JP2016117858A - Colored curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a color filter having excellent brightness.SOLUTION: A colored curable resin composition according to the present invention comprises a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E), where the colorant (A) comprises a dye (A-1), and as the dye (A-1), a compound represented by formula (AI) or formula (AII) and a macrocyclic compound (H) are comprised.SELECTED DRAWING: None

Description

  The present invention relates to a colored curable resin composition and the like.

The colored curable resin composition is used, for example, for producing a color filter such as a liquid crystal display device.
For color filters, there is a demand for color filters with high transmittance and high brightness for the purpose of reducing power consumption. As green colorants used in such colored curable resin compositions, C . I. A polyhalogenated zinc phthalocyanine pigment such as CI Pigment Green 58 is known (Patent Document 1, Non-Patent Document 1).

JP 2003-161827 A (Example 3)

DIC technical review no. 14/2008 Chem. Eur. J. et al. , 2006, 12, 4684-4690.

The color filter produced from the above colored curable resin composition was not sufficiently satisfactory as a color filter for a display device such as a liquid crystal display device in terms of brightness. Accordingly, an object of the present invention is to obtain a color filter with excellent brightness.
By the way, Non-Patent Document 2 discloses that a rotaxane type molecule having squarylium as an axial molecule is disclosed and can be used as a molecular probe or the like. However, squarylium is unstable due to the high reactivity of the central cyclobutane skeleton. The Non-Patent Document 2 teaches that squarylium is stabilized in water by using a rotaxane-type molecule, but the stability of squarylium in the presence of highly reactive compounds such as polymerization initiators is not known. The rotaxane molecule taught in Non-Patent Document 2 is assumed to be used as a molecular probe, and is not known at all for use in a color filter.

The present invention includes the following inventions.
[1] A colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E) are included, and the colorant (A) includes a dye (A-1). A colored curable resin composition comprising, as the dye (A-1), a compound represented by the following formula (AI) or (AII) and a macrocyclic compound (H).

[In Formula (AI) or Formula (AII),
R ^{a1 to} R ^a4 and R ^{a13 to} R ^a16 are each independently a hydrogen atom, a halogen atom, a hydroxy group, a monovalent aromatic hydrocarbon-containing group which may have a substituent, or carbon Represents a monovalent saturated hydrocarbon group of 1 to 20, wherein R ^a1 and R ^a5 , R ^a2 and R ^a6 , R ^a3 and R ^a7 , R ^a4 and R ^a8 are the same as the carbon atom to which they are bonded, respectively. R ^a1 and R ^a9 , R ^a2 and R ^a10 , R ^a3 and R ^a11 , R ^a4 and R ^a12 together with the nitrogen atom and the carbon atom to which they are bonded, respectively, To form a ring. R ^a14 and R ^a17 , R ^a15 and R ^a18 may be combined with carbon atoms to which they are bonded to form a ring, and R ^a13 and R ^a19 , R ^a14 and R ^a20 , R ^a15 and R ^a21 , R ^a16 and R ^a22 may form a ring together with the nitrogen atom and carbon atom to which they are bonded, respectively.
R ^{a5 to} R ^a8 , R ^a17 and R ^a18 each independently represent a hydrogen atom, a hydroxyl group, a —SH group, a —CF ₃ group, or —NHCO—R ^a23 .
R ^{a9 to} R ^a12 are each independently a monovalent aromatic hydrocarbon-containing group having 8 or more carbon atoms which may have a substituent, a monovalent saturated hydrocarbon group having 8 to 20 carbon atoms, or A monovalent unsaturated aliphatic hydrocarbon group having 8 to 20 carbon atoms, wherein the monovalent saturated hydrocarbon group or the methylene group constituting the monovalent unsaturated aliphatic hydrocarbon group is an oxygen atom, sulfur An atom, —N (R ^a24 ) —, a sulfonyl group, or a carbonyl group may be substituted, and a hydrogen atom contained in the monovalent saturated hydrocarbon group is a halogen atom, a cyano group, a nitro group, or a carbamoyl group. , A sulfamoyl group, a hydroxy group, or an amino group may be substituted. R ^a9 and R ^a10 and R ^a11 and R ^a12 may form a ring together with the nitrogen atom to which they are bonded.
R ^{a19 to} R ^a22 are each independently a monovalent aromatic hydrocarbon-containing group ^optionally having a substituent, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. Of the monovalent unsaturated aliphatic hydrocarbon group, and the methylene group constituting the monovalent saturated hydrocarbon group or the monovalent unsaturated aliphatic hydrocarbon group is an oxygen atom, a sulfur atom, -N ( R ^a24 ) —, a sulfonyl group or a carbonyl group may be substituted, and the hydrogen atom contained in the monovalent saturated hydrocarbon group is a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a hydroxy group or It may be substituted with an amino group. R ^a19 and R ^a20 , R ^a21 and R ^a22 may be combined with the nitrogen atom to which they are bonded to form a ring.
R ^a23 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the methylene group constituting the monovalent saturated hydrocarbon group includes an oxygen atom, a sulfur atom, —N (R ^a25 ) —, sulfonyl A hydrogen atom contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a hydroxy group or an amino group. May be.
R ^a24 and R ^{a25 each} represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]
R ^a19 to R ^a22 [2] the above formula (AII) are, independently of one another, have a substituent is a monovalent saturated hydrocarbon group which may having 1 to 20 carbon atoms [1] according to Colored curable resin composition.
[3] The colored curable composition according to [1] or [2], wherein the macrocyclic compound (H) is represented by cyclodextrin, crown ether, cyclophane, calixarene, or the following formula (AIII): Resin composition.

[In the formula (AIII),
R ^a26 and R ^a27 each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a hydroxy group, an amino group, or a monovalent hydrocarbon group having 1 to 20 carbon atoms. And the methylene group constituting the monovalent hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, -N (R ^a28 )-, a sulfonyl group, or a carbonyl group, and the monovalent hydrocarbon The hydrogen atom contained in the group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a hydroxy group, or an amino group.
R ^a28 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. The methylene group constituting the monovalent hydrocarbon group may be replaced with an oxygen atom, a sulfur atom, —N (R ^a29 ) —, a sulfonyl group, or a carbonyl group, and the monovalent hydrocarbon group The hydrogen atom contained may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a hydroxy group, or an amino group.
R ^a29 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ^a29 are present, they are the same or different from each other.
p and q each independently represent an integer of 0 to 3, n represents an integer of 1 to 8, and Z represents a carbon atom or a nitrogen atom. ]
[4] The colored curable resin composition according to [3], wherein Z is a nitrogen atom.
[5] The colored curable resin composition according to [3] or [4], wherein n is 1.
[6] The colored curable resin composition according to any one of [3] to [5], wherein p or q is 0.
[7] The colored curable resin composition according to any one of [1] to [6], wherein the colorant (A) further contains a pigment (A-2).
[8] The colored curable resin composition according to [7], wherein the pigment (A-2) is a yellow pigment or a green pigment.
[9] The yellow pigment is C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 150, C.I. I. The colored curable composition according to [8], comprising at least one selected from the group consisting of CI Pigment Yellow 185.
[10] An integrated compound in which the compound represented by the following formula (AII) penetrates the macrocyclic compound (H).

[In the formula (AII),
R ^{a13 to} R ^a16 are each independently a hydrogen atom, a halogen atom, a hydroxy group, a monovalent aromatic hydrocarbon-containing group which may have a substituent, or a monovalent aromatic group having 1 to 20 carbon atoms. Represents a saturated hydrocarbon group, and R ^a14 and R ^a17 , R ^a15 and R ^a18 may each form a ring together with the carbon atom to which they are bonded, and R ^a13 , R ^a19 and R ^a14 And R ^a20 , R ^a15 and R ^a21 , R ^a16 and R ^a22 may form a ring together with the nitrogen atom and carbon atom to which they are bonded.
R ^a17 and R ^a18 each independently represent a hydrogen atom, a hydroxyl group, a —SH group, a —CF ₃ group, or NHCO—R ^a23 .
R ^{a19 to} R ^a22 each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and the methylene group constituting the monovalent saturated hydrocarbon group is , An oxygen atom, a sulfur atom, —N (R ^a24 ) —, a sulfonyl group or a carbonyl group, and the hydrogen atom contained in the monovalent saturated hydrocarbon group is a halogen atom, a cyano group or a nitro group , Carbamoyl group, sulfamoyl group, hydroxy group or amino group may be substituted. R ^a19 and R ^a20 , R ^a21 and R ^a22 may be combined with the nitrogen atom to which they are bonded to form a ring.
R ^a23 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the methylene group constituting the monovalent saturated hydrocarbon group includes an oxygen atom, a sulfur atom, —N (R ^a25 ) —, sulfonyl A hydrogen atom contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a hydroxy group or an amino group. May be.
R ^a24 and R ^{a25 each} represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]
[11] A color filter formed from the colored curable composition according to any one of [1] to [9].
[12] A display device including the color filter according to [11].

  The colored curable resin composition of the present invention is excellent as a colored curable resin composition used for a color filter of a display device such as a liquid crystal display device because the color filter produced therefrom has good brightness.

  The colored curable resin composition of the present invention includes a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), and the colorant (A) is A compound represented by the following formula (AI) or formula (AII) (hereinafter referred to as “compound (AI)”, “compound (AII)”): And a macrocyclic compound (H).

[In Formula (AI) or Formula (AII),
R ^{a1 to} R ^a4 and R ^{a13 to} R ^a16 are each independently a hydrogen atom, a halogen atom, a hydroxy group, a monovalent aromatic hydrocarbon-containing group which may have a substituent, or carbon Represents a monovalent saturated hydrocarbon group of 1 to 20, wherein R ^a1 and R ^a5 , R ^a2 and R ^a6 , R ^a3 and R ^a7 , R ^a4 and R ^a8 are the same as the carbon atom to which they are bonded, respectively. R ^a1 and R ^a9 , R ^a2 and R ^a10 , R ^a3 and R ^a11 , R ^a4 and R ^a12 together with the nitrogen atom and the carbon atom to which they are bonded, respectively, To form a ring. R ^a14 and R ^a17 , R ^a15 and R ^a18 may be combined with carbon atoms to which they are bonded to form a ring, and R ^a13 and R ^a19 , R ^a14 and R ^a20 , R ^a15 and R ^a21 , R ^a16 and R ^a22 may form a ring together with the nitrogen atom and carbon atom to which they are bonded, respectively.
R ^{a5 to} R ^a8 , R ^a17 and R ^a18 each independently represent a hydrogen atom, a hydroxyl group, a —SH group, a —CF ₃ group, or NHCO—R ^a23 .
R ^{a9 to} R ^a12 are each independently a monovalent aromatic hydrocarbon-containing group having 8 or more carbon atoms which may have a substituent, a monovalent saturated hydrocarbon group having 8 to 20 carbon atoms, or A monovalent unsaturated aliphatic hydrocarbon group having 8 to 20 carbon atoms, wherein the monovalent saturated hydrocarbon group or the methylene group constituting the monovalent unsaturated aliphatic hydrocarbon group is an oxygen atom, sulfur An atom, —N (R ^a24 ) —, a sulfonyl group, or a carbonyl group may be substituted, and a hydrogen atom contained in the monovalent saturated hydrocarbon group is a halogen atom, a cyano group, a nitro group, or a carbamoyl group. , A sulfamoyl group, a hydroxy group, or an amino group may be substituted. R ^a9 and R ^a10 and R ^a11 and R ^a12 may form a ring together with the nitrogen atom to which they are bonded.
R ^{a19 to} R ^a22 are each independently a monovalent aromatic hydrocarbon-containing group ^optionally having a substituent, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. Of the monovalent unsaturated aliphatic hydrocarbon group, and the methylene group constituting the monovalent saturated hydrocarbon group or the monovalent unsaturated aliphatic hydrocarbon group is an oxygen atom, a sulfur atom, -N ( R ^a24 ) —, a sulfonyl group or a carbonyl group may be substituted, and the hydrogen atom contained in the monovalent saturated hydrocarbon group is a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a hydroxy group or It may be substituted with an amino group. R ^a19 and R ^a20 , R ^a21 and R ^a22 may be combined with the nitrogen atom to which they are bonded to form a ring.
R ^a23 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the methylene group constituting the monovalent saturated hydrocarbon group includes an oxygen atom, a sulfur atom, —N (R ^a25 ) —, sulfonyl A hydrogen atom contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a hydroxy group or an amino group. May be.
R ^a24 and R ^{a25 each} represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]

In formulas (AI) and (AII), a halogen atom in R ^{a1 to} R ^a4 , R ^{a13 to} R ^a16 , and a monovalent saturated hydrocarbon group of R ^{a9 to} R ^a12 , R ^{a19 to} R ^a22 , R ^a23 Examples of the halogen atom that may be substituted for the hydrogen atom contained in are fluorine atom, chlorine atom, bromine atom or iodine atom.

In the formula (AI) and formula (AII), as the monovalent aromatic hydrocarbon-containing group which may have a substituent of R ^{a1 to} R ^a4 , R ^{a13 to} R ^a16 , R ^{a19 to} R ^a22 , It is preferable that it is C5-C20, and it is more preferable that it is C6-C10.
In addition, examples of the substituent that may be substituted for the monovalent aromatic hydrocarbon-containing group include alkyl having 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Group: alkenyl group having 1 to 6 carbon atoms such as vinyl group, propenyl group, butenyl group, pentenyl group and hexenyl group; carbon number such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group and hexyloxy group 1-6 alkyloxy groups; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkyl groups containing fluorine atom such as trifluoromethyl group; and the like.

Specific examples of the monovalent aromatic hydrocarbon-containing group which may have a substituent of R ^{a1 to} R ^a4 , R ^{a13 to} R ^a16 , R ^{a19 to} R ^a22 include a phenyl group, a toluyl group, Aryl group such as xylyl group, mesityl group, cumenyl group, biphenylyl group, naphthyl group, anthryl group, phenanthryl group; aralkyl group such as benzyl group, phenylethyl group, phenylbutyl group; aryloxy group such as phenoxy group; benzyloxy Aralkyloxy groups such as groups; perfluorophenyl group, perfluoro (o-tolyl) group, perfluoro (m-tolyl) group, perfluoro (p-tolyl) group, perfluoroxylyl group, perfluoromesityl group , Perfluoro (o-cumenyl) group, perfluoro (m-cumenyl) group, perfluoro (p-cumenyl) group, perfluorobenzyl group Perfluorophenenylethyl group, perfluorobiphenylyl group, perfluoro (1-naphthyl) group, perfluoro (2-naphthyl) group, 1-trifluoromethylphenyl group, 2-trifluoromethylphenyl group, 3-trifluoro And aromatic hydrocarbon-containing groups containing a fluorine atom such as a fluoromethylphenyl group and a 4-trifluoromethylphenyl group.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ^{a1 to} R ^a4 , R ^{a13 to} R ^a16 and R ^{a19 to} R ^a25 preferably has 1 to 12 carbon atoms, more preferably 1 carbon atom. -10, more preferably 1 to 8 carbon atoms, particularly preferably 1 to 7 carbon atoms. Specifically, for example, carbon number 1 such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group and icosyl group. A linear alkyl group of -20; an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1-ethylpentyl group, a 2-ethylhexyl group, etc. An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group.

The methylene group constituting the monovalent saturated hydrocarbon group of R ^{a19 to} R ^a22 was replaced with an oxygen atom, a sulfur atom, —N (R ^a24 ) —, —N (R ^a25 ) —, a sulfonyl group or a carbonyl group. As the group or a group in which a hydrogen atom contained in a monovalent saturated hydrocarbon group is substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a hydroxy group or an amino group, for example, a monovalent group The methylene group constituting the saturated hydrocarbon group is replaced with at least one of an oxygen atom, a sulfur atom, —N (R ^a24 ) —, —N (R ^a25 ) —, a sulfonyl group, and a carbonyl group; A group in which a hydrogen atom contained in a valent saturated hydrocarbon group is substituted with a halogen atom or the like is preferable, and a group in which these are combined may also be used.

Examples of the group in which the methylene group constituting the monovalent saturated hydrocarbon group is replaced with an oxygen atom include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group. Group, alkyloxy groups such as pentyloxy group; and the like.
Examples of the group in which the methylene group constituting the monovalent saturated hydrocarbon group is replaced with an oxygen atom or a carbonyl group include alkyloxycarbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group; an acetoxy group A group having an ester bond such as an alkylcarbonyloxy group such as benzoyloxy group;

Furthermore, examples of the group in which the methylene group constituting the monovalent saturated hydrocarbon group is replaced by —N (R ^a24 ) —, —N (R ^a25 ) —, and a carbonyl group include an N-methylcarbamoyl group, N -Ethylcarbamoyl group, N-propylcarbamoyl group, N-isopropylcarbamoyl group, N-butylcarbamoyl group, N-isobutylcarbamoyl group, N-sec-butylcarbamoyl group, N-tert-butylcarbamoyl group, N-pentylcarbamoyl group N- (1-ethylpropyl) carbamoyl group, N- (1,1-dimethylpropyl) carbamoyl group, N- (1,2-dimethylpropyl) carbamoyl group, N- (2,2-dimethylpropyl) carbamoyl group N- (1-methylbutyl) carbamoyl group, N- (2-methylbutyl) carbamoyl group, N- (3-methylbutyl) carbamoyl group, N-cyclopentylcarbamoyl group, N-hexylcarbamoyl group, N- (1,3-dimethylbutyl) carbamoyl group, N- (3,3-dimethylbutyl) carbamoyl group, N-heptylcarbamoyl Group, N- (1-methylhexyl) carbamoyl group, N- (1,4-dimethylpentyl) carbamoyl group, N-octylcarbamoyl group, N- (2-ethylhexyl) carbamoyl group, N- (1,5-dimethyl) (Hexyl) N-substituted carbamoyl group such as carbamoyl group, N- (1,1,2,2-tetramethylbutyl) carbamoyl group;
N, N-dimethylcarbamoyl group, N, N-ethylmethylcarbamoyl group, N, N-diethylcarbamoyl group, N, N-propylmethylcarbamoyl group, N, N-isopropylmethylcarbamoyl group, N, N-tert-butyl Such as methylcarbamoyl group, N, N-butylethylcarbamoyl group, N, N-bis (1-methylpropyl) carbamoyl group, N, N-heptylmethylcarbamoyl group, N, N-bis (2-ethylhexyl) carbamoyl group, etc. An N, N-2 substituted carbamoyl group;
Etc.

Examples of the group in which the methylene group constituting the monovalent saturated hydrocarbon group is replaced with a sulfonyl group, and —N (R ^a24 ) — and —N (R ^a25 ) — include an N-methylsulfamoyl group, N -Ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N -Tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) ) Sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) Sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethyl Butyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2- N-1-substituted sulfamoyl groups such as ethylhexyl) sulfamoyl group, N- (1,5-dimethylhexyl) sulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group;
N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfa Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl An N, N-2 substituted sulfamoyl group such as a group, N, N-bis (2-ethylhexyl) sulfamoyl group;
Etc.

Examples of the group in which the methylene group constituting the monovalent saturated hydrocarbon group is replaced by -N (R ^a24 ) ^-or -N (R ^a25 ) ^-include N-methylamino group, N-ethylamino group, N- Propylamino group, N-isopropylamino group, N-butylamino group, N-isobutylamino group, N-sec-butylamino group, N-tert-butylamino group, N-pentylamino group, N- (1-ethyl) Propyl) amino group, N- (1,1-dimethylpropyl) amino group, N- (1,2-dimethylpropyl) amino group, N- (2,2-dimethylpropyl) amino group, N- (1-methylbutyl) ) Amino group, N- (2-methylbutyl) amino group, N- (3-methylbutyl) amino group, N-cyclopentylamino group, N-hexylamino group, N- (1,3-dimethylbutyl) amino group N- (3,3-dimethylbutyl) amino group, N-heptylamino group, N- (1-methylhexyl) amino group, N- (1,4-dimethylpentyl) amino group, N-octylamino group, N-alkylamino groups such as N- (2-ethylhexyl) amino group, N- (1,5-dimethylhexyl) amino group, N- (1,1,2,2-tetramethylbutyl) amino group;
N, N-dimethylamino group, N, N-ethylmethylamino group, N, N-diethylamino group, N, N-propylmethylamino group, N, N-isopropylmethylamino group, N, N-tert-butylmethyl N such as amino group, N, N-butylethylamino group, N, N-bis (1-methylpropyl) amino group, N, N-heptylmethylamino group, N, N-bis (2-ethylhexyl) amino group, etc. , N-dialkylamino group;
N-methylaminomethyl group, N-ethylaminomethyl group, N-propylaminomethyl group, N-isopropylaminomethyl group, N-butylaminomethyl group, N-isobutylaminomethyl group, N-sec-butylaminomethyl group N-tert-butylaminomethyl group, N-pentylaminomethyl group, N- (1-ethylpropyl) aminomethyl group, N- (1,1-dimethylpropyl) aminomethyl group, N- (1,2- Dimethylpropyl) aminomethyl group, N- (2,2-dimethylpropyl) aminomethyl group, N- (1-methylbutyl) aminomethyl group, N- (2-methylbutyl) aminomethyl group, N- (3-methylbutyl) Aminomethyl group, N-cyclopentylaminomethyl group, N-hexylaminomethyl group, N- (1,3-dimethylbutyl) a Nomethyl group, N- (3,3-dimethylbutyl) aminomethyl group, N-heptylaminomethyl group, N- (1-methylhexyl) aminomethyl group, N- (1,4-dimethylpentyl) aminomethyl group, N-octylaminomethyl group, N- (2-ethylhexyl) aminomethyl group, N- (1,5-dimethylhexyl) aminomethyl group, N- (1,1,2,2-tetramethylbutyl) aminomethyl group An N-alkylaminomethyl group such as
N, N-dimethylaminomethyl group, N, N-ethylmethylaminomethyl group, N, N-diethylaminomethyl group, N, N-propylmethylaminomethyl group, N, N-isopropylmethylaminomethyl group, N, N -Tert-butylmethylaminomethyl group, N, N-butylethylaminomethyl group, N, N-bis (1-methylpropyl) aminomethyl group, N, N-heptylmethylaminomethyl group, N, N-bis ( N, N-dialkylaminomethyl groups such as 2-ethylhexyl) aminomethyl group;
Etc.

Examples of the group in which a hydrogen atom contained in a monovalent saturated hydrocarbon group is substituted with a halogen atom include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoro (isopropyl) group, and a perfluoro (iso) group. Propenyl) group, perfluoro (1-propenyl) group, perfluoro (2-propenyl) group, perfluorobutyl group, perfluoro (isobutyl) group, perfluoro (sec-butyl) group, perfluoro (tert-butyl) Group, perfluoro (2-butenyl) group, perfluoro (1,3-butadienyl) group, perfluoropentyl group, perfluoro (isopentyl) group, perfluoro (3-pentyl) group, perfluoro (neopentyl) group, Perfluoro (tert-pentyl) group, perfluoro (1-methylpentyl) Perfluoro (2-methylpentyl) group, perfluoro (2-pentenyl) group, perfluorohexyl group, perfluoro (isohexyl) group, perfluoro (5-methylhexyl) group, perfluoro (2-ethylhexyl) group , An aliphatic hydrocarbon group containing a fluorine atom such as a perfluoroheptyl group, a perfluorooctyl group, a perfluorononyl group, a perfluorodecyl group, a perfluoroundecyl group, a perfluorododecyl group, a perfluorooctadecyl group;
Perfluorocyclopropyl group, perfluorocyclobutyl group, perfluorocyclopentyl group, perfluorocyclohexyl group, perfluorocyclohexenyl group, perfluorocycloheptyl group, perfluoro (1-methylcyclohexyl) group, perfluoro (2-methyl) Cyclohexyl) group, perfluoro (3-methylcyclohexyl) group, perfluoro (4-methylcyclohexyl) group, perfluoro (1,2-dimethylcyclohexyl) group, perfluoro (1,3-dimethylcyclohexyl) group, perfluoro (1,4-dimethylcyclohexyl) group, perfluoro (2,3-dimethylcyclohexyl) group, perfluoro (2,4-dimethylcyclohexyl) group, perfluoro (2,5-dimethylcyclohexyl) group, perfluoro (2,6-dimethylcyclohexyl) group, perfluoro (3,4-dimethylcyclohexyl) group, perfluoro (3,5-dimethylcyclohexyl) group, perfluoro (2,2-dimethylcyclohexyl) group, perfluoro (3 , 3-dimethylcyclohexyl) group, perfluoro (4,4-dimethylcyclohexyl) group, perfluoro (2,4,6-trimethylcyclohexyl) group, perfluoro (2,2,6,6-tetramethylcyclohexyl) group An alicyclic hydrocarbon group containing a fluorine atom such as a perfluoro (3,3,5,5-tetramethylcyclohexyl) group;
Etc.

Examples of the group in which the methylene group constituting the monovalent saturated hydrocarbon group is replaced with an oxygen atom and the hydrogen atom contained in the monovalent saturated hydrocarbon group is substituted with a halogen atom include a perfluoromethoxy group, Fluoroethoxy group, perfluoropropoxy group, perfluoro (isopropoxy) group, perfluorobutoxy group, perfluoro (isobutoxy) group, perfluoro (sec-butoxy) group, perfluoro (tert-butoxy) group, perfluoropentyl Oxy group, perfluorophenoxy group, perfluorobenzyloxy group, 2,2,2-trifluoroethoxy group, (perfluoroethyl) methoxy group, (perfluoropropyl) methoxy group, (perfluoro (isopropyl)) methoxy group , (Perfluoro (isopropenyl)) methoxy , (Perfluoro (1-propenyl)) methoxy group, (perfluoro (2-propenyl)) methoxy group, (perfluorobutyl) methoxy group, (perfluoro (isobutyl)) methoxy group, (perfluoro (sec-butyl) )) Methoxy group, (perfluoro (tert-butyl)) methoxy group, (perfluoro (2-butenyl)) methoxy group, (perfluoro (1,3-butadienyl)) methoxy group, (perfluoropentyl) methoxy group , (Perfluoro (isopentyl)) methoxy group, (perfluoro (3-pentyl)) methoxy group, (perfluoro (neopentyl)) methoxy group, (perfluoro (tert-pentyl)) methoxy group, (perfluoro (1 -Methylpentyl)) methoxy group, (perfluoro (2-methylpentyl) Methoxy group, (perfluoro (2-pentenyl)) methoxy group, (perfluorohexyl) methoxy group, (perfluoro (isohexyl)) methoxy group, (perfluoro (5-methylhexyl)) methoxy group, (perfluoro ( 2-ethylhexyl)) methoxy group, (perfluoroheptyl) methoxy group, (perfluorooctyl) methoxy group, (perfluorononyl) methoxy group, (perfluorodecyl) methoxy group, (perfluoroundecyl) methoxy group, An alkyloxy group containing a fluorine atom such as a perfluorododecyl) methoxy group or a (perfluorooctadecyl) methoxy group;
Bis (trifluoromethyl) phenylmethyl group; and the like.

The ring formed by R ^a1 and R ^a5 , R ^a2 and R ^a6 , R ^a3 and R ^a7 , R ^a4 and R ^a8 together with the carbon atom to which they are bonded is represented by the following formula: Examples include the structure. In the formula, R ^A1 represents the same group as R ^{a1 to} R ^a4 , R ^A2 represents the same group as R ^{a5 to} R ^a8, and R ^A3 represents the same group as R ^{a9 to} R ^a12 . * Represents a bond.

^{Examples of} the ring formed by R ^a14 and R ^a17 and R ^a15 and R ^a18 together with the carbon atom to which they are bonded include structures represented by the following formulas. In the formula, R ^A4 represents the same group as R ^{a13 to} R ^a16, and R ^A6 represents the same group as R ^{a19 to} R ^a21 . * Represents a bond.

The ring formed by R ^a1 and R ^a9 , R ^a2 and R ^a10 , R ^a3 and R ^a11 , R ^a4 and R ^a12 together with the nitrogen atom and carbon atom to which they are bonded is represented by the following formula: Examples include the structure represented. In the formula, R ^A1 represents the same group as R ^{a1 to} R ^a4 , R ^A2 represents the same group as R ^{a5 to} R ^a8, and R ^A3 represents the same group as R ^{a9 to} R ^a12 . * Represents a bond.

The ring formed by R ^a13 and R ^a19 , R ^a14 and R ^a20 , R ^a15 and R ^a21 , R ^a16 and R ^a22 together with the nitrogen atom and carbon atom to which they are bonded, respectively, Examples include the structure represented by the formula. In the formula, R ^A4 represents the same group as R ^{a13 to} R ^a16 , R ^A5 represents the same group as R ^{a17 to} R ^a18, and R ^A6 represents the same group as R ^{a19 to} R ^a22 . * Represents a bond.

The monovalent aromatic hydrocarbon-containing group having 8 or more carbon atoms, which may have a substituent in R ^{a9 to} R ^a12 , more preferably has 18 or less carbon atoms, and more preferably has 15 or less carbon atoms. is there. As the monovalent aromatic hydrocarbon-containing group represented by R ^{a9 to} R ^a12 , for example, an aryl group having 8 to 12 carbon atoms and an aralkyl group having 8 to 12 carbon atoms are preferable. The aryl group is particularly preferably a phenyl group, and the aralkyl group is particularly preferably a benzyl group. The aryl group and aralkyl group preferably have a substituent, and the substituent is an aliphatic hydrocarbon group having 1 to 5 carbon atoms (preferably having 1 to 3 carbon atoms) (preferably an alkyl group or alkenyl group). preferable. In addition, the aryl group preferably has a substituent at the o-position of the bond, and the aralkyl group preferably has a substituent at the o-position of the alkylene group. Specific examples of the aromatic hydrocarbon-containing group represented by R ^{a9 to} R ^a12 include groups represented by the following formulas. In the formula, * represents a bond hand.

Examples of the monovalent saturated hydrocarbon group having 8 to 20 carbon atoms in R ^{a9 to} R ^a12 include linear alkyl groups such as octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, and icosyl group. Branched alkyl groups such as 2-ethylhexyl group; Furthermore, as the monovalent unsaturated aliphatic hydrocarbon group having 8 to 20 carbon atoms in R ^{a9 to} R ^a12 , for example, octenyl group, nonenyl group, decenyl group, dodecenyl group, hexadecenyl group, icosenyl group and the like A chain alkenyl group; and the like.

^{Examples of the} monovalent aromatic hydrocarbon-containing group that may have a substituent in R ^{a19 to} R ^a22 include an aryl group such as a toluyl group; an aralkyl group such as a benzyl group; or R ^{a9 to} R ^a12 Among these groups, groups having 8 to 20 carbon atoms are exemplified. Furthermore, ^{examples of the} monovalent unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms in R ^{a19 to} R ^a22 include, for example, a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, Linear alkenyl groups such as nonenyl group, decenyl group, dodecenyl group, hexadecenyl group, and icocenyl group; and the like.

The ring formed by R ^a9 and R ^a10 , R ^a11 and R ^a12 , R ^a19 and R ^a20 , R ^a21 and R ^a22 together with the nitrogen atom to which they are bonded has the structure represented by the following formula, etc. Is mentioned.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ^a24 and R ^a25 include a benzyl group, a phenylethyl group, and a phenylbutyl group.

Among these, in formula (AI), R ^{a1 to} R ^a4 are preferably hydrogen atoms.
R ^{a5 to} R ^a8 are preferably a hydrogen atom, a hydroxyl group, or NHCO-R ^a23 , more preferably a hydrogen atom or a hydroxyl group, and still more preferably a hydrogen atom.
As R ^{a9 to} R ^{a12, an optionally} substituted monovalent aromatic hydrocarbon-containing group having 8 to 20 carbon atoms or a monovalent saturated hydrocarbon group having 8 to 20 carbon atoms is preferable. More preferably, it is a monovalent aromatic hydrocarbon-containing group having 8 to 20 carbon atoms which may have a substituent.
R ^a23 is preferably a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, more preferably a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, and still more preferably 1 having 1 to 4 carbon atoms. Is a saturated saturated hydrocarbon group.
R ^a24 and R ^a25 are preferably a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, more preferably a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, still more preferably 1 to 1 carbon atoms. 4 is a monovalent saturated hydrocarbon group.

In Formula (AII), R ^{a13 to} R ^a16 are preferably hydrogen atoms.
R ^a17 and R ^a18 are preferably a hydrogen atom, a hydroxyl group, or NHCO-R ^a23 , more preferably a hydrogen atom or a hydroxyl group, and still more preferably a hydrogen atom.
As R ^{a19 to} R ^a22 , an ^optionally substituted monovalent aromatic hydrocarbon-containing group having 8 to 20 carbon atoms or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms is preferable. More preferably, it is a monovalent aromatic hydrocarbon-containing group having 8 to 20 carbon atoms which may have a substituent.
R ^a23 is preferably a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, more preferably a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, and still more preferably 1 having 1 to 4 carbon atoms. Is a saturated saturated hydrocarbon group.
R ^a24 and R ^a25 are preferably a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, more preferably a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, still more preferably 1 to 1 carbon atoms. 4 is a monovalent saturated hydrocarbon group.

  Also, the following formulas (x-1) and (x-2)

Examples of the group represented by formula (I) include groups represented by formula (A1-1) to formula (A1-7). In these formulas, * represents a bond.

  Moreover, following formula (y-1), (y-2)

Examples of the group represented by formula (A2-1) to (A2-6) include, in addition to the groups represented by formulas (A1-1) to (A1-7) shown above. Group. * Represents a binding hand.

  In Table 1, specific examples of the compound represented by the formula (AI) include compounds (AI-1) to (AI-14) based on the following formula (AI-a), but are not limited thereto. It is not something.

In the formula (AI-a) and Table 1, R ^{a1 to} R ^a8 are respectively synonymous with R ^{a1 to} R ^a8 in the above formula (AI), and X ^a1 and X ^a2 are each represented by the formula (x-1 ), (X-2)

Means a group represented by In Table 1, (AI-1) to (AI-7) mean that they correspond to groups represented by Formula (AI-1) to Formula (AI-7), respectively. In the above formula, * represents a bond hand.

  From the viewpoint of raw material availability, the compound (AI-1) to the compound (AI-7) are more preferable.

  In Tables 2 to 4, specific examples of the compound represented by Formula (AII) include Compound (AII-1) to Compound (AII-77) based on Formula (AII-a), but are not limited thereto. Is not to be done.

In the formula (AII-a) and Tables 2 to 4, R ^{a13 to} R ^a18 have the same meaning as R ^{a13 to} R ^a18 in the above formula (AII), and Y ^a1 and Y ^a2 represent the formula (A y-1), (y-2)

Means a group represented by In Tables 2 to 4, (AI-1) to (AI-7) and (AII-1) to (AII-6) are represented by formula (AI-1) to formula (AI-7), formula ( AII-1) to the group represented by formula (AII-6). In the above formula, * represents a bond hand. Furthermore, in Tables 3 and 4, NHCO-EHC is

The group represented by these is shown. * Represents a binding hand.

  From the viewpoint of raw material availability, compound (AII-1) to compound (AII-6) are more preferable, among which compound (AII-2) and compound (AII-6) are preferable, and compound (AII-2) is particularly preferable. .

  The macrocycle compound (H) that forms an integrated compound (AH) with the compounds (AI) and (AII) has one or more rings (these may share some of the constituent elements with each other). It is preferable that when the ring having the largest number of constituent elements is selected among the rings that do not include other rings inside, the number of constituent elements of the ring is preferably 10 or more, The number of constituent elements of the ring is preferably 12 or more, more preferably 16 or more, still more preferably 20 or more, for example, preferably 40 or less, and more preferably 30 or less.

  The macrocyclic compound (H) preferably contains a heteroatom other than a carbon atom, more preferably contains a heteroatom in the ring portion, and a heterocycle capable of forming a hydrogen bond such as a nitrogen atom or an oxygen atom. More preferably, the ring contains an atom.

  Specific examples of the macrocyclic compound (H) include cyclodextrin, crown ether, cyclophane, calixarene, and cyclic amide compounds.

  Examples of the cyclodextrin include α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin and the like.

  Crown ether means a compound in which ethyleneoxy units are bonded to form a ring, and the ethylene group of some ethyleneoxy units is replaced with a divalent aromatic hydrocarbon group such as a phenylene group. The oxygen atom of some ethyleneoxy units may be replaced with a —NH— group. Specific examples of the crown ether include 12-crown-4-ether (1,4,7,10-tetraoxacyclododecane) and 15-crown-5-ether (1,4,7,10,13- Pentaoxacyclopentadecane), 18-crown-6-ether, (1,4,7,10,13,16-hexacyclooctadecane), dibenzo-18-crown-6-ether, diaza-18-crown-6 Examples include ether.

  In the cyclophane, a divalent aromatic hydrocarbon group such as a phenylene group and a divalent aliphatic hydrocarbon group such as an alkylene group (preferably an alkylene group having 1 to 5 carbon atoms) are alternately bonded. This means a compound forming a ring, and the methylene group contained in the divalent aliphatic hydrocarbon group may be replaced with a sulfur atom or a —NH— group. Specific examples of the cyclophane include compounds having a repeating number of a divalent aromatic hydrocarbon group and a divalent aliphatic hydrocarbon group of preferably 1 to 10, more preferably 1 to 6. It is done.

  Furthermore, the calixarene is composed of a divalent aromatic hydrocarbon group having a phenolic hydroxy group such as a hydroxyphenylene group or a tert-butyl-hydroxyphenylene group, and an alkylene group (preferably an alkylene group having 1 to 5 carbon atoms). Means a compound in which divalent aliphatic hydrocarbon groups such as the above are alternately bonded to form a ring, and the methylene group contained in the divalent aliphatic hydrocarbon group is a sulfur atom or- It may be replaced by an NH-group. Specifically, as calixarene, the repeating number of a divalent aromatic hydrocarbon group having a phenolic hydroxy group and a divalent aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 6. The compound etc. which are are mentioned.

  The cyclic amide compound has at least one amide bond in the ring portion, and is selected from an amide bond, a divalent aromatic hydrocarbon group, a divalent aromatic heterocyclic group, and a divalent aliphatic hydrocarbon group. It is intended to mean a compound in which at least one of them is bonded to form a ring. The number of amide bonds contained in the ring part is preferably 2 or more, more preferably 3 or more, and preferably 6 or less, more preferably 5 or less. Moreover, it is preferable that a cyclic amide compound contains bivalent aromatic heterocyclic groups, such as bivalent aromatic hydrocarbon groups, such as a phenylene group, or a pyridinyl group, in a ring part. As a preferable cyclic amide compound, a compound represented by the following formula (AIII) can be given.

[In the formula (AIII), R ^a26 and R ^a27 each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a hydroxy group, an amino group, or a monovalent group having 1 to 20 carbon atoms. Represents a hydrocarbon group. The methylene group constituting the monovalent hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, -N (R ^a28 )-, a sulfonyl group, or a carbonyl group, and the monovalent hydrocarbon group The hydrogen atom contained may be substituted with a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, hydroxy group or amino group.
R ^a28 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. The methylene group constituting the monovalent hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, -N (R ^a29 )-, a sulfonyl group or a carbonyl group, and is included in the monovalent hydrocarbon group. The hydrogen atom may be substituted with a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, hydroxy group or amino group.
R ^a29 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ^a29 are present, they are the same or different from each other. p and q each independently represent an integer of 0 to 3, n represents an integer of 1 to 8, and Z represents a carbon atom or a nitrogen atom. ]

In the formula (AIII), R ^a26 , R ^a27 halogen atom and R ^{a26 to} R ^a28 monovalent hydrocarbon group which may be substituted with a hydrogen atom may be substituted with R ^{a1 to} R Examples thereof include the same groups as those exemplified as the halogen atom for ^a4 .

^Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms of R ^{a26 to} R ^a29 include a monovalent saturated hydrocarbon group and a monovalent unsaturated hydrocarbon group, and a monovalent saturated hydrocarbon group. Examples thereof include the same groups as those exemplified as the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms of R ^{a1 to} R ^a4 .
Further, a methylene group constituting a monovalent hydrocarbon group of R ^a26 to R ^a28 is an oxygen atom, a sulfur ^{atom, -N (R a28) -,} - N (R a29) -, a sulfonyl group, or a carbonyl group Or a group in which a hydrogen atom contained in a monovalent hydrocarbon group is substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a hydroxy group, or an amino group, Examples include the same groups as those exemplified as the group in which the methylene group constituting the monovalent saturated hydrocarbon group of R ^{a19 to} R ^a22 is replaced with each substituent, or the group in which the hydrogen atom is substituted with each substituent. be able to.
The monovalent unsaturated hydrocarbon group for R ^{a26 to} R ^a29 is the same as the group exemplified as the monovalent aromatic hydrocarbon-containing group which may have a substituent for R ^{a1 to} R ^a4 . Group; monovalent unsaturated aliphatic hydrocarbon group such as vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, hexadecenyl group, icosenyl group; Etc.

Furthermore, in Formula (AIII), R ^a26 or R ^a27 is preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.
n represents an integer of 1 to 8, and n is preferably 1 among them.
p or q represents an integer of 0 to 3. Among them, the case where p or q is 0 is preferable, and the case where p and q are 0 is particularly preferable.
Z represents a carbon atom or a nitrogen atom, and among them, a nitrogen atom is preferable.

  Examples of the compound represented by the formula (AIII) include compounds represented by the formulas (e-1) to (e-6).

  In the present invention, these compounds (AI) and (AII) and the macrocyclic compound (H) are included as the dye (A-1), and the compounds (AI) and (AII) and the macrocyclic compound (H) ) Are integrated to form an integrated compound (hereinafter sometimes referred to as “compound (AH)” or “integrated compound (AH)”). In this integrated compound (AH), it is preferable that the compounds (AI) and (AII) penetrate the space inside the ring of the macrocyclic compound (H) in a direction perpendicular to the ring. By setting it as such an integrated compound (AH), the brightness characteristic of compound (AI) and (AII) can be exhibited effectively.

According to a study by the present inventors, in order to form an integrated state of the integrated compound (AH), the ring part of the macrocyclic compound (H) is bonded to the above compounds (AI) and (AII). It is preferable that the size is such that the central portion (squarylium portion) can be surrounded. In order to maintain the integrated state of the integrated compound (AH), the ends of the compounds (AI) and (AII) (for example, R ^{a9 to} R ^a12 , R ^{a19 to} R ^a22 ) are used as bulky groups. It is preferable to do. This makes it possible for the macrocyclic compound (H) to form a rotaxane structure that is geometrically constrained by the compounds (AI) and (AII). Furthermore, it is preferable that the macrocyclic compound (H) can form a hydrogen bond. Thereby, the macrocyclic compound (H) and the compounds (AI) and (AII) are integrated by the action of hydrogen bonding. In this case, it is possible to form a pseudo-rotaxane structure in which the macrocyclic compound (H) and the compounds (AI) and (AII) are integrated even if the end portion is not a bulky group.

  From such a point of view, the following compound (AH-1) to compound (AH-29) are exemplified as the compound (AH) by a preferred combination of the compounds (AI) and (AII) and the macrocyclic compound (H). . In Table 5, S column represents the number of the formula of the group exemplified in the specific example of formula (AI) or formula (AII), and T column is the number of the formula of the group exemplified in the specific example of formula (AIII). Represents.

  From the viewpoint of raw material availability, the compound (AH-9) or the compound (AH-13) is preferable.

  Examples of the method for producing the compound represented by the formula (AI) or (AII) include a method described in JP-A No. 2002-363434, an amine derivative and squaric acid (3,4-dihydroxy-3-cyclobutene- 1,2-dione).

  Next, as a method for producing an integrated compound (AH) penetrating through the cavity of the macrocyclic compound (H), Chem. Eur. J. et al. , 2006, 12, 4684-4690. The manufacturing method as described in above.

  For example, the compound represented by the formula (AI) or the formula (AII) can be produced by bringing the compound represented by the formula (Aa1) and the formula (Aa2) into contact with each other, preferably by stirring, May coexist. The reaction temperature is preferably −20 ° C. to 60 ° C., more preferably 12 ° C. to 35 ° C., and the reaction time is preferably 1 hour to 60 hours, more preferably 12 hours to 18 hours. is there.

(In the formula, R ^a26 , R ^a27 , p, q, n and Z have the same meaning as in formula (AIII).)

  Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform, alcohol solvents such as methanol, ethanol and butanol, and nitro hydrocarbons such as nitrobenzene. Examples thereof include a system solvent, a ketone solvent such as methyl isobutyl ketone, an amide solvent such as 1-methyl-2-pyrrolidone, or a mixed solvent thereof.

  The method for obtaining the target compound (AH) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, water can be added to the reaction mixture to precipitate crystals, which can be collected by filtration. Crystals collected by filtration were water; acetonitrile; alcohol solvents such as methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol and 1-octanol; ether solvents such as tetrahydrofuran; ketone solvents such as acetone; Ester solvents such as acetic acid and ethyl acetate; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene; halogenated hydrocarbon solvents such as dichloromethane, chloroform and tetrachloromethane; Etc., and then dried. Moreover, you may further refine | purify as needed by well-known methods, such as the method of dissolving in the said solvent, wash | cleaning with sodium hydroxide aqueous solution, and drying, column chromatography or recrystallization.

  The colorant (A) may contain other dyes as the dye (A-1) in addition to the compound (AH). Examples of such dyes include oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamides of acid dyes. For example, the Color Index (published by The Society of Dyers and Colorists) provides solvent and acid dyes. , Basic, reactive, direct, disperse, moldant, vat and the like, and known dyes described in Dyeing Notes (Color Dyeing). In addition, according to the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, and the like can be given. These dyes may be used alone or in combination of two or more.

Specifically, C.I. I. Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted, and only the number is described), 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82 83, 89, 94, 98, 99, 162;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56;
C. I. Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;
C. I. Solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;
C. I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
C. I. Solvent Green 1, 3, 5, 28, 29, 32, 33; I. Solvent dyes,
C. I. 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;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;
C. I. Acid Red 73, 80, 91, 92, 97, 138, 151, 211, 274, 289;
C. I. Acid Green 3, 5, 9, 25, 27, 28, 41;
C. I. Acid Violet 34, 120;
C. I. Acid Blue 25, 27, 40, 45, 78, 80, 112; I. Acid dyes,

  C. I. C. such as Basic Green 1; I. Basic dyes,

C. I. Reactive Yellow 2, 76, 116;
C. I. Reactive Orange 16; I. Reactive dyes,

C. I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;
C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct blue 40; I. Direct dyes,

C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse violet 26, 27;
C. I. Disperse Blue 1, 14, 56, 60; I. Disperse dyes,

C. I. As the mold dye, C.I. I. Moldant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; etc. . I. Moldant dyes,

  C. I. C. of Bat Green 1 etc. I. Examples include vat dyes.

  In the dye (A-1), the content of the compound (AH) is preferably 70% by mass or more and 100% by mass or less, more preferably 80% by mass or more, based on the total amount of the dye (A-1). , 100% by mass or less, more preferably 85% by mass or more and 100% by mass or less. When the content of the compound (AH) is within the above range, the brightness when a color filter is obtained is preferable.

The colorant (A) preferably contains a pigment (A-2). The pigment (A-2) is not particularly limited, and a known pigment can be used. For example, pigments classified as pigments in the color index (published by The Society of Dyers and Colorists) can be mentioned, and these can be used alone or in combination of two or more.
Examples of the pigment (A-2) include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, Yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. A brown pigment such as CI Pigment Brown 23 and 25; and C.I. I. And black pigments such as CI Pigment Black 1 and 7.

  Examples of the pigment (A-2) include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 185, 194, 214; I. Green pigments such as C.I. Pigment Green 7, 36 and 58 are preferred; I. Pigment yellow 138, 150, 185 and C.I. I. Pigment Green 58 is more preferable, and C.I. I. Pigment yellow 138 and C.I. I. Pigment Green 58 is more preferable. By including the pigment, the transmission spectrum can be easily optimized, and the light resistance and chemical resistance of the color filter are improved.

If necessary, the pigment can be atomized by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment on the pigment surface with a polymer compound, sulfuric acid atomization method, etc. A treatment, a cleaning treatment with an organic solvent or water for removing impurities, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed.
The pigment preferably has a uniform particle size. By carrying out a dispersion treatment by containing a pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

Examples of the pigment dispersant include surfactants, and any of cationic, anionic, nonionic and amphoteric surfactants may be used. Specific examples include polyester-based, polyamine-based, acrylic-based surfactants, and the like. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Geneca Corporation), EFKA (registered trademark) (BASF) ), Ajisper (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by Big Chemie), and the like.
When the pigment dispersant is used, the amount used is preferably 1% by mass or more and 100% by mass or less, more preferably 5% by mass or more and 50% by mass or less, with respect to the total amount of the pigment (A-2). . When the amount of the pigment dispersant used is in the above range, there is a tendency that a pigment dispersion in a uniform dispersion state is obtained.

  When the pigment (A-2) is included, the content ratio of the dye (A-1) and the pigment (A-2) in the colorant (A) is usually on a mass basis, and is 45:55 to 1:99. Yes, preferably 40:60 to 2:98, more preferably 38:62 to 3:97.

  The content of the colorant (A) is preferably 5% by mass or more and 60% by mass or less, more preferably 8% by mass or more and 55% by mass or less, and still more preferably based on the total amount of the solid content. It is 10 mass% or more and 50 mass% or less. When the content of the colorant (A) is within the above range, the color density when it is used as a color filter is sufficient, and the resin (B) and the polymerizable compound (C) are contained in a necessary amount in the composition. Therefore, a pattern with sufficient mechanical strength can be formed. Here, the “total amount of solid content” in this specification refers to an amount obtained by removing the content of the solvent from the total amount of the colored curable resin composition. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and is a polymer having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. More preferably. Examples of the resin (B) include the following resins [K1] to [K6].
Resin [K1]; at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (Ba) (hereinafter sometimes referred to as “(Ba)”), and a cyclic ether having 2 to 4 carbon atoms A copolymer of a monomer (Bb) having a structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(Bb)”);
Resin [K2]; (Ba), (Bb), and monomer (Bc) copolymerizable with (Ba) (however, different from (Ba) and (Bb)) (hereinafter referred to as “(Bc)”) In some cases)
Resin [K3]; Copolymer of (Ba) and (Bc);
Resin [K4]; a resin obtained by reacting (Bb) with a copolymer of (Ba) and (Bc);
Resin [K5]; a resin obtained by reacting (Ba) with a copolymer of (Bb) and (Bc);
Resin [K6]: A resin obtained by reacting (Ba) with a copolymer of (Bb) and (Bc) and further reacting with a carboxylic acid anhydride.

Specific examples of (Ba) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 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 Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an alkaline aqueous solution.

(Bb) is, for example, a polymerizable compound having a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Say. (Bb) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  Examples of (Bb) include a monomer (Bb1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(Bb1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. A monomer (Bb2) (hereinafter sometimes referred to as “(Bb2)”), a monomer (Bb3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(Bb3)”), etc. Can be mentioned.

  As (Bb1), for example, a monomer (Bb1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(Bb1-1)”) And a monomer (Bb1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(Bb1-2)”).

  (Bb1-1) is preferably a monomer having a glycidyl group and an ethylenically unsaturated bond. Specific examples of (Bb1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinyl. Benzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis ( Glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris ( Glycidyloxy Methyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4, Examples include 6-tris (glycidyloxymethyl) styrene.

  Examples of (Bb1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide (registered trademark) 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) Acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), represented by the formula (BI) And a compound represented by the formula (BII).

[In Formula (BI) and Formula (BII), R ^b1 and R ^b2 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group May be substituted.
X ^b1 and X ^b2 represents a single ^{bond, * - R b3 -, *} - R b3 -O -, * - R b3 -S- or * -R ^b3 represents a -NH-.
R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms of R ^b1 and R ^b2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
^Examples of the alkyl group in which the hydrogen atoms of R ^b1 and R ^b2 are substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxy Examples include propyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like. .
R ^b1 and R ^b2 are preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Specifically, a hydrogen atom, a methyl group, an ethyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are preferable, and a hydrogen atom and a methyl group are more preferable.

^Examples of the alkanediyl group of R ^b3 include a linear or branched alkanediyl group, and specifically include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4- And linear alkanediyl groups such as a diyl group, pentane-1,5-diyl group, and hexane-1,6-diyl group; branched alkanediyl groups such as a propane-1,2-diyl group.
The X ^b1 and X ^b2, a single bond, * - R ^b3 -, or * -R ^b3 -O-, more preferably a single bond, or * -R ^b3 -O-, and specifically preferably It is a single bond, a methylene group, an ethylene group, * - CH ₂ -O- and * -CH ₂ CH ₂ -O- and the like, more preferably a single bond, * - CH ₂ CH ₂ -O- and the like ( * Represents a bond with O).

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

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

  The compound represented by the formula (BI) and the compound represented by the formula (BII) may be used alone or in combination of two or more. When the compound represented by the formula (BI) and the compound represented by the formula (BII) are used in combination, these content ratios [compound represented by the formula (BI): compound represented by the formula (BII)] are: On a molar basis, it is preferably 5:95 to 95: 5, more preferably 20:80 to 80:20.

  (Bb2) is more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. As (Bb2), 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane , 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

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

  (Bb) is preferably (Bb1) in that the color filter obtained can have higher reliability such as heat resistance and chemical resistance. Furthermore, (Bb1-2) is more preferable in that the storage stability of the colored curable resin composition is excellent.

Examples of (Bc) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, it is called “dicyclopentanyl (meth) acrylate” as a common name. In the case of “tricyclodecyl (meth) acrylate”) ) (In the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) Cyclo [5.2.1.0 ^{2, 6]} decene-8-yl (meth) acrylate, dicyclopenta Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylic acid esters of
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene and p-methoxystyrene; vinyl group-containing nitriles such as acrylonitrile and methacrylonitrile; vinyl chloride and vinylidene chloride Halogenated hydrocarbons such as: vinyl group-containing amides such as acrylamide and methacrylamide; esters such as vinyl acetate; dienes such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene; It is done.
Of these, (Bc) is preferably a vinyl group-containing aromatic compound, a dicarbonylimide derivative, or a bicyclounsaturated compound from the viewpoint of copolymerization reactivity and heat resistance. Specifically, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable.

In the resin [K1], the ratio of the structural unit derived from each is the total structural unit constituting the resin [K1]
Structural unit derived from (Ba); 2 to 60 mol%
Structural unit derived from (Bb); 40 to 98 mol%
It is preferable that
Structural unit derived from (Ba); 10-50 mol%
Structural unit derived from (Bb); 50-90 mol%
It is more preferable that
When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter are excellent. Tend.

  The resin [K1] is, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and the document Can be produced with reference to the cited references described in 1.

  Specifically, a predetermined amount of (Ba) and (Bb), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, for example, by substituting oxygen with nitrogen to create a deoxygenated atmosphere and stirring, The method of heating and heat retention is mentioned. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and those usually used in the field can be used. For example, as polymerization initiators, azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) As the solvent, any solvent that dissolves each monomer may be used. Examples of the solvent (E) for the colored curable resin composition of the present invention include a solvent described later.

  In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during the polymerization, the solution after the reaction is used as it is for the preparation of the colored curable resin composition of the present invention. Therefore, the manufacturing process of the colored curable resin composition of the present invention can be simplified.

In the resin [K2], the ratio of the structural units derived from each of the structural units in the resin [K2]
Structural unit derived from (Ba); 2 to 45 mol%
Structural unit derived from (Bb); 2-95 mol%
Structural unit derived from (Bc); 1 to 65 mol%
It is preferable that
Structural unit derived from (Ba); 5 to 40 mol%
Structural unit derived from (Bb); 5 to 80 mol%
Structural unit derived from (Bc); 5-60 mol%
It is more preferable that
When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter, There is a tendency to be excellent in heat resistance and mechanical strength.

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

In the resin [K3], the proportion of structural units derived from each of the structural units constituting the resin [K3]
Structural unit derived from (Ba); 2 to 60 mol%
Structural unit derived from (Bc); 40-98 mol%
It is preferable that
Structural unit derived from (Ba); 10-50 mol%
Structural unit derived from (Bc); 50-90 mol%
It is more preferable that
Resin [K3] can be produced, for example, in the same manner as described for the production method of resin [K1].

Resin [K4] obtains a copolymer of (Ba) and (Bc), and (Ba) has a carboxylic acid and / or carboxylic acid anhydride (Ba) having a cyclic ether having 2 to 4 carbon atoms of (Bb). It can manufacture by adding to.
First, a copolymer of (Ba) and (Bc) is produced in the same manner as described for the production method of the resin [K1]. In this case, it is preferable that the ratio of the structural unit derived from each is the same as that described for the resin [K3].

Next, the C2-C4 cyclic ether which (Bb) has is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (Ba) in the copolymer.
Subsequent to the production of the copolymer of (Ba) and (Bc), the atmosphere in the flask is replaced with nitrogen to air, and (Bb), a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris ( Dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (eg, hydroquinone, etc.) are placed in a flask and reacted, for example, at 60-130 ° C. for 1-10 hours to produce resin [K4]. it can.
The amount of (Bb) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (Ba). By adjusting the amount of (Bb) used within this range, the storage stability of the colored curable resin composition, the developability when forming the pattern, and the solvent resistance, heat resistance, and mechanical strength of the resulting pattern are obtained. And the balance of sensitivity tends to be good. Since the reactivity of the cyclic ether is high and unreacted (Bb) hardly remains, (Bb1) is preferable as (Bb1), and (Bb1-1) is more preferable as the resin [K4].
The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (Ba), (Bb) and (Bc). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (Ba), (Bb) and (Bc).
The reaction conditions such as the charging method of each reagent, the reaction temperature, and the reaction time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like. In addition, like the polymerization conditions, the charging 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.

When the resin [K5] is produced, as a first step, a copolymer of (Bb) and (Bc) is obtained in the same manner as in the production method of the resin [K1] described above. Similarly to the above, the obtained copolymer may be used as it is after the reaction, or may be a concentrated or diluted solution, or may be solid (powder) by a method such as reprecipitation. You may use what was taken out as.
In the first stage, the ratio of the structural units derived from (Bb) and (Bc) is relative to the total number of moles of all structural units constituting the copolymer of (Bb) and (Bc), respectively.
Structural unit derived from (Bb); 5-95 mol%
Structural unit derived from (Bc); 5-95 mol%
It is preferable that
Structural unit derived from (Bb); 10 to 90 mol%
Structural unit derived from (Bc); 10-90 mol%
It is more preferable that

Furthermore, as a second step, the carboxylic acid of (Ba) is added to the cyclic ether derived from (Bb) of the copolymer of (Bb) and (Bc) under the same conditions as in the method for producing the resin [K4]. Alternatively, the resin [K5] can be obtained by reacting a carboxylic acid anhydride.
In the second stage, the amount of (Ba) to be reacted with the copolymer of (Bb) and (Bc) is preferably 5 to 80 mol per 100 mol of (Bb). Since the reactivity of the cyclic ether is high and unreacted (Bb) hardly remains, (Bb1) is preferable as (Bb1) used for the resin [K5], and (Bb1-1) is more preferable.

The resin [K6] is a resin obtained by further reacting the carboxylic acid anhydride with the resin [K5]. It can be produced by reacting a carboxylic acid anhydride with a hydroxy group generated by the reaction of the cyclic ether derived from (Bb) and the carboxylic acid or carboxylic acid anhydride of (Ba).
Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride, and the like. As for the usage-amount of a carboxylic acid anhydride, 0.5-1 mol is preferable with respect to the usage-amount 1 mol of (Ba).

As the resin (B), specifically, 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] Resin such as decyl acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meta ) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- ( Resin such as (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate / (meth) Resin such as acrylic acid copolymer, styrene / (meth) acrylic acid copolymer [K3]; resin obtained by adding glycidyl (meth) acrylate to benzyl (meth) acrylate / (meth) acrylic acid copolymer, tri Resin with glycidyl (meth) acrylate added to cyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer Resin [K4], such as a resin obtained by adding glycidyl (meth) acrylate to the coalescence; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, tricyclo Copolymerization of decyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resin such as a resin obtained by reacting (meth) acrylic acid with [K5]; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, and tetrahydrophthal Examples thereof include a resin [K6] such as a resin reacted with an acid anhydride.
Especially, as resin (B), resin [K1] and resin [K2] are preferable.

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. . When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film ratio is high, the solubility of the unexposed portion in the developer is good, and the resolution of the colored pattern tends to be improved.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

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

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

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

Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more of ethylenically unsaturated bonds. Examples of such a polymerizable compound include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the above-described (Ba). , Compounds having one ethylenically unsaturated bond, such as the compounds exemplified as (Bb) and (Bc);
1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A and Compounds having two ethylenically unsaturated bonds such as 3-methylpentanediol di (meth) acrylate;
Compounds having three ethylenically unsaturated bonds such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate;
It has four ethylenically unsaturated bonds such as pentaerythritol tetra (meth) acrylate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate and the like. Compound;
Compounds having 5 ethylenically unsaturated bonds such as dipentaerythritol penta (meth) acrylate;
Ethylenically unsaturated bonds such as dipentaerythritol hexa (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate A compound having six
Compounds having 7 or more ethylenically unsaturated bonds such as tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, etc. Is mentioned.
Among these, the polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds, and more preferably a polymerizable compound having 5 to 6 ethylenically unsaturated bonds. . Of these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are particularly preferable.

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

  The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to the total amount of the solid content. is there. When the content of the polymerizable compound (C) is within the above range, the remaining film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

The content ratio of the resin (B) and the polymerizable compound (C) [resin (B): polymerizable compound (C)] is preferably 20:80 to 80:20 on a mass basis, and more Preferably it is 35: 65-80: 20.
<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used. Examples of the polymerization initiator that generates an active radical include an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a biimidazole compound.

  The O-acyloxime compound is a compound having a partial structure represented by the formula (Dd1). Hereinafter, * represents a bond.

  Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2, 4-Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) may be used. Among these, O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1 At least one selected from the group consisting of -on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferred, and N-benzoyloxy -1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred. When these O-acyloxime compounds are used, a color filter with high brightness tends to be obtained.

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

Examples of the compound having a partial structure represented by the formula (Dd2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4 -Morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one Etc. Commercial products such as Irgacure 369, 907, 379 (above, manufactured by BASF) may be used.
Examples of the compound having a partial structure represented by the formula (Dd3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2 -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxy Examples include acetophenone and benzyl dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (Dd2).

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

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.

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

(In the formula, R ^{d1 to} R ^d6 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 of R ^{d1 to} R ^d6 include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, and a naphthyl group, and is preferably a phenyl group.
Examples of the substituent that may substitute the aryl group of R ^{d1 to} R ^d6 include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example, Preferably it is a chlorine atom. As a C1-C4 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group are mentioned, Preferably it is a methoxy group.

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

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

  Examples of the polymerization initiator that generates an acid include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxy Onium salts such as phenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate And benzoin tosylate.

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

  The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, so the productivity of the color filter is improved.

<Polymerization initiation aid (D1)>
The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator. When the polymerization initiation assistant (D1) is included, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

  Examples of the amine compound include alkanolamines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylbenzoate. Aminobenzoic acid esters such as aminoethyl and 4-dimethylaminobenzoic acid 2-ethylhexyl; N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis ( Alkylaminobenzophenone such as diethylamino) benzophenone and 4,4′-bis (ethylmethylamino) benzophenone; and the like. Among them, alkylaminobenzophenone is preferable, and 4,4′-bis (diethylamino). Benzophenone is preferable. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

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

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

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

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

<Solvent (E)>
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used individually or in combination of 2 or more types. For example, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (intramolecular) Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O-,- A solvent not containing CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide and the like.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, and the like phenetol and methyl anisole.

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

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

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

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

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

  Among the above solvents, an organic solvent having a boiling point of 120 ° C. or more and 210 ° C. or less at 1 atm is preferable from the viewpoints of coating properties and drying properties. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N-methylpyrrolidone and N, N-dimethylformamide are preferred, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 3-ethoxypropionic acid More preferred are ethyl, N-methylpyrrolidone and N, N-dimethylformamide.

  Content of a solvent (E) becomes like this. Preferably it is 70-95 mass% with respect to the total amount of the colored curable resin composition of this invention, More preferably, it is 75-92 mass%. In other words, the total amount of the solid content of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good. .

<Leveling agent (F)>
Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan GK) Can be mentioned.

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

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

  The content of the leveling agent (F) is preferably 0.001% by mass to 0.2% by mass, and preferably 0.002% by mass to 0.1%, based on the total amount of the colored curable resin composition. It is not more than mass%, more preferably not less than 0.005 mass% and not more than 0.05 mass%. This content does not include the content of the pigment dispersant. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

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

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention includes, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E) used as necessary. It can be prepared by mixing the leveling agent (F), the polymerization initiation assistant (D1) and other components.
The pigment (A-2) is preferably mixed with a part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. The desired colored curable resin composition can be prepared by mixing the remaining components in the pigment dispersion thus obtained so as to have a predetermined concentration.
Alternatively, the dye (A-1) may be dissolved in part or all of the solvent (E) in advance to prepare a solution. Further, the solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.
The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.1 to 10 μm.

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

  As the substrate, quartz glass, borosilicate glass, alumina silicate glass, glass plate such as soda lime glass coated with silica on the surface, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the substrate In addition, aluminum, silver, or a silver / copper / palladium alloy thin film is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

Formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be produced as follows.
First, a colored curable resin composition is applied on a substrate, dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth colored composition layer is obtained.
Examples of the coating method include spin coating, slit coating, and slit and spin coating.
30-120 degreeC is preferable and the temperature in the case of performing heat drying has more preferable 50-110 degreeC. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
When performing vacuum drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.
The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specifically, examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.
Use an exposure device such as a mask aligner or a stepper because the entire exposure surface can be illuminated with parallel rays uniformly, or the photomask can be accurately aligned with the substrate on which the colored composition layer is formed. Is preferred.

A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.

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

  According to the colored curable resin composition of the present invention, a color filter having particularly excellent brightness can be produced. The color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.
In the following synthesis examples, the compound was identified by NMR (JNM-EX-270; (manufactured by JEOL Ltd.)).

Synthesis Example 1 Synthesis of Compound Represented by Formula (AH-9) 18.7 parts of N, N-dibutylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), 3,4-dihydroxy-3-cyclobutene-1, 4.6 parts of 2-dione (manufactured by Tokyo Chemical Industry Co., Ltd.), 542.3 parts of 1-butanol and 362.6 parts of toluene were mixed. The resulting mixture was stirred at 125 ° C. for 5 hours while removing water produced using a Dean-Stark tube. After completion of the reaction, the solvent was distilled off, a small amount of toluene was added, 200 parts of water was added, and the aqueous layer was discarded. The operation of washing with water was repeated twice, 100 parts of hexane was added, and the precipitated solid was collected by filtration. The solid collected by filtration was dispersed in 10 parts of tetrahydrofuran and filtered, and then the solid was washed with 20 parts of tetrahydrofuran and then with 50 parts of hexane. The obtained solid was dried under reduced pressure at 60 ° C. for 24 hours to obtain 3.94 parts of a compound represented by the formula (AII-2).

¹ H-NMR of compound represented by formula (AII-2) (270 MHz, δ value (ppm, TMS standard), CDCl ₃ )
δ 0.98 (t, 12H), 1.40 (m, 8H), 1.61 (m, 8H), 3.44 (t, 8H), 6.70 (d, 2H), 8.35 ( d, 2H)

  Next, 2.0 parts of the compound represented by the formula (AII-2) and 4.1 parts of triethylamine were added to 400 parts of chloroform, followed by stirring at 25 ° C. for 12 hours. Thereafter, 3.3 parts of 2,6-pyridinedicarbonyl dichloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 2.2 parts of p-xylylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was added at 12 ° C. at 25 ° C. Stir for hours. Thereafter, chloroform was distilled off, and the obtained solid was purified by silica gel column chromatography (elution solvent: chloroform) to obtain 0.3 parts of a compound of formula (AH-9).

¹ H-NMR (270 MHz, δ value (ppm, TMS standard), CDCl ₃ ) of the compound represented by the formula (AH-9)
δ 0.93 (m, 12H), 1.31 (m, 8H), 1.58 (m, 8H), 3.28 (t, 8H), 4.53 (d, 8H), 6.10 ( d, 4H), 6.61 (s, 8H), 8.02 (d, 2H), 8.02 (d, 4H), 8.11 (t, 2H), 8.51 (d, 4H), 10.1 (t, 4H)

Synthesis Example 2: Synthesis of compound represented by formula (AH-13) 10.0 parts of N, N-dibenzylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), 3,4-dihydroxy-3-cyclobutene-1 , 2-dione (Tokyo Chemical Industry Co., Ltd.) 2.1 parts, 1-butanol 270.0 parts and toluene 180.0 parts were mixed. The resulting mixture was stirred at 125 ° C. for 5 hours while removing water produced using a Dean-Stark tube. After completion of the reaction, the mixture was cooled for 6 hours, and the precipitated solid was collected by filtration. The solid collected by filtration was dispersed in 10 parts of methanol and filtered. The obtained solid was dried under reduced pressure at 60 ° C. for 24 hours to obtain 0.76 part of a compound represented by the formula (AII-6).

¹ H-NMR (270 MHz, δ value (ppm, TMS standard), CDCl ₃ ) of the compound represented by the formula (AII-6)
δ 4.79 (s, 8H), 6.88 (d, 4H), 7.30 (m, 20H), 8.37 (d, 4H)

  Next, 0.5 part of the compound represented by the formula (AII-6) and 0.8 part of triethylamine were added to 150 parts of chloroform, followed by stirring at 25 ° C. for 12 hours. Thereafter, 0.7 part of 2,6-pyridinedicarbonyl dichloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.5 part of p-xylylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was added at 12 ° C. at 25 ° C. Stir for hours. Thereafter, chloroform was distilled off, and the obtained solid was purified by silica gel column chromatography (elution solvent: chloroform) to obtain 0.2 parts of a compound of the formula (AH-13).

¹ H-NMR of the compound represented by the formula (AH-13) (500 MHz, δ value (ppm, TMS standard), CDCl ₃ )
δ 4.48 (d, 8H), 4.66 (s, 8H), 6.26 (d, 4H), 6.54 (s, 8H), 7.30 (m, 20H), 7.99 ( d, 4H), 8.06 (d, 2H), 8.37 (d, 4H), 9.85 (t, 4H)

Synthesis example 3
In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and gas introduction tube, nitrogen was flowed at 0.02 L / min to form a nitrogen atmosphere, and 305 parts of propylene glycol monomethyl ether acetate was added while stirring. Heated to ° C. Then 36 parts of acrylic acid; and 4,5-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate {ie monomer (BI-1)} and 3,4-epoxytri Cyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate {ie monomer (BII-1)} mixture {monomer (BI-1) in mixture: monomer (BII -1) molar ratio = 50: 50} 264 parts; was dissolved in 140 parts of propylene glycol monomethyl ether acetate to prepare a monomer solution. The monomer solution was dropped into a flask kept at 70 ° C. for 4 hours using a dropping funnel. On the other hand, a polymerization initiator solution in which 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 225 parts of propylene glycol monomethyl ether acetate was added for 4 hours using another dropping funnel. And dropped into the flask. After completion of the dropwise addition of the polymerization initiator solution, the solution was kept at 70 ° C. for 4 hours, and then cooled to room temperature, weight average molecular weight Mw: 9000, molecular weight distribution: 2.0, solid content 33%, solid content acid value 90 mg. A resin B1 solution of -KOH / g was obtained.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured using the GPC method under the following conditions.
Apparatus; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector; RI
Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The polystyrene-converted weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was defined as molecular weight distribution.

Examples 1 to 6 and Comparative Example 1
<Preparation of colored curable resin composition>
Each component was mixed so that it might become a composition shown in Table 6, and the colored curable resin composition was obtained.

In Table 6, each component represents the following. Moreover, resin (B) showed the mass part of solid content conversion.
Dye (A-1): A-1-1: Compound represented by formula (AH-9) Dye (A-1): A-1-2: Compound represented by formula (AH-13) Pigment ( A-2): A-2-1: C.I. I. Pigment Yellow 138
Pigment (A-2): A-2-2: C.I. I. Pigment Green 58 (FASTOGEN (registered trademark) Green A110; manufactured by DIC Corporation)
Pigment dispersant: Acrylic pigment dispersant Resin (B): Resin B1
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D): N-1919 (manufactured by ADEKA; O-acyloxime compound)
Solvent (E): E-1: Propylene glycol monomethyl ether acetate Solvent (E): E-2: N-methylpyrrolidone Leveling agent (F): Polyether-modified silicone oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.) Made)

<Preparation of colored coating film>
On a 5 cm square glass substrate (Eagle XG; manufactured by Corning), the colored curable resin composition was applied by spin coating so that the film thickness after post-baking was 2.2 μm, and then 3 ° C. at 100 ° C. Pre-baked for minutes. After standing to cool, light exposure was performed using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) in an air atmosphere at an exposure amount of 60 mJ / cm ² (based on 365 nm). After light irradiation, post-baking was performed in an oven at 160 ° C. for 20 minutes to obtain a colored coating film.

<Film thickness measurement>
About the obtained colored coating film, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product). The results are shown in Table 7.

<Chromaticity evaluation>
About the obtained colored coating film, spectrum was measured using a colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity in the XYZ color system of CIE using the characteristic function of the C light source. The coordinates (x, y) and the tristimulus value Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Table 7.

<Contrast measurement>
About the obtained colored coating film, contrast was measured by using a contrast colorimeter (CT-1; manufactured by Aisaka Electric Co., Ltd .; detector: BM-5A, light source: F-10) with a blank value of 30000. A measurement sample was obtained by sandwiching the glass substrate on which the coating film was formed with a polarizing film (POLAX-38S; manufactured by Luceo Co., Ltd.). The results are shown in Table 7.

  From the above results, it was confirmed that the colored pattern formed from the colored curable resin composition of the present invention was excellent in lightness. From this, it is understood that a display device having excellent color performance can be produced by using a color pattern formed from the colored curable resin composition of the present invention as a color filter.

  The colored curable resin composition of the present invention is excellent as a colored curable resin composition used for a color filter of a display device such as a liquid crystal display device because the color filter produced therefrom has high brightness.

Claims (12)

A colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E);
The colorant (A) contains a dye (A-1),
A colored curable resin composition comprising a compound represented by the following formula (AI) or formula (AII) and a macrocyclic compound (H) as the dye (A-1).


[In Formula (AI) or Formula (AII),
R ^{a1 to} R ^a4 and R ^{a13 to} R ^a16 are each independently a hydrogen atom, a halogen atom, a hydroxy group, a monovalent aromatic hydrocarbon-containing group which may have a substituent, or carbon Represents a monovalent saturated hydrocarbon group of 1 to 20, wherein R ^a1 and R ^a5 , R ^a2 and R ^a6 , R ^a3 and R ^a7 , R ^a4 and R ^a8 are the same as the carbon atom to which they are bonded, respectively. R ^a1 and R ^a9 , R ^a2 and R ^a10 , R ^a3 and R ^a11 , R ^a4 and R ^a12 together with the nitrogen atom and the carbon atom to which they are bonded, respectively, To form a ring. R ^a14 and R ^a17 , R ^a15 and R ^a18 may be combined with carbon atoms to which they are bonded to form a ring, and R ^a13 and R ^a19 , R ^a14 and R ^a20 , R ^a15 and R ^a21 , R ^a16 and R ^a22 may form a ring together with the nitrogen atom and carbon atom to which they are bonded, respectively.
R ^{a5 to} R ^a8 , R ^a17 and R ^a18 each independently represent a hydrogen atom, a hydroxyl group, a —SH group, a —CF ₃ group, or —NHCO—R ^a23 .
R ^{a9 to} R ^a12 are each independently a monovalent aromatic hydrocarbon-containing group having 8 or more carbon atoms which may have a substituent, a monovalent saturated hydrocarbon group having 8 to 20 carbon atoms, or A monovalent unsaturated aliphatic hydrocarbon group having 8 to 20 carbon atoms, wherein the monovalent saturated hydrocarbon group or the methylene group constituting the monovalent unsaturated aliphatic hydrocarbon group is an oxygen atom, sulfur An atom, —N (R ^a24 ) —, a sulfonyl group, or a carbonyl group may be substituted, and a hydrogen atom contained in the monovalent saturated hydrocarbon group is a halogen atom, a cyano group, a nitro group, or a carbamoyl group. , A sulfamoyl group, a hydroxy group, or an amino group may be substituted. R ^a9 and R ^a10 and R ^a11 and R ^a12 may form a ring together with the nitrogen atom to which they are bonded.
R ^{a19 to} R ^a22 are each independently a monovalent aromatic hydrocarbon-containing group ^optionally having a substituent, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. Of the monovalent unsaturated aliphatic hydrocarbon group, and the methylene group constituting the monovalent saturated hydrocarbon group or the monovalent unsaturated aliphatic hydrocarbon group is an oxygen atom, a sulfur atom, -N ( R ^a24 ) —, a sulfonyl group or a carbonyl group may be substituted, and the hydrogen atom contained in the monovalent saturated hydrocarbon group is a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a hydroxy group or It may be substituted with an amino group. R ^a19 and R ^a20 , R ^a21 and R ^a22 may be combined with the nitrogen atom to which they are bonded to form a ring.
R ^a23 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the methylene group constituting the monovalent saturated hydrocarbon group includes an oxygen atom, a sulfur atom, —N (R ^a25 ) —, sulfonyl A hydrogen atom contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a hydroxy group or an amino group. May be.
R ^a24 and R ^{a25 each} represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ] 2. The colored curability according to claim 1, wherein R ^{a19 to} R ^{a22 in the} formula (AII) are each independently a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. Resin composition. The colored curable resin composition according to claim 1, wherein the macrocyclic compound (H) is represented by cyclodextrin, crown ether, cyclophane, calixarene, or the following formula (AIII).

[In the formula (AIII),
R ^a26 and R ^a27 each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a hydroxy group, an amino group, or a monovalent hydrocarbon group having 1 to 20 carbon atoms. And the methylene group constituting the monovalent hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, -N (R ^a28 )-, a sulfonyl group, or a carbonyl group, and the monovalent hydrocarbon The hydrogen atom contained in the group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a hydroxy group, or an amino group.
R ^a28 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. The methylene group constituting the monovalent hydrocarbon group may be replaced with an oxygen atom, a sulfur atom, —N (R ^a29 ) —, a sulfonyl group, or a carbonyl group, and the monovalent hydrocarbon group The hydrogen atom contained may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a hydroxy group, or an amino group.
R ^a29 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ^a29 are present, they are the same or different from each other.
p and q each independently represent an integer of 0 to 3, n represents an integer of 1 to 8, and Z represents a carbon atom or a nitrogen atom. ]   The colored curable resin composition according to claim 3, wherein Z is a nitrogen atom.   The colored curable resin composition according to claim 3 or 4, wherein n is 1.   p or q is 0, The colored curable resin composition in any one of Claims 3-5.   The colored curable resin composition according to any one of claims 1 to 6, wherein the colorant (A) further contains a pigment (A-2).   The colored curable resin composition according to claim 7, wherein the pigment (A-2) is a yellow pigment or a green pigment.   The yellow pigment is C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 150, C.I. I. The colored curable composition according to claim 8, comprising at least one selected from the group consisting of CI Pigment Yellow 185. The integrated compound in which the compound represented by the following formula (AII) penetrates the macrocyclic compound (H).

[In the formula (AII),
R ^{a13 to} R ^a16 are each independently a hydrogen atom, a halogen atom, a hydroxy group, a monovalent aromatic hydrocarbon-containing group which may have a substituent, or a monovalent aromatic group having 1 to 20 carbon atoms. Represents a saturated hydrocarbon group, and R ^a14 and R ^a17 , R ^a15 and R ^a18 may each form a ring together with the carbon atom to which they are bonded, and R ^a13 , R ^a19 and R ^a14 And R ^a20 , R ^a15 and R ^a21 , R ^a16 and R ^a22 may form a ring together with the nitrogen atom and carbon atom to which they are bonded.
R ^a17 and R ^a18 each independently represent a hydrogen atom, a hydroxyl group, a —SH group, a —CF ₃ group, or NHCO—R ^a23 .
R ^{a19 to} R ^a22 each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and the methylene group constituting the monovalent saturated hydrocarbon group is , An oxygen atom, a sulfur atom, —N (R ^a24 ) —, a sulfonyl group or a carbonyl group, and the hydrogen atom contained in the monovalent saturated hydrocarbon group is a halogen atom, a cyano group or a nitro group , Carbamoyl group, sulfamoyl group, hydroxy group or amino group may be substituted. R ^a19 and R ^a20 , R ^a21 and R ^a22 may be combined with the nitrogen atom to which they are bonded to form a ring.
R ^a23 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the methylene group constituting the monovalent saturated hydrocarbon group includes an oxygen atom, a sulfur atom, —N (R ^a25 ) —, sulfonyl A hydrogen atom contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a hydroxy group or an amino group. May be.
R ^a24 and R ^{a25 each} represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]   The color filter formed with the colored curable composition in any one of Claims 1-9.   A display device comprising the color filter according to claim 11.