 ° C, and more preferably 20 ° C to 130 ° C. The reaction time is preferably from 1 hour to 24 hours, and more preferably from 1 hour to 8 hours.

The amount of the compound (Vb) used is preferably 1 mol or more and 30 mol or less, more preferably 2 mol or more and 20 mol or less, relative to 1 mol of the compound (IIIb).

The method for obtaining the target compound (Ib) from the reaction mixture is not particularly limited, and various known methods can be used. For example, the reaction mixture can be mixed with an acid (such as acetic acid, etc.), and then the precipitated crystals can be filtered. The acid is preferably prepared by preparing an acid aqueous solution and adding a reaction mixture to the aqueous solution. The temperature when adding the reaction mixture is preferably 10 ° C to 50 ° C, more preferably 20 to 50 ° C, and even more preferably 20 to 30 ° C. After adding the reaction mixture to the acidic aqueous solution, it is preferable to stir at about 0.5 to 2 hours at the same temperature. The crystals collected by filtration are preferably washed with water and then dried. Furthermore, if necessary, it can be further purified by conventional methods such as recrystallization.

The third compound of the present invention is a compound represented by formula (Ic) (hereinafter also referred to as "compound (Ic)"). The compounds of the present invention also include their tautomers.

[X ¹ and X ² are different from each other and each represents an alkyl group having 1 to 8 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atom may be substituted with an alkoxy group having 1 to 3 carbon atoms. Ar ¹ and Ar ² each independently represent a group represented by formula (i).

(R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a halogen atom; m represents an integer of 1 to 5, and when m is 2 or more, a plurality of R may be the same Or different; * represents a bonding bond with a nitrogen atom)]].

X ¹ and X ² are different from each other.

Examples of the alkyl group having 1 to 8 carbon atoms represented by X ¹ and X ² include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. Linear alkyl groups such as isopropyl; isopropyl, isobutyl, secondary butyl, isopentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methyl Amyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethyl Pentyl, 2-ethylpentyl, 3-ethylpentyl, 1-propylbutyl, 1- (1-methylethyl) butyl, 1- (1-methylethyl) -2 -Methylpropyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 1- Ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 1-n-propylpentyl, 2-propylpentyl, 1- (1-methylethyl) pentyl, 1-butylbutyl, tertiary butyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl Group, 2,3-dimethylbutyl, 1-ethyl-2-methylpropyl, 1,1-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethyl base Group, 1,4-dimethylpentyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl Methyl, 3,4-dimethylpentyl, 1-ethyl-1-methylbutyl, 1-ethyl-2-methylbutyl, 1-ethyl-3-methylbutyl, 2- Ethyl-1-methylbutyl, 2-ethyl-3-methylbutyl, 1,1-dimethylhexyl, 1,2-dimethylhexyl, 1,3-dimethylhexyl, 1 , 4-dimethylhexyl, 1,5-dimethylhexyl, 2,2-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethyl Hexyl, 3,3-dimethylhexyl, 3,4-dimethylhexyl, 3,5-dimethylhexyl, 4,4-dimethylhexyl, 4,5-dimethylhexyl, 1- Ethyl-2-methylpentyl, 1-ethyl-3-methylpentyl, 1-ethyl-4-methylpentyl, 2-ethyl-1-methylpentyl, 2-ethyl 2-methylpentyl, 2-ethyl-3-methylpentyl, 2-ethyl-4-methylpentyl, 3-ethyl-1-methylpentyl, 3-ethyl-2 -Methylpentyl, 3-ethyl-3-methylpentyl, 3-ethyl-4-methylpentyl, 1-propyl-1-methylbutyl, 1-propyl-2-methyl Butyl, 1-propyl-3-methylbutyl, 1- (1-methylethyl) -1-methylbutyl, 1- (1-methylethyl) -2- Branched chain alkyl groups such as butyl, 1- (1-methylethyl) -3-methylbutyl, 1,1-diethylbutyl, 1,2-diethylbutyl; etc. .

The hydrogen atom contained in the alkyl group having 1 to 8 carbon atoms may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the aromatic hydrocarbon group having 6 to 10 carbon atoms may be exemplified by phenyl, naphthyl, and tolyl , Ethylphenyl, n-propylphenyl, isopropylphenyl and the like. The hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted by an alkoxy group having 1 to 3 carbon atoms. Examples of the alkoxy group having 1 to 3 carbon atoms include methoxy, ethoxy, N-propoxy, isopropoxy.

Examples of the group in which a hydrogen atom contained in the alkyl group is substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms include the following groups.

(* Indicates a bond with a nitrogen atom)

X ¹ and X ² are mutually different, and more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl or 2-ethylhexyl.

Examples of the alkyl group having 1 to 3 carbon atoms represented by R include methyl, ethyl, n-propyl, isopropyl, and the like. A hydrogen atom contained in the alkyl group having 1 to 3 carbon atoms is substituted with a halogen atom. Examples thereof include the following.

-CF ₃ -CH ₂ Cl -CH ₂ Br -CH ₂ F

-C ₂ H ₄ Cl -C ₂ H ₄ Br -C ₂ H ₄ F

-C ₂ H ₄ -CH ₂ Cl -C ₂ H ₄ -CH ₂ Br -C ₂ H ₄ -CH ₂ F

m represents an integer of 1 to 5, and 1 or 2 is preferred from the viewpoint of obtaining raw materials.

Examples of the group represented by the formula (i) include the following groups. Among them, a base represented by formula (C-0), a base represented by formula (C-1), or a base represented by formula (C-2) is preferred. It is preferable that Ar ¹ and Ar ² be the same base.

(* Indicates a bond with a nitrogen atom)

Examples of the compound (Ic) include the compounds shown in Table 3. In Table 3, Me represents -CH ₃ , Et represents -CH ₂ CH ₃ , Pr represents -CH ₂ CH ₂ CH ₃ , i-Pr represents -CH (CH ₃ ) ₂ , and Bu represents -CH ₂ CH ₂ CH ₂ CH ₃ , t-Bu represents -C (CH ₃ ) ₃ , and EtHex represents -CH ₂ CH (C ₂ H ₅ ) (CH ₂ ) ₃ CH ₃ . In the description in the column X ^{1 in} Table 3, the numbers starting with A indicate the numbers of the above formulas as the bases represented by X ¹ . Ar ¹ and Ar ² bar to the beginning of line number represents a C Ar ¹ and Ar represents a group of the formula of No. ² illustrated.

Among them, from the viewpoint of particularly excellent solubility in organic solvents, compounds (Ic-1), compounds (Ic-7), compounds (Ic-132), compounds (Ic-134), compounds (Ic-138), and Compound (Ic-140) is preferred.

Next, a method for producing the compound (Ic-1) will be described.

Examples of the method for producing compound (Ic-1) include a compound represented by formula (IIc) (hereinafter also referred to as "compound (IIc)") and a compound represented by formula (IIIc) (hereinafter also referred to as "compound (IIIc) ) ") After reacting in an organic solvent to obtain a compound represented by formula (IVc) (hereinafter also referred to as" compound (IVc) "), the compound (IVc) and a compound represented by formula (Vc) (hereinafter also referred to as A method for producing a compound (Vc) by reacting it in an organic solvent.

[In formula (IIIc), X ¹ , R, and m each have the same meaning as described above]

[In formula (IVc), X ¹ , R, and m each have the same meaning as described above]

[In formula (Vc), X ² , R, and m each have the same meaning as described above]

Examples of the organic solvent in the reaction between the compound (IIc) and the compound (IIIc) include: hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, and butanol; Nitrocarbon solvents such as nitrobenzene; ketone solvents such as methyl isobutyl ketone; amine solvents such as 1-methyl-2-pyrrolidone; etc.

In the reaction between the compound (IIc) and the compound (IIIc), the reaction temperature is preferably 0 ° C to 100 ° C, and more preferably 20 ° C to 80 ° C. The reaction time is preferably from 1 hour to 12 hours, and more preferably from 1 hour to 8 hours.

The amount of the compound (IIIc) used is preferably 1 mol or more and 30 mol or less, and more preferably 2 mol or more and 20 mol or less relative to 1 mol of the compound (IIc).

Examples of the organic solvent in the reaction between the compound (IVc) and the compound (Vc) include: hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, and butanol; Nitrocarbon solvents such as nitrobenzene; ketone solvents such as methyl isobutyl ketone; amine solvents such as 1-methyl-2-pyrrolidone; etc.

In the reaction between the compound (IVc) and the compound (Vc), the reaction temperature is preferably 30 ° C to 180 ° C, and more preferably 20 ° C to 130 ° C. The reaction time is preferably from 1 hour to 24 hours, and more preferably from 1 hour to 8 hours.

The amount of the compound (Vc) to be used is preferably 1 mol or more and 30 mol or less, more preferably 2 mol or more and 20 mol or less, relative to 1 mol of the compound (IIIc).

The method for obtaining the target compound (Ic) from the reaction mixture is not particularly limited, and various known methods can be used. For example, the reaction mixture can be mixed with an acid (such as acetic acid, etc.), and then the precipitated crystals can be filtered. The acid is preferably prepared by preparing an acid aqueous solution and adding a reaction mixture to the aqueous solution. The temperature when adding the reaction mixture is preferably 10 ° C to 50 ° C, more preferably 20 to 50 ° C, and even more preferably 20 to 30 ° C. After adding the reaction mixture to the acidic aqueous solution, it is preferable to stir at about 0.5 to 2 hours at the same temperature. The crystals collected by filtration are washed with water or the like and then dried. Furthermore, if necessary, it can be further refined by conventional methods such as recrystallization.

The compound (Ia), the compound (Ib), and the compound (Ic) (hereinafter may also be referred to as the "compound (I)" in general) are used as dyes. Since they exhibit high solubility in organic solvents, they are particularly useful. Dyes used in color filters of display devices such as liquid crystal display devices.

The content of the compound (I) contained in the coloring curable resin composition forming the color filter is preferably 0.025 mass% to 48 mass%, and 0.08 mass% to 42 mass% with respect to the total solid content. The following is more preferred, and more preferably from 0.1% by mass to 30% by mass. Here, the "total amount of solid content" in the present specification means an amount after removing the solvent content from the total amount of the coloring curable resin composition. The total amount of the solid content and the content of each component relative thereto can be measured, for example, by a known analysis tool such as a liquid chromatograph or a gas chromatograph.

The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E). It may further contain a leveling agent (F).

The colorant (A) preferably contains the compound (I), and preferably contains a pigment (A1), and may further contain a dye (A2) different from the compound (I).

When the colorant (A) contains both the pigment (A1) and / or the pigment (A2) and the compound (I), the content of the compound (I) is 0.5% by mass or more and 80% by mass relative to the total amount of the colorant (A). It is preferably at most 1%, more preferably at least 1% by mass and at most 70% by mass, and even more preferably at least 1% by mass and at most 50% by mass.

<Pigment (A1)>

The pigment (A1) is not particularly limited, and conventional pigments can be used, and examples thereof include compounds classified into pigments by a color index (published by The Society of Dyers and Colourists).

Examples of the pigment include CI Pigment Yellow 1 (hereinafter, the description of CI Pigment Yellow is omitted and only the number is described), 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83 , 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; CI pigment orange 13, 31 , 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168 , 175, 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 Blue pigments such as 80 and 80; CI pigments purple 1, 19, 23, 29, 32, 36, 38 and other purple pigments; CI pigments green 7, 36, 58 and other green pigments; CI pigments brown 23 and 25 and other brown pigments; CI Black pigments such as Pigment Black 1, 7.

These pigments can be used individually or in mixture of 2 or more types.

Pigments are yellow pigments such as CI Pigment Yellow 138, 139, 150; red pigments such as CI Pigment Red 177, 242, 254; blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60, etc. And CI pigment purple 1, 19, 23, 29, 32, 36, 38 and other purple pigments are preferred. By including the pigment, the transmission spectrum of the color filter using the coloring curable resin composition of the present invention can be easily optimized, and the light resistance and chemical resistance of the color filter can be improved.

Pigment (A1) can be subjected to rosin treatment if necessary, surface treatment using pigment derivatives introduced with acidic or basic groups, grafting treatment on the pigment surface with polymer compounds, etc., and sulfuric acid atomization method, etc. Atomization treatment, organic solvent or water cleaning for removing impurities, and removal processing for removing ionic impurities by ion exchange method.

The pigment (A1) is preferably one having a uniform particle size. By dispersing a pigment dispersant, a pigment dispersion liquid can be obtained in a state where the pigment is uniformly dispersed in the solution.

Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants can be used alone or in combination of two or more. Examples of the pigment dispersant include: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOWLEN (manufactured by Kyoeisha Chemical Co., Ltd.), SOLSPERSE (manufactured by ZENECA Co., Ltd.), EFKA (manufactured by BASF), AJISPER ( (Ajinomoto Fine Chemical Co., Ltd.), Disperbyk (by BYK-CHEMIE), etc.

When a pigment dispersant is used, it is preferably used in an amount of 1 mass% or more and 100 mass% or less, and more preferably 5 mass% or more and 50 mass% or less with respect to the pigment (A1). When the amount of the pigment dispersant used is within the above range, there is a tendency that a pigment dispersion liquid in a uniformly dispersed state can be obtained.

When the colorant (A) contains the pigment (A1), the content of the pigment (A1) is preferably 20% by mass or more and 99.5% by mass or less, and 30% by mass or more and 99% by mass or less with respect to the total amount of the colorant (A). Better.

<Dye (A2)>

Examples of the dye (A2) include oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes, and examples thereof include: Materials Index (published by The Society of Dyers and Colourists), compounds classified as dyes, and conventional dyes described in Dyeing Notes (Dyeing Society). In addition, examples of the chemical structure include azo dyes, cyanine dyes, triphenylmethane dyes, dibenzopiperan dyes, phthalocyanine dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, and azo dyes. Methylene dye, squarylium dye, acridine dye, styrene dye, coumarin dye, quinoline dye, and nitro dye. Among these, organic solvent-soluble dyes are preferred.

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

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

These dyes can be appropriately selected in accordance with the required spectral spectrum of the color filter. These dyes can be used alone or in combination of two or more.

When the dye (A2) is contained, the content of the dye (A2) 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 or less.

The content of the colorant (A) is preferably 5 mass% to 70 mass%, more preferably 5 mass% to 60 mass%, and more preferably 5 mass% to 50 mass% with respect to the total solid content. The following is even better. When the content of the colorant (A) is within the above range, a desired spectrum and color density can be obtained.

<Resin (B)>

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

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

Resin [K1] at least one monomer (a) (hereinafter also referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides and a cyclic ether structure having 2 to 4 carbon atoms Copolymers of monomers (b) (hereinafter also referred to as "(b)") with ethylenically unsaturated bonds; resins [K2] (a) and (b), and monomers (c) copolymerizable with (a) ) (But (a) and (b) are different) (hereinafter also referred to as "(c)"); copolymers of resin [K3] (a) and (c); resin [K4] makes (a ) Resin that reacts with (c) copolymer and (b); Resin [K5] Resin that makes (b) copolymer with (c) and (a); Resin [K6] that makes (b) and (c) The copolymer of) and (a) react to further react the resin with carboxylic anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; maleic acid, fumaric acid, citraconic acid, Zhongconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetracarboxylic acid Unsaturated dicarboxylic acids such as hydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2 -Ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] Hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] Hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene And other bicyclic unsaturated compounds containing carboxyl groups; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2 , 3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride and other unsaturated dicarboxylic anhydrides; succinic acid mono [ 2- (meth) acryloxyethyl] ester, phthalic acid mono [2- (meth) acryloxyethyl] Unsaturated mono [(meth) acryloxyalkyl] esters of polycarboxylic acids with an equivalent of 2 or more; such as α- (hydroxymethyl) acrylic unsaturated acrylates containing hydroxyl and carboxyl groups in the same molecule Wait.

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

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

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

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

Examples of (b) include monomers (b1) having an epoxyethyl group and an ethylenically unsaturated bond (hereinafter also referred to as "(b1)"), monomers having an epoxypropyl group and an ethylenically unsaturated bond (B2) (hereinafter also referred to as "(b2)"), a monomer (b3) (hereinafter also referred to as "(b3)") having a tetrahydrofuranyl group and an ethylenically unsaturated bond.

Examples of (b1) include, for example, a monomer (b1-1) (hereinafter also referred to as "(b1-1)") having an epoxidized structure of a linear or branched aliphatic unsaturated hydrocarbon. A monomer (b1-2) having an epoxidized structure of an alicyclic unsaturated hydrocarbon (hereinafter also referred to as "(b1-2)").

Examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, and glycidyl vinyl ether. , O-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2, 4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3, 4-gins (glycidyloxymethyl) styrene, 2,3,5-gins (glycidyloxymethyl) styrene, 2,3,6-gins (glycidyloxymethyl) styrene, 3,4,5-ginseng (glycidyloxymethyl) styrene, 2,4,6-ginseng (glycidyloxymethyl) styrene, etc.

(b1-2) Examples include vinyl cyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example: CELLOXIDE 2000; manufactured by DAICEL Co., Ltd.), 3,4- Epoxy cyclohexyl methyl (meth) acrylate (eg: CYCLOMER A400; manufactured by DAICEL Co., Ltd.), 3,4-epoxy cyclohexyl methyl (meth) acrylate (eg: CYCLOMER M100; DAICEL Co., Ltd.), a compound represented by formula (VI), a compound represented by formula (VII), and the like.

[In formulae (VI) and (VII), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by 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 an alkanediyl group having a carbon number of 1 to 6; * represents the binding to O key]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, tertiary butyl and the like.

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

Preferred examples of R ^a and R ^b include a hydrogen atom, a methyl group, a methylol group, 1-hydroxyethyl group, and 2-hydroxyethyl group, and more preferred examples include a hydrogen atom and a methyl group.

Examples of alkanediyl groups having 1 to 6 carbon atoms include methylene, ethylidene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, and pentyl. Alkane-1,5-diyl, hexane-1,6-diyl, etc.

Preferred examples of X ^a and X ^b include single bonds, methylene groups, ethylidene groups, * -CH ₂ -O- and * -CH ₂ CH ₂ -O-, and more preferred examples include: single Bond, * -CH ₂ CH ₂ -O- (* represents a bond with O).

Examples of the compound represented by the formula (VI) include compounds represented by any one of the formulae (VI-1) to (VI-15). Among them, formula (VI-1), formula (VI-3), formula (VI-5), formula (VI-7), formula (VI-9), or formula (VI-11) to formula (VI-15) The compound represented by) is more preferable, and the compound represented by formula (VI-1), formula (VI-7), formula (VI-9) or formula (VI-15) is more preferable.

Examples of the compound represented by the formula (VII) include compounds represented by any one of the formula (VII-1) to the formula (VII-15). Among them, (VII-1), (VII-3), (VII-5), (VII-7), (VII-9), or (VII-11) to (VII-15) The compound represented by the formula is preferable, and the compound represented by the formula (VII-1), the formula (VII-7), the formula (VII-9) or the formula (VII-15) is more preferable.

The compound represented by the formula (VI) and the compound represented by the (VII) may be used alone, or a compound represented by the formula (VI) and a compound represented by the (VII) may be used in combination. When these are used in combination, the molar ratio of the compound represented by formula (VI) and the compound represented by (VII) is preferably 5:95 to 95: 5, and 10:90 to 90:10 More preferably, 20:80 to 80:20 is even better.

(b2) A monomer having an epoxypropyl group and a (meth) acrylic fluorenyloxy group is more preferable. (b2) Examples include 3-methyl-3-methacryloxymethyl propylene oxide, 3-methyl-3-propenyloxymethyl propylene oxide, and 3-ethyl-3- Methacryloxymethyl propylene oxide, 3-ethyl-3-propenyloxymethyl propylene oxide, 3-methyl-3-methacryloxyethyl propylene oxide, 3- Methyl-3-propenyloxyethyl propylene oxide, 3-ethyl-3-methacryloxyethyl propylene oxide, 3-ethyl-3-propenyloxyethyl propylene oxide Wait.

(b3) A monomer having a tetrahydrofuranyl group and a (meth) acrylfluorenyl group is more preferable. (b3) Specific examples include tetrahydrofuran methyl acrylate (e.g., VISCOAT V # 150; manufactured by Osaka Organic Chemical Industry Co., Ltd.), and tetrahydrofuran methyl (meth) acrylate.

In terms of (b), from the viewpoint that the reliability of the obtained color filter can be further improved, such as heat resistance and chemical resistance, (b1) is preferred. Furthermore, (b1-2) is more preferable from the viewpoint of excellent storage stability of the colored curable resin composition.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, secondary butyl (meth) acrylate, and tributyl (meth) acrylate. Butyl, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate Ester, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate (in this technology In the field, the name "dicyclopentyl (meth) acrylate" is commonly used. Also, it is also called "tricyclodecyl (meth) acrylate"), tricyclo [5.2.1.0 ^2,6 ] decene-8 -Based (meth) acrylate (in this technical field, the name of "dicyclopentenyl (meth) acrylate" is commonly used), dicyclopentyloxyethyl (meth) acrylate, (meth) acrylic acid Isoamyl ester, adamantane (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, (meth) ) (Meth) acrylates such as benzyl acrylate; 2-hydroxyethyl (meth) acrylate (Hydroxy) -containing (meth) acrylates such as 2-hydroxypropyl (meth) acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl iconate; Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2 .1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5- Methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6 -Dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1 ] Hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Tertiary butoxycarbonyl bicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonyl bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonyl bicyclo [2.2.1] heptane -2-ene, 5,6-bis (tertiary butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] heptane- 2-ene and other bicyclic unsaturated compounds; N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimide-3- Maleimide imino benzoate, N-succinimide imino-4-maleimide butyrate, N-succinimide imino-6-maleimide hexanoate, N- Dicarboimide derivatives such as succinimide-3-maleimide imine propionate, N- (9-acridyl) maleimide, styrene, α-methylstyrene , M-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylic acid Lamine, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

Among these, from the viewpoints of copolymerization reactivity and heat resistance, styrene, vinyltoluene, benzyl (meth) acrylate, tricyclic [5.2.1.0 ^2,6 ] decane-8-yl (methyl ) Acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo [2.2.1] hept-2-ene are preferred.

Resin [K1], the proportion of the structural unit of each source, in all the structural units constituting the resin [K1], the structural unit derived from (a) is 2 to 60 mol% and derived from (b) The construction unit is preferably 40 to 98 mol%, more preferably the construction unit derived from (a) is 10 to 50 mol% and the construction unit derived from (b) is 50 to 90 mol%.

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

The resin [K1] can be referred to, for example, the method described in the document "Experimental Methods for Polymer Synthesis" (by Otsu Takayuki; Issuing Chemical Co., Ltd., 1st edition, 1st issue, March 1, 1972) and the document Manufactured by cited documents.

Specific examples include a method of adding a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like to a reaction container, forming a deoxygenated environment by replacing oxygen with nitrogen, and heating and holding while stirring. . The polymerization initiator, solvent, and the like used herein are not particularly limited, and those generally used in the technical field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic compounds. The oxide (such as benzamidine peroxide) and the solvent may be those that dissolve each monomer. Examples of the solvent (E) of the colored curable resin composition of the present invention include solvents described below.

In addition, the obtained copolymer may be directly used as a solution after the reaction, a solution after being concentrated or diluted, or a solid (powder) taken out by a method such as reprecipitation. In particular, the solvent used in the polymerization is the solvent contained in the colored curable resin composition of the present invention, so that the solution after the reaction can be directly used in the preparation of the colored curable resin composition of the present invention. Therefore, the manufacturing steps of the colored curable resin composition of the present invention can be simplified.

Resin [K2], the proportion of structural units from each source, in all the structural units constituting resin [K2], the structural unit derived from (a) is 2 to 45 mol%, and the source derived from (b) The construction unit is 2 to 95 mol% and the construction unit derived from (c) is preferably 1 to 65 mol%, and the construction unit derived from (a) is 5 to 40 mol%, derived from (b The construction unit of) is 5 to 80 mol% and the construction unit derived from (c) is 5 to 60 mol%.

If the ratio of the structural unit of the resin [K2] is within the above range, there will be storage stability of the coloring curable resin composition, developability when a colored pattern is formed, and solvent resistance, heat resistance, and mechanical strength of the obtained color filter. Excellent tendency.

The resin [K2] can be produced by, for example, the same method described in the method for producing the resin [K1].

Resin [K3], the proportion of the structural unit of each source, in all the structural units constituting the resin [K3], the structural unit derived from (a) is 2 to 60 mol% and derived from (c) The construction unit is preferably 40 to 98 mol%, more preferably the construction unit derived from (a) is 10 to 50 mol% and the construction unit derived from (c) is 50 to 90 mol%.

The resin [K3] can be produced in the same manner as described in the method for producing the resin [K1].

The resin [K4] can be obtained by copolymerizing (a) and (c), and adding a cyclic ether having 2 to 4 carbon atoms in (b) to a carboxylic acid in (a) and / Or carboxylic anhydride.

First, the copolymers of (a) and (c) were produced in the same manner as described in the production method of the resin [K1]. At this time, the ratio of the structural units of each source is preferably the same ratio as listed in the resin [K3].

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

Continuing the manufacture of the copolymers of (a) and (c), replacing the nitrogen in the flask environment with air, and reacting the catalyst of (b), carboxylic acid or carboxylic anhydride with cyclic ether (for example: (dimethylamine Methylmethyl) phenol, etc.) and polymerization inhibitors (eg, hydroquinone, etc.) are added to the flask, and the resin [K4] can be produced by, for example, reacting at 60 to 130 ° C for 1 to 10 hours.

The amount of (b) used is preferably 5 to 80 mols, more preferably 10 to 75 mols, relative to 100 mols of (a). Within this range, there is a tendency that the balance between the storage stability of the colored curable resin composition, the developability at the time of pattern formation, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern will be improved. Since the cyclic ether has high reactivity and does not easily leave unreacted (b), (b) used in the resin [K4] is preferably (b1), and more preferably (b1-1).

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

The reaction conditions such as the feeding method, reaction temperature, and time can be appropriately adjusted in consideration of the heat generated by the manufacturing equipment and polymerization. In addition, as with the polymerization conditions, the feeding method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

In the first stage, the resin [K5] was subjected to the same operation as the method for producing the resin [K1] to obtain a copolymer of (b) and (c). As described above, the obtained copolymer may be used directly after the reaction, a solution after concentration or dilution, or a solid (powder) taken out by a method such as reprecipitation.

The ratio of the structural units derived from (b) and (c) is 5 to 95 mol% of the structural units derived from (b) relative to the total number of moles of the total structural units constituting the above-mentioned copolymer. The construction unit of (c) is 5 to 95 mol%, and the construction unit derived from (b) is 10 to 90 mol%, and the construction unit derived from (c) is 10 to 90 mol%. Better.

Furthermore, under the same conditions as in the method for producing the resin [K4], the cyclic ether derived from (b) and the carboxylic acid possessed by (a) are possessed by the copolymer of (b) and (c). Or react with carboxylic anhydride to obtain resin [K5].

The amount of (a) to be reacted in the copolymer is preferably 5 to 80 moles relative to 100 moles of (b). Since the cyclic ether has high reactivity and does not easily leave unreacted (b), (b) used in the resin [K5] is preferably (b1), and more preferably (b1-1).

The resin [K6] is a resin in which the resin [K5] further reacts with a carboxylic acid anhydride.

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

Examples of the carboxylic acid anhydride include: maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3 , 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride, etc. The amount of carboxylic anhydride used is preferably 0.5 to 1 mole relative to the amount of (a) used.

Specific examples of the resin (B) include: 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic copolymer, 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] Decyl (meth) acrylate / (meth) acrylic copolymer resins [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymerization Product, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (formyl) ) Acrylic acid / N-cyclohexylmaleimide imide copolymer, 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / vinyl Resins [K2] such as toluene copolymer, 3-methyl-3- (meth) acryloxymethyl propylene oxide / (meth) acrylic acid / styrene copolymer; benzyl (meth) acrylate / (Meth) acrylic copolymer, styrene / (meth) acrylic copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic copolymer, etc. [K3] ; Addition of glycidyl (meth) acrylate in benzyl (meth) acrylate / (meth) acrylic acid copolymer Resin, tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer obtained by adding glycidyl (meth) acrylate, and tricyclodecyl (meth) acrylate Resin [K4], such as a resin obtained by adding glycidyl (meth) acrylate, to an ester / benzyl (meth) acrylate / (meth) acrylic acid copolymer; tricyclodecyl (meth) acrylate / (Meth) acrylic acid glycidyl ester copolymer and (meth) acrylic acid reacted resin, tricyclodecyl (meth) acrylic acid ester / styrene / (meth) acrylic acid glycidyl ester copolymer and (formaldehyde) Resin [K5], such as acrylic resin; Resin that reacts the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, and further reacts with tetrahydrophthalide Resin [K6], etc. for acid anhydride reaction resins.

The resin (B) is preferably at least one member selected from the group consisting of the resin [K1], the resin [K2], and the resin [K3], and at least one member selected from the group consisting of the resin [K2] and the resin [K3]. Is better. With these resins, the developability of the colored curable resin composition is excellent. From the viewpoint of adhesion between the colored pattern and the substrate, resin [K2] is more preferable.

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

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

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

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and even more preferably 17 to 55% by mass with respect to the total solid content. When 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 capable of polymerizing living radicals and / or acids generated by the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and the like. Preferably, a (meth) acrylate compound is used.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropylacrylate, and 2-ethylhexylcarbitol Acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone and the like, and (a), (b) and (c) described above.

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

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, and dineopentyl. Tetraol penta (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, trinepentaerythritol octa (meth) acrylate, trinepentaerythritol hexa (meth) acrylate, Neopentaerythritol deca (meth) acrylate, tetranepentaerythritol nona (meth) acrylate, ginseng (2- (meth) acryloxyethyl) isocyanurate, ethylene glycol modification N-pentaerythritol tetra (meth) acrylate modified by ethylene glycol, N-pentaerythritol hexa (meth) acrylate modified by ethylene glycol, N-pentaerythritol tetra (meth) acrylate modified by propylene glycol, propylene glycol Modified dipentaerythritol hexa (meth) acrylate, caprolactone modified neopentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (methyl) Among the acrylates, dipentaerythritol penta (meth) acrylate and dinepentaerythritol hexa (meth) acrylate are preferred.

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

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

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 by mass, and 35:65 to 80:20 is better.

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

<Polymerization initiator (D)>

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

Examples of the polymerization initiator (D) include: O-fluorenyl oxime compounds, alkyl phenone compounds, biimidazole compounds, Compounds, and fluorenylphosphine oxide compounds.

The O-fluorenyl oxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * indicates a bonding bond.

Examples of the O-fluorenyl oxime compound include N-benzyloxy-1- (4-phenylmercaptophenyl) butane-1-one-2-imine, and N-benzyloxy 1- (4-phenylmercaptophenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylmercaptophenyl) -3-cyclopentyl Propane-1-one-2-imine, N-ethoxyl-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] ethane -1-imine, N-ethoxyl-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxetanyl (Methyloxy) benzamidine} -9H-carbazol-3-yl] ethane-1-imine, N-acetamyloxy-1- [9-ethyl-6- (2-methyl Benzamidine) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzyloxy-1- [9-ethyl-6- (2-methyl Benzamidine) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one-2-imine and the like. Commercial products such as IRGACURE OXE01, OXE02 (the above are manufactured by BASF), and N-1919 (made by ADEKA) can also be used. The O-fluorenyl oxime compound is selected from the group consisting of N-benzyloxy-1- (4-phenylmercaptophenyl) butane-1-one-2-imine, and N-benzyloxy- 1- (4-phenylmercaptophenyl) octane-1-one-2-imine and N-benzyloxy-1- (4-phenylmercaptophenyl) -3-cyclopentylpropane- Preferably, at least one of the groups formed by 1-keto-2-imine is N-benzyloxy-1- (4-phenylmercaptophenyl) octan-1-one-2-imine. Better.

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

Compounds having a partial structure represented by formula (d2) include, for example, 2-methyl-2-morpholinyl-1- (4-methylmercaptophenyl) propane-1-one, 2-di Methylamino-1- (4-morpholinylphenyl) -2-benzylbutane-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 (all of which are manufactured by BASF) can also be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one and 2-hydroxy-2-methyl-1- [4 -(2-hydroxyethoxy) phenyl] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- [4-isopropenylphenyl) propane-1 -Oligomers of ketones, α, α-diethoxyacetophenone, benzophenone dimethyl ketal and the like.

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

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

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

Examples of the aryl group having 6 to 10 carbon atoms include phenyl, tolylmethyl, xylyl, ethylphenyl, and naphthyl, and phenyl is preferred.

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

Examples of the biimidazole compound include: 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (refer to, for example, 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'-tetrakis (dialkoxyphenyl) biimidazole, 2,2' -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62- 174204, etc.), imidazole compounds in which the phenyl group at the 4,4 ', 5,5'-position is substituted with an alkoxycarbonyl group (see, for example, Japanese Patent Application Laid-Open No. 7-10913). Among them, a compound represented by the following formula and a mixture thereof are preferred.

Above three Examples of compounds include: 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-piperyl-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-tris , 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-tris Wait.

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

Furthermore, examples of the polymerization initiator (D) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether. Compounds; diphenyl ketone, methyl o-benzylidene benzoate, 4-phenyl diphenyl ketone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3 ', Diphenyl ketone compounds such as 4,4'-tetrakis (tert-butylperoxycarbonyl) diphenyl ketone, 2,4,6-trimethyldiphenyl ketone; 9,10-phenanthrenequinone, 2-ethyl Quinone compounds such as anthraquinone, camphorquinone; 10-butyl-2-chloroacridone, benzodiazone, methyl phenylglyoxylate, titanocene compound, etc.

These are preferably used in combination with a polymerization initiation aid (D1) (in particular, amines) described later.

The polymerization initiator (D) contains at least one selected from the group consisting of an alkyl phenone compound, Polymerization initiators in the group of compounds, fluorenylphosphine oxide compounds, O-fluorenyl oxime compounds, and biimidazole compounds are preferred, and polymerization initiators containing O-fluorenyl oxime compounds are more preferred.

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

<Polymerization starter (D1)>

The polymerization initiator (D1) is a compound or a sensitizer used to promote the polymerization of a polymerizable compound that is polymerized by a polymerization initiator. When a polymerization initiator (D1) is included, it is generally used in combination with a polymerization initiator (D).

Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thiaxanthone compounds, and carboxylic acid compounds.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethyl Amyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethyl-p-toluidine, 4,4 ' -Bis (dimethylamino) diphenyl ketone (commonly known as Michelin), 4,4'-bis (diethylamino) diphenyl ketone, 4,4'-bis (ethylmethyl) Amine) diphenyl ketone and the like are preferably 4,4'-bis (diethylamino) diphenyl ketone. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

Examples of the alkoxyanthracene compound 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, and the like.

Examples of the above-mentioned thioanthrone compound include: 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone Anthrone, 1-chloro-4-propoxythioanthrone and the like.

Examples of the carboxylic acid compound include phenyl mercaptoacetic acid, methyl phenyl mercaptoacetic acid, ethyl phenyl mercaptoacetic acid, methyl ethyl phenyl mercaptoacetic acid, dimethyl phenyl mercaptoacetic acid, methoxyphenyl mercaptoacetic acid, and dimethoxy Phenylmercaptoacetic acid, chlorobenzenemercaptoacetic acid, dichlorobenzenemercaptoacetic acid, N-phenylglycinic acid, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycolic acid, naphthyloxyacetic acid, and the like.

When using these polymerization initiation aids (D1), the content is preferably 0.1 to 30 parts by mass and 1 to 20 parts by mass based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Serve better. When the amount of the polymerization initiator (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent generally used in the technical field can be used. For example: ester solvents (solvents containing -COO-, -O-free), ether solvents (solvents containing -O-, -COO-free), ether ester solvents (containing -COO- Solvents with -O-), ketone solvents (solvents containing -CO-, non-COO- in the molecule), alcohol solvents (solvents containing OH, -O-, -CO- and -COO- free) ), Aromatic hydrocarbon solvents, amidine solvents, dimethylarsine and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, cyclohexane Alcohol acetate, γ-butyrolactone, etc.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethyl ether. 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 Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether, Methyl anisole and so on.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-methoxypropionate. Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate Esters, Propyl 2-methoxypropionate, Methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate, Methyl 2-methoxy-2-methylpropionate, 2-ethyl Ethyloxy-2-methylpropanoate, 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 Esters, dipropylene glycol methyl ether acetate, and the like.

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

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

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

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

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

Among them, preferred are propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and diethylene glycol. Alcohol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamidine, N-methylpyrrolidone, etc., more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate , Ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, N-methylpyrrolidone.

The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass with respect to the total amount of the colored curable resin composition. That is, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass.

When the content of the solvent (E) is within the above range, the flatness at the time of coating is improved, and when the color filter is formed, there is a tendency that the display characteristics are improved because the color density is sufficient.

<Leveling agent (F)>

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

Examples of the polysiloxane-based surfactant include a surfactant having a siloxane bond in the molecule. Specific examples include: TORAY SILICONE DC3PA, the same series of SH7PA, the same series of DC11PA, the same series of SH21PA, the same series of SH28PA, the same series of SH29PA, the same series of SH30PA, the same series of SH8400 (product name: DOW CORNING TORAY Co., Ltd.); KP321, KP322, KP323, KP324, KP326, KP340, KP341 (made by Shin-Etsu Chemical Industry Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (MOMENTIVE PERFORMANCE MATERIALS JAPAN Co., Ltd.).

Examples of the fluorine-based surfactant include a surfactant having a carbon-fluorine bond in the molecule. Specific examples include: FLUORAD (registered trademark) FC430, the same series of FC431 (SUMITOMO 3M Co., Ltd.); MEGAFAC (registered trademark) F142D, the same series of F171, the same series of F172, the same series of F173, the same series F177, same series F183, same series F554, same series R30, same series RS-718-K (manufactured by DIC Corporation); EFTOP (registered trademark) EF301, same series EF303, same series EF351 , The same series of EF352 (Mitsubishi Materials Electronic Chemical Co., Ltd.); SURFLON (registered trademark) S381, the same series of S382, the same series of SC101, the same series of SC105 (made by Asahi Glass Co., Ltd.) and E5844 (Daikin Fine Chemical Research Institute Co., Ltd.) and so on.

Examples of the polysiloxane-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples include: MEGAFAC (registered trademark) R08, BL20 of the same series, F475 of the same series, F477 of the same series, and F443 (made by DIC Corporation) of the same series.

When the leveling agent (F) is contained, its 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 or less, and more preferably 0.005% by mass relative to the total amount of the coloring curable resin composition. It is more preferably 0.07% by mass or more. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>

The colored curable resin composition of the present invention may contain fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and other conventional additives in the technical field, if necessary.

<Manufacturing method of colored curable resin composition>

The colored hardening resin composition of the present invention can be mixed by, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), and depending on the location. The leveling agent (F), polymerization initiation aid (D1), and other components used as needed are prepared.

When the pigment (A1) is contained, the pigment is mixed with a part or all of the solvent (E) in advance so that the average particle diameter of the pigment becomes about 0.2 μm or less, and it is preferably dispersed by a bead mill or the like. At this time, part or all of the pigment dispersant and resin (B) may be blended as necessary. In the pigment dispersant obtained in this way, the remaining components are mixed so as to have a predetermined concentration, whereby the intended coloring curable resin composition can be prepared.

The compound (I) is preferably prepared by dissolving a part or all of the solvent (E) in advance to prepare a solution. The above solution is preferably filtered through a filter having a pore size of about 0.01 to 1 μm.

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

<Manufacturing method of color filter>

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

The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted according to the purpose and application, and is, for example, 0.1 to 30 m, more preferably 0.1 to 20 m, and more preferably 0.5 to 6 m.

The substrate can be made of glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, and soda-lime glass coated with silicon; resin plates such as polycarbonate, polymethyl methacrylate, and polyethyl terephthalate ; Silicon, aluminum, silver, silver / copper / palladium alloy films, etc. are formed on the substrate. Other color filter layers, resin layers, transistors, and circuits may be formed on these substrates.

The formation of pixels of various colors by photolithography can be performed using conventional or commonly used devices or conditions. It can be produced, for example, by the following operations.

First, a colored curable resin composition is coated on a substrate, and volatile components such as solvents are removed by drying (pre-baking) and / or drying under reduced pressure to dry, thereby obtaining a smooth colored 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.

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

When drying under reduced pressure, it is preferably performed at a pressure in the range of 50 to 150 Pa and in a temperature range of 20 to 25 ° C.

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

Next, the colored composition layer is exposed through a mask for forming a desired colored pattern. The pattern on the photomask is not particularly limited, and a pattern depending on the purpose can be used.

The light source used for the exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, the light below 350nm is blocked by a filter that blocks the wavelength range, or the light near 436nm, 408nm, and 365nm is selectively extracted by a band-pass filter in those wavelength ranges. Specific examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.

Because the entire exposure surface can be irradiated with parallel light uniformly, or the photomask can be attached to the substrate with the colored composition layer in the correct position, a mask aligner and stepper are used. ) And other exposure devices are preferred.

A colored pattern is formed on the substrate by contacting and developing the colored composition layer after exposure with a developing solution. After development, the unexposed portion of the colored composition layer is dissolved in the developing solution and removed.

The developing solution is preferably an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of the alkaline compound in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. Furthermore, the developing solution may include a surfactant.

The developing method may be any of a paddle method, a dipping method, and a spray method. The substrate can be further inclined at any angle during development. After development, washing with water is preferred.

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

By using the coloring curable resin composition of the present invention, a color filter with extremely high brightness can be manufactured. The color filters described above can be used as color filters used in display devices (for example, liquid crystal display devices, organic EL devices, and electronic paper) and solid-state imaging devices.

    [Example]    

Next, examples are given to explain the present invention more specifically. In the examples, the percentages and parts of the content or the amount used are all based on quality unless otherwise specified.

In the following examples, the structure of the compound was confirmed by mass analysis (LC: Model 1200 manufactured by Agilent; MASS: Model LC / MSD manufactured by Agilent).

[Example 1a]

50.0 parts of a compound represented by the formula (IIIa) and 350 parts of isopropanol (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, and 18.1 parts of diethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed with A temperature exceeding 20 ° C was dropped into the mixture, and stirred at 20 ° C for 3 hours. The reaction solution was poured into 2100 parts of 10% hydrochloric acid. The obtained precipitate was taken out as a residue by suction filtration, washed with 373 parts of ion-exchanged water, and dried to obtain 23.6 parts of a compound represented by the formula (C1-22). The yield is 43%.

Identification of the compound represented by formula (C1-22)

(Mass analysis) Free mode = ESI ⁺ : m / z = [M + H] ⁺ 442.1

Exact Mass: 441.1

5.0 parts of a compound represented by formula (C1-22) and 35 parts of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, and dipropylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed at room temperature. ) 3.4 parts were dropped into the mixture at a temperature not exceeding 20 ° C, and the temperature was raised to 80 ° C, followed by stirring for 3 hours. After the reaction solution was cooled to room temperature, 3.4 parts of concentrated hydrochloric acid was added. The obtained mixture was poured into 315 parts of saturated saline. The obtained precipitate was taken out as a residue by suction filtration, washed with 630 parts of ion-exchanged water, and then dried to obtain 3.9 parts of a compound represented by the formula (Ia-7). The yield was 69%.

Identification of compounds represented by formula (Ia-7)

(Mass analysis) Free mode = ESI ⁺ : m / z = [M + H] ⁺ 507.7

Exact Mass: 506.7

[Example 2a]

2.0 parts of the compound represented by formula (C1-22) and 14 parts of chloroform (manufactured by Wako Pure Chemical Industries, Ltd.) are mixed at room temperature, and will be numbered [0149] to [0154] in Japanese Special Table 2011-513193 paragraphs 2.3 parts of formula (VIa-O4) obtained by the described manufacturing method was dropped into the mixture at a temperature not exceeding 20 ° C, and the temperature was raised to 80 ° C, followed by stirring for 22 hours. After the reaction solution was cooled to room temperature, it was washed twice with 98% of 10% hydrochloric acid, twice with 10% saline, and twice with 98 parts of ion-exchanged water, and then chloroform was distilled off and dried to obtain the formula (Ia -69) 1.2 parts of the compound shown. The yield was 41%.

(Mass analysis) Free mode = ESI ⁺ : m / z = [M + H] ⁺ 641.3

Exact Mass: 640.3

[Example 3a]

7.5 parts of a compound represented by formula (C1-22) and 52.5 parts of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, and 2- (ethylamino) ethanol (Tokyo (Manufactured by Chemical Industry Co., Ltd.) 4.5 parts were dropped into the mixture at a temperature not exceeding 20 ° C, and stirred at 60 ° C for 8 hours. After the reaction solution was cooled to room temperature, 263 parts of 10% saline was added. The obtained precipitate was taken out as a residue by suction filtration, washed with 263 parts of ion-exchanged water, and then dried to obtain 23.6 parts of a compound represented by the formula (Ia-78). The yield is 43%.

Identification of compounds represented by formula (Ia-78)

(Mass analysis) Free mode = ESI ⁺ : m / z = [M + H] ⁺ 494.3

Exact Mass: 494.2

[Example 4a]

10.0 parts of a compound represented by the formula (C1-22), 90 parts of ion-exchanged water, 7.3 parts of 4-piperidine acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 7.8 parts of potassium carbonate were mixed at room temperature and mixed at 80 Stir at 6 ° C for 6 hours. After the reaction solution was cooled to room temperature, 115 parts of 10% hydrochloric acid was added. The obtained precipitate was taken out as a residue by suction filtration, washed with 345 parts of ion-exchanged water, and then dried to obtain 10.9 parts of a compound represented by the formula (Ia-90). The yield was 95%.

Identification of compounds represented by formula (Ia-90)

(Mass analysis) Free mode = ESI ⁺ : m / z = [M + H] ⁺ 535.2

Exact Mass: 534.2

[Example 5a]

25.0 parts of a compound represented by the formula (IIIa), 100 parts of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.), and 27.8 parts of 2- (methylamino) ethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were kept at room temperature. Mix down and stir at 80 ° C for 2.5 hours. After the reaction solution was cooled to room temperature, it was poured into 1,225 parts of saturated saline, and the obtained precipitate was taken out as a residue by suction filtration. 625 parts of 10% hydrochloric acid was added to the residue, and after stirring for 1 hour, the slurry was suction-filtered, and the residue was taken out, washed with 625 parts of ion-exchanged water, and dried to obtain 12.4 parts of a compound represented by formula (Ia-42). The yield was 42%.

Identification of compounds represented by formula (Ia-42)

(Mass analysis) Free mode = ESI ⁺ : m / z = [M + H] ⁺ 483.2

Exact Mass: 482.2

[Example 6a]

10.0 parts of a compound represented by formula (C1-22), 70.0 parts of N, N-dimethylformamide, and 4.8 parts of diethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed at room temperature, and the temperature was 60 ° C. Stir for 6 hours. After the reaction solution was cooled to room temperature, it was charged into 840 parts of ion-exchanged water. The obtained precipitate was taken out as a residue by suction filtration, washed with 219 parts of ion-exchanged water, and then dried to obtain 8.2 parts of a compound represented by the formula (Ia-43). The yield was 71%.

Identification of compounds represented by formula (Ia-43)

(Mass analysis) Free mode = ESI ⁺ : m / z = [M + H] ⁺ 511.2

Exact Mass: 510.2

[Example 7a]

8.0 parts of a compound represented by the formula (C1-22), 56.0 parts of ion-exchanged water, and 8.8 parts of N-methyl-D-glucosamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed at room temperature and mixed at 80 ° C. Stir at 4 ° C for 4 hours. After the reaction solution was cooled to room temperature, it was poured into 73 parts of saturated saline. The obtained precipitate was taken out as a residue by suction filtration, washed three times with 20 parts of 10% saline, then washed with 20 parts of ion-exchanged water, and then dried to obtain 6.4 parts of a compound represented by formula (Ia-100). The yield was 59%.

Identification of compounds represented by formula (Ia-100)

(Mass analysis) Free mode = ESI ⁺ : m / z = [M + H] ⁺ 601.2

Exact Mass: 600.2

[Example 8a]

16.0 parts of a compound represented by formula (C1-22), 112.0 parts of ion-exchanged water, 48 parts of isopropanol (manufactured by Wako Pure Chemical Industries, Ltd.), and N-methyl-D-glucosamine (Tokyo Chemical Industry Co., Ltd.) 18.9 parts) were mixed at room temperature, and stirred at 80 ° C for 13 hours. After the reaction solution was cooled to room temperature, it was poured into 112 parts of saturated saline. The obtained precipitate was taken out as a residue by suction filtration, washed three times with 30 parts of 10% saline, then washed with 30 parts of ion-exchanged water, and then dried to obtain 6.4 parts of a compound represented by formula (Ia-101). The yield was 59%.

Identification of compounds represented by formula (Ia-101)

(Mass analysis) Ionization mode = ESI ⁺ : m / z = [M + H] ⁺ 615.2

Exact Mass: 614.2

[Example 9a]

4.0 parts of the compound represented by formula (IIIa), 40 parts of isopropanol (manufactured by Wako Pure Chemical Industries, Ltd.), 20 parts of ion-exchanged water, and N-methyl-D-glucosamine (Tokyo Chemical Industry Co., Ltd. 8.8 parts were mixed at room temperature and stirred at 75 ° C for 6 hours. After the reaction solution was cooled to room temperature, the resulting precipitate was taken out as a suction-filtered residue. 57 parts of isopropyl alcohol was added to the residue, and after stirring for 1 hour, the slurry was suction-filtered and the residue was taken out. 57 parts of alcohol and 57 parts of ion-exchanged water were washed and dried to obtain 4.7 parts of a compound represented by formula (Ia-104). The yield was 66%.

Identification of compounds represented by formula (Ia-104)

(Mass analysis) Ionization mode = ESI ⁺ : m / z = [M + H] ⁺ 723.2

Exact Mass: 722.2

[Example 10a]

3.0 parts of the compound represented by formula (C1-22), 9 parts of ion-exchanged water, 1.5 parts of sarcosinic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.4 parts of potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) Mix at room temperature and stir at 75 ° C for 7 hours. The reaction solution was cooled to room temperature, and then poured into 135 parts of 5% hydrochloric acid. The obtained precipitate was taken out as a residue by suction filtration, washed with 47 parts of ion-exchanged water, and then dried to obtain 1.6 parts of a compound represented by the formula (Ia-110). The yield was 48%.

Identification of compounds represented by formula (Ia-110)

(Mass analysis) Free mode = ESI ⁺ : m / z = [M + H] ⁺ 494.3

Exact Mass: 494.2

[Example 11a]

3.0 parts of the compound represented by formula (C1-22), 9 parts of ion-exchanged water, 2.3 parts of imine diacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 2.4 parts of potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) Mix at room temperature and stir at 75 ° C for 7 hours. The reaction solution was cooled to room temperature, and then poured into 135 parts of 5% hydrochloric acid. The obtained precipitate was taken out as a residue by suction filtration, washed with 47 parts of ion-exchanged water, and then dried to obtain 1.5 parts of a compound represented by the formula (Ia-112). The yield was 42%.

Identification of compounds represented by formula (Ia-112)

(Mass analysis) Free mode = ESI ⁺ : m / z = [M + H] ⁺ 538.2

Exact Mass: 538.1

[Example 12a]

8.0 parts of a compound represented by formula (IIIa), 72 parts of ion-exchanged water, and 8.1 parts of 2- (ethylamino) ethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed at room temperature, and stirred at 80 ° C. for 6 hour. The reaction solution was cooled to room temperature, and then poured into 120 parts of saturated saline. The obtained precipitate was taken out as a residue of suction filtration. 60 parts of 10% hydrochloric acid was added to the residue, and after stirring for 1 hour, the residue was suction-filtered, and the residue was taken out, washed with 60 parts of ion-exchanged water, and dried to obtain 4.2 parts of a compound represented by formula (I-44). Yield: 42%

Identification of compounds represented by formula (Ia-44)

(Mass analysis) Free mode = ESI ⁺ : m / z = [M + H] ⁺ 510.3

Exact Mass: 510.2

[Comparative Example 1]

10.0 parts of a compound represented by formula (IIIa) and 40 parts of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, and 7.2 parts of diethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped into The mixture was heated to 65 ° C and stirred for 3 hours. The reaction solution was cooled to room temperature, and then poured into 280 parts of 0.5% saline. The obtained precipitate was taken out as a residue by suction filtration, washed with 200 parts of ion-exchanged water, and then dried to obtain 8.0 parts of a compound represented by the formula (a). The yield was 68%.

Identification of compounds represented by formula (a)

(Mass analysis) Free mode = ESI ⁺ : m / z = [M + H] ⁺ 479.3

Exact Mass: 478.2

<Measurement of solubility>

The solubility of the compounds obtained in Examples 1a to 12a and the compounds obtained in Comparative Example 1a in propylene glycol monomethyl ether (hereinafter simply referred to as PGME) was determined as follows.

In a 10 mL sample tube, the compound and the solvent were mixed in the following ratio, and then the sample tube was sealed, and the ultrasonic vibrator was shaken at 30 ° C for 3 minutes. Then, after standing at room temperature for 30 minutes, suction filtration was performed, and the residue was observed with the naked eye. When the insoluble matter cannot be confirmed, the solubility is judged to be good, and when the insoluble matter is confirmed, the solubility is judged to be poor. The maximum concentration determined to be good in solubility is shown in Table 4. × means those who are not good at 1%.

10% compound 0.10g, solvent 0.90g

7% compound 0.07g, solvent 0.93g

5% compound 0.05g, solvent 0.95g

1% compound 0.01g, solvent 0.99g

<Measurement of absorbance>

Respectively Examples 1a to 12a The resultant 0.35g of compound was dissolved in chloroform or N, N- dimethylformamide (hereinafter abbreviated as DMF) volume of manipulation becomes 250cm ^3, in which the 2cm ³ chloroform or ethyl lactate (Hereinafter abbreviated as EL) was diluted to make a volume of 100 cm ³ and adjusted to a solution having a concentration of 0.028 g / L. For the above solution, the maximum absorption wavelength (λ max) and the maximum absorption wavelength (λ max) were measured using an ultraviolet-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz dish, optical path length: 1 cm). Absorptance at place. The results are shown in Table 5.

[Example 1b]

40 parts of compound (IIb) and 146 parts of diethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) as compound (IIIb) are mixed in the presence of 100 parts of 1-methyl-2-pyrrolidone and under light-shielding conditions, The resulting solution was stirred at 30 ° C for 3 hours. The resulting reaction solution was cooled to room temperature, and then added to a mixed solution of 400 parts of water and 20 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were taken out as a residue by suction filtration, and then dried to obtain 40 parts of a compound represented by the formula (Ib-37A).

Next, 44.1 parts of the compound represented by the formula (Ib-37A) and 27.1 parts of N-methyl-o-toluidine (made by Nanjing Chemical Industry Co., Ltd.) were present in 50 parts of 1-methyl-2-pyrrolidone. Then, it heated at 130 degreeC for 5 hours. The obtained reaction solution was cooled to room temperature, filtered, washed with 100 parts of water, and the obtained crystal was dried to obtain 48.6 parts of a compound represented by the formula (Ib-37).

Identification of compounds represented by formula (Ib-37)

(Mass analysis) Free mode = ESI ⁺ : m / z = [M + H] ⁺ 541.2

Exact Mass: 540.2

[Examples 2b to 5b]

The same operation as in Example 1b was performed to obtain the compound represented by Formula (Ib-8) (Example 2b), the compound represented by Formula (Ib-36) (Example 3b), and (Ib-38). The compound represented by (Example 4b) and the compound represented by formula (Ib-101) (Example 5b).

Identification of compounds represented by formula (Ib-8)

(Mass analysis) Free mode = ESI ⁺ : m / z = [M + H] ⁺ 512.3

Exact Mass: 512.2

Identification of compounds represented by formula (Ib-36)

(Mass analysis) Ionization mode = ESI ⁺ : m / z = [M + H] ⁺ 526.3

Exact Mass: 526.2

Identification of compounds represented by formula (Ib-38)

(Mass analysis) Free mode = ESI ⁺ : m / z = [M + H] ⁺ 555.2

Exact Mass: 554.2

Identification of compounds represented by formula (Ib-101)

(Mass analysis) Free mode = ESI ⁺ : m / z = [M + H] ⁺ 597.3

Exact Mass: 596.3

<Measurement of solubility>

The compounds obtained in Examples 1b to 5b and rose red B (manufactured by Tokyo Chemical Industry Co., Ltd.) were respectively propylene glycol monomethyl ether (hereinafter referred to as PGME), ethyl lactate (hereinafter referred to as EL), and propylene glycol monomethyl ether ethyl. The solubility of an acid ester (hereinafter abbreviated as PGMEA) was determined as follows.

In a 50 mL sample tube, the compound and the solvent were mixed in the following ratio, and then the sample tube was sealed, and the ultrasonic vibrator was shaken at 30 ° C for 3 minutes. Then, after standing at room temperature for 30 minutes, suction filtration was performed, and the residue was observed with the naked eye. When the insoluble matter cannot be confirmed, it is judged that the solubility is good and it is described as ○ in Table 6. When the insoluble matter is confirmed, it is judged that the solubility is not good and it is described as X in Table 6.

10% compound 0.1g, solvent 1g

15% compound 0.15g, solvent 1g

1% compound 0.01g, solvent 1g

[Example 1c]

20 parts of compound (IIc) and 14 parts of N-ethyl-o-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) as compound (IIIc) were present in the presence of 50 parts of 1-methyl-2-pyrrolidone It was mixed under light-shielding conditions, and the obtained solution was stirred at 30 ° C for 3 hours. The obtained reaction solution was cooled to room temperature, and then added to a mixed solution of 400 parts of water and 20 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were taken out as a residue by suction filtration and then dried to obtain 25 parts of a compound represented by the formula (Ic-132A).

Next, 50 parts of a compound represented by the formula (Ic-132A) and 10.7 parts of N-methyl-aniline (manufactured by Wako Pure Chemical Industries, Ltd.) were placed in the presence of 50 parts of 1-methyl-2-pyrrolidone. , And heated at 100 ° C for 5 hours. The obtained reaction solution was cooled to room temperature, filtered, washed with 100 parts of water, and the obtained crystal was dried to obtain 50 parts of a compound represented by the formula (Ic-132).

Identification of the compound represented by formula (Ic-132)

(Mass analysis) Free mode = ESI ⁺ : m / z = [M + H] ⁺ 575.2

Exact Mass: 574.1

[Examples 2c to 6c]

The same operation as in Example 1c was performed to obtain the compound represented by Formula (Ic-1) (Example 2c), the compound represented by Formula (Ic-7) (Example 3c), and Formula (Ic-134). The compound represented by (Example 4c), the compound represented by Formula (Ic-138) (Example 5c), and the compound represented by Formula (Ic-140) (Example 6c).

Identification of the compound represented by formula (Ic-1)

(Mass analysis) Free mode = ESI ⁺ : m / z = [M + H] ⁺ 561.3

Exact Mass: 560.2

Identification of the compound represented by formula (Ic-7)

(Mass analysis) Free mode = ESI ⁺ : m / z = [M + H] ⁺ 561.3

Exact Mass: 560.2

Identification of compound represented by formula (Ic-134)

(Mass analysis) Free mode = ESI ⁺ : m / z = [M + H] ⁺ 589.2

Exact Mass: 588.2

Identification of the compound represented by formula (Ic-138)

(Mass analysis) Free mode = ESI ⁺ : m / z = [M + H] ⁺ 575.3

Exact Mass: 574.2

Identification of the compound represented by formula (Ic-140)

(Mass analysis) Free mode = ESI ⁺ : m / z = [M + H] ⁺ 589.2

Exact Mass: 588.2

<Measurement of solubility>

The compounds obtained in Examples 1c to 6c and rose red B (manufactured by Tokyo Chemical Industry Co., Ltd.) in propylene glycol monomethyl ether (hereinafter referred to as PGME), ethyl lactate (hereinafter referred to as EL), and Solubility of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA).

In a 50 mL sample tube, the compound and the solvent were mixed in the following ratio, and then the sample tube was sealed, and the ultrasonic vibrator was shaken at 30 ° C for 3 minutes. Then, after standing at room temperature for 30 minutes, suction filtration was performed, and the residue was observed with the naked eye. When insoluble matter cannot be confirmed, it is judged that the solubility is good and it is described as ○ in Table 7. When insoluble matter is confirmed, it is judged that it is poor in solubility and it is described as X in Table 7.

10% compound 0.1g, solvent 1g

15% compound 0.15g, solvent 1g

1% compound 0.01g, solvent 1g

[Synthesis of Resin (B-1)]

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen gas was flowed into a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was added, and heated to 85 ° C while stirring. Then, in the flask, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, and 3,4-epoxy were used using a dropping funnel. Tricyclo [5.2.1.0 ^2,6 ] decane-9-yl acrylate mixture (content ratio 50:50 in molar ratio) (trade name "E-DCPA"; manufactured by DAICEL Co., Ltd.) 171 A solution of 40 parts of propylene glycol monomethyl ether acetate was added dropwise over about 5 hours. On the other hand, an additional dropping funnel was used to dissolve 26 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate. It was dripped into the flask over about 5 hours. After the completion of dripping of the polymerization initiator, the solution was kept at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin (B-1)) having a solid content of 43.5%. The weight average molecular weight of the obtained resin (B-1) was 8000, the molecular weight distribution was 1.98, and the acid value in terms of solid content was 53 mg-KOH / g.

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

Device: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG2000HXL

Column temperature: 40 ℃

Solvent: THF

Flow rate: 1.0mL / min

Solid concentration of test liquid: 0.001 to 0.01% by mass

Injection volume: 50 μL

Detector: RI

Calibration Standard: TSK Standard Polystyrene

F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

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

[Preparation of colored curable resin composition (a)]

The following compounds were mixed to obtain a colored curable resin composition (a). Colorant (A): Formula (Ia-7), Formula (Ia-69), Formula (Ia-78), Formula (Ia-90), Formula (Ia-42), Formula (Ia-43), Formula ( Ia-100), Formula (Ia-101), Formula (Ia-104), Formula (Ia-110), Formula (Ia-112) or Formula (Ia-44); 2.6 parts of the compound; CI Pigment Blue 15 : 6 30.1 parts; 13 parts of acrylic pigment dispersant; alkali-soluble resin (B): 53 parts of resin (B-1) (in terms of solid content); polymerizable compound (C): dipentaerythritol hexaacrylate ( KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts; polymerization initiator (D): N-benzyloxy-1- (4-phenylmercaptophenyl) octane-1- 10 parts of keto-2-imine (IRGACURE (registered trademark) OXE-01; manufactured by BASF Corporation; O-fluorenyl oxime compound); solvent (E): 700 parts of propylene glycol monomethyl ether acetate; solvent (E): 80 parts of propylene glycol monomethyl ether; and leveling agent (F): 0.1 part of MEGAFAC (registered trademark) F554 (manufactured by DIC Corporation).

[Preparation of colored curable resin composition (b)]

The following compounds were mixed to obtain a colored curable resin composition (b). Colorant (A): 2.5 parts of the compound represented by formula (Ib-37), formula (Ib-8), formula (Ib-36), formula (Ib-38) or formula (Ib-101); CI pigment blue 15: 6 30.1 parts; 13 parts of acrylic pigment dispersant; alkali-soluble resin (B): resin (B-1) (solid content conversion) 50 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts; polymerization initiator (D): N-benzyloxy-1- (4-phenylmercaptophenyl) octane-1 -10 parts of keto-2-imine (IRGACURE (registered trademark) OXE-01; manufactured by BASF Corporation; O-fluorenyl oxime compound); solvent (E): 720 parts of propylene glycol monomethyl ether acetate; solvent (E) : 80 parts of propylene glycol monomethyl ether; and leveling agent (F): 0.1 part of MEGAFAC (registered trademark) F554 (manufactured by DIC Corporation).

[Preparation of colored curable resin composition (c)]

Colorant (A): Formula (Ic-132), Formula (Ic-1), Formula (Ic-7), Formula (Ic-134), Formula (Ic-138) or Formula (Ic-140) Compound 2.6 parts; CI Pigment Blue 15: 6 30.1 parts; acrylic pigment dispersant 13 parts; alkali-soluble resin (B): resin (B-1) (solid content conversion) 53 parts; polymerizable compound (C): two 50 parts of neopentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.); polymerization initiator (D): N-benzyloxy-1- (4-phenylmercapto 10 parts of phenyl) octane-1-one-2-imine (IRGACURE (registered trademark) OXE-01; manufactured by BASF Corporation; O-fluorenyl oxime compound); solvent (E): propylene glycol monomethyl ether acetate 700 parts; solvent (E): 80 parts of propylene glycol monomethyl ether; and leveling agent (F): 0.1 part of MEGAFAC (registered trademark) F554 (manufactured by DIC Corporation).

[Formation of the pattern]

A color-hardening composition (a), (b), or (c) was applied on a 2-square-inch glass substrate (EAGLE XG; manufactured by CORNING) by spin coating, and then prebaked at 100 ° C for 3 hours. Minutes, a composition layer was obtained. After cooling, the gap between the glass substrate on which the composition layer was formed and the mask made of quartz glass was 100 μm. Using an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.), the exposure amount was 150 mJ / cm ² in the air. (365nm standard) Light irradiation was performed. As the photomask, a 100 μm line / space pattern was used. After the light was irradiated, the coating film was immersed and developed at 23 ° C for 80 seconds in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide. After washing with water, it was carried out in an oven at 220 ° C. After 20 minutes of post-baking, a pattern was obtained.

[Industrial availability]

The compound of the present invention is excellent in solubility in an organic solvent. It is expected that the color filter formed from the color-setting curable resin composition containing the compound of the present invention has higher brightness.

Claims (11)

A compound represented by formula (Ib), R ^1b , R ^2b and R ^3b each independently represent an alkyl group having 1 to 8 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen contained in the aromatic hydrocarbon group The atom may be substituted by an alkoxy group having 1 to 3 carbon atoms; Ar represents a group represented by formula (i), R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom; m represents an integer of 1 to 5; when m is 2 or more, a plurality of R may be each the same or Different; * indicates a bond with a nitrogen atom. The compound according to item 1 of the scope of patent application, wherein R ^1b , R ^2b and R ^3b are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl or 2-ethylhexyl.     The compound according to item 1 of the scope of patent application, wherein R is methyl.         The compound as described in claim 1 or 2, wherein m is 1 or 2.     The compound as described in item 1 of the scope of patent application, wherein Ar is a base represented by formula (C-0), a base represented by formula (C-1), or a base represented by formula (C-2), * Indicates a bonding bond with a nitrogen atom.     A coloring agent, which includes the compound described in the first patent application scope.         The coloring agent according to item 6 of the patent application range further comprises a pigment.         A coloring curable resin composition includes a coloring agent, a resin, a polymerizable compound, a polymerization initiator, and a solvent as described in item 6 of the scope of patent application.         A coating film formed by the colored hardening resin composition described in item 8 of the scope of patent application.         A color filter is formed by the color-hardening resin composition described in item 8 of the scope of patent application.         A display device includes the color filter described in item 10 of the scope of patent application.