TW201510106A - Coloring composition, coloring curable film and display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition for forming a coloring curable film with extremely high brightness. SOLUTION: A coloring composition includes (A) a colorant, (B) a binding resin and (C) a polymerization compound, and is characterized in that the above-described colorant (A) comprises (a1) a cyanine-based compound and (a2) at least one compound selected from the group consisting of a pyridone azo compound, a dibenzo furans piperazine based compound, an azo methine-based compound, a quinophthalone-based compound, a coumarin-based compound, a pyrazoline-based compound.

Description

Coloring composition, coloring cured film, and display element

The present invention relates to a coloring composition, a colored cured film, and a display element. In particular, the coloring composition of a color hardening film for forming a solid-state imaging element such as a transmissive or reflective type color liquid crystal display element, an organic EL display element, an electronic paper, or the like, and a CMOS image sensor or the like A colored cured film formed of the colored composition and a display element including the colored cured film.

When a color filter is produced using a coloring composition, a method is known in which a pigment-dispersed radiation-sensitive coloring composition is applied onto a substrate to form a coating film, and then the coating film is exposed to a desired pattern shape and developed. Thus, pixels of respective colors are obtained (Patent Documents 1 and 2). As a method of producing a black matrix, a method of performing the same operation using a carbon black dispersion type radiation sensitive coloring composition is known (Patent Document 3). In addition, there is also known a method of coating by an inkjet method. The coloring composition of the pigment dispersion type is hardened, thereby forming pixels of respective colors (Patent Document 4). However, it has been reported that in order to achieve high luminance of a display element, high color purity, or high definition of a solid-state image sensor, it is effective to use a dye as a colorant. For example, Patent Document 5 proposes the use of a cyanine dye having a specific structure.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2-144502

[Patent Document 2] Japanese Patent Laid-Open No. 3-53201

[Patent Document 3] Japanese Patent Laid-Open No. Hei 6-35188

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2000-310706

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2009-235392

However, in recent years, there has been a strong demand for energy saving in the society, for example, a display element requiring less power consumption while maintaining high-quality display performance. In order to cope with this requirement, an attempt has been made to suppress the power consumption by suppressing the brightness of the backlight while improving the brightness of the color filter, thereby maintaining the display quality. Therefore, the demand for high luminance of display elements has become increasingly strict, and the brightness level of a known dye-type coloring composition has become insufficient.

Accordingly, it is an object of the present invention to provide a colored composition which forms a colored cured film having an extremely high brightness. The present invention also provides a colored cured film having an extremely high brightness and a display element including the colored cured film.

As a result of intensive studies, the present inventors have found that the above object can be attained by using a plurality of dyes satisfying specific conditions as a coloring agent.

That is, the present invention relates to the coloring composition comprising a coloring composition of (A) a coloring agent, (B) a binder resin, and (C) a polymerizable compound, The coloring agent (A) contains: (a1) a cyanine-based compound, and (a2) is selected from the group consisting of a pyridone azo compound, a dibenzopyran-based compound, and an azomethine-based compound. a quinophthalone compound, a coumarin compound, a pyrazolone compound, a compound having a structure represented by the following formula (M1), a compound having a structure represented by the following formula (M2), and a CI basicity At least one compound in the group of yellow 11.

The present invention also relates to a colored cured film characterized by comprising: (a1) a cyanine compound, and (a2) selected from the group consisting of pyridone azo compounds, dibenzopyrans a compound, an azomethine compound, a quinophthalone compound, a coumarin compound, a pyrazolone compound, a compound having a structure represented by the following formula (M1), and having the following formula (M2); At least one of the compound of the structure shown and the group of CI basic yellow 11 is characterized in that the display element has the colored cured film.

In the present specification, the "coloring cured film" is a concept including various color pixels, a black matrix, a black spacer, and the like used in various display elements, solid-state imaging elements, and the like.

In the formula (M1), R ^M1 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and R ^M2 represents an alkanediyl group having 1 to 8 carbon atoms. R ^M3 and R ^M4 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms. ]

[In the formula (M2), R ^M5 represents a cyano group, an aminomethyl fluorenyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylaminocarbonyl group, or a benzimidazolyl group, and R ^M6 represents a hydrogen atom, an alkylcarbonyl group, Or a trialkylcarbinyl group, R ^M7 and R ^M8 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and R ^M7 and R ^M8 may be bonded to each other to form a nitrogen-containing group. Heterocyclic. ]

When the colored composition of the present invention is used, it is possible to form a colored cured film having an extremely high luminance, and it is also possible to suppress generation of foreign matter. Therefore, the colored composition of the present invention can be particularly suitably used for coloring used in a transmissive or reflective type color liquid crystal display element, an organic EL display element, a display element such as an electronic paper, and a solid-state imaging element such as a CMOS image sensor. Formation of a cured film.

The display element having the colored cured film formed of the colored composition of the present invention has extremely high brightness.

[Formation of the Invention]

Hereinafter, the present invention will be described in detail.

The colored composition of the present invention contains at least (A) a colorant, (B) a binder resin, and (C) a polymerizable compound.

<(A) Colorant>

The (A) colorant contained in the color former composition of the present invention contains at least: (a1) a cyanine compound (hereinafter also referred to as "colorant (a1)"), and (a2) is selected from the group consisting of a pyridone azo compound, a dibenzopipelanium compound, an azomethine compound, a quinophthalone compound, a coumarin compound, and a pyrazolone compound, and has the above formula At least one compound of the compound of the structure represented by (M1), the compound of the structure represented by the above formula (M2), and the group of CI basic yellow 11 (hereinafter, also referred to as "colorant (a2)) ").

[Colorant (a1)]

For the cyanine-based compound of the coloring agent (a1) of the present invention, for example, the components (A-2) to (A-6) described in the examples of JP-A-2009-235392, and JP-A 2012 can be used. a compound described in paragraphs [0096] to [0108] of JP-A-212089, and a compound described in paragraphs [0054] to [0063] of JP-A-2012-214718, and JP-A-2012-214719. 0050]~[0054] The compound to be carried, etc., is preferably at least one selected from the group consisting of a compound having a structure represented by the following formula (C) and a group of C.I. Solvent Orange 107.

[In the formula (C), R ¹ to R ³ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group.

The Z ^1A ring and the Z ^2A ring each independently represent a substituted or unsubstituted aromatic hydrocarbon ring.

Q ¹ and Q ² each independently represent -O-, -S- or -CR ¹³ R ¹⁴ -.

R ¹¹ to R ¹⁴ each independently represent a substituted or unsubstituted hydrocarbon group. ]

Examples of the hydrocarbon group in R ¹ to R ³ and R ¹¹ to R ¹⁴ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

The aliphatic hydrocarbon group may be saturated or unsaturated, and examples thereof include an alkyl group, an alkenyl group, and an alkynyl group. The number of carbon atoms of these aliphatic hydrocarbon groups is preferably from 1 to 30, more preferably from 1 to 24, particularly preferably from 1 to 20. Further, these aliphatic hydrocarbon groups may be linear or branched. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a hexyl group, a heptyl group, and an octyl group. Indenyl, fluorenyl, undecyl, 1-methylindenyl, dodecyl, 1-methylundecyl, 1-ethylindenyl, tridecyl, tetradecyl, tri Grade dodecyl, pentadecyl, 1-heptyloctyl, cetyl, octadecane Base, behenyl-1-yl, docosa-1-yl, eicosyl-1-yl, tetracos-1-yl and the like. Examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 1,3-butadienyl group, a 1-pentenyl group, and a 2- Pentenyl, 1-hexenyl, 2-ethyl-2-butenyl, 2-octenyl, (4-vinyl)-5-hexenyl, 2-decenyl and the like. Further, examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a 1-pentynyl group, a 3-pentynyl group, a 1-hexynyl group, and a 2-ethyl-2- group. Butynyl, 2-octynyl, (4-ethynyl)-5-hexynyl, 2-decynyl and the like.

The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 30 carbon atoms. The alicyclic hydrocarbon group may be saturated or unsaturated, and examples thereof include a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a crosslinked cyclic hydrocarbon group, a spirocyclic hydrocarbon group, and a cyclic terpene group. More specifically, a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a tert-butylcyclohexyl group, a cycloheptyl group or a cyclooctyl group; a ring such as a 1-cyclohexenyl group; Alkenyl; condensed polycyclic hydrocarbon group such as tricyclodecyl, decahydro-2-naphthyl, adamantyl; tricyclo[5.2.1.0 ^2,6 ]decane-8-yl, pentacyclopentadecyl, different a cross-linked cyclic hydrocarbon group such as a dicyclopentenyl group or a tricyclopentenyl group; a spiro ring such as a monovalent group from which one hydrogen atom is removed from spiro[3,4]heptane or spiro[3,4]octane; Hydrocarbyl group A cyclic decyl group such as a monovalent group in which one hydrogen atom is removed, such as an alkane, a decane or a decane. In the above cycloalkyl group and cycloalkenyl group, it is more preferred that the number of carbon atoms is 3 to 12.

The aromatic hydrocarbon group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms. The aromatic hydrocarbon group may, for example, be an aryl group. In the present specification, the term "aryl" means a monocyclic to tricyclic aromatic hydrocarbon group, and specific examples thereof include a phenyl group, a benzyl group, an o-tolyl group, and the like. M-tolyl, p-tolyl, xylyl, naphthyl, anthracenyl, phenanthryl, anthracenyl, 9-fluorenyl and the like.

Among them, as the hydrocarbon group in R ¹ to R ³ , an aliphatic hydrocarbon group is preferred, and an alkyl group is more preferred. The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.

In particular, the hydrocarbon group in R ¹¹ to R ¹² is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms. The alkyl group is more preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group, an ethyl group, a propyl group or a butyl group.

Further, the hydrocarbon group in R ¹³ to R ¹⁴ is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms. An alkyl group is particularly preferably a methyl group or an ethyl group.

As the R ¹ ~ R ^3, preferably a hydrogen atom.

Q ¹ and Q ^{2 are} preferably -O-, -CR ¹³ R ¹⁴ -.

Further, as the aromatic hydrocarbon ring in the Z ^1A ring and the Z ^2A ring, an aromatic hydrocarbon ring having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon ring having 6 to 10 carbon atoms, is further preferable. It is a benzene ring or a naphthalene ring.

Examples of the substituent of the aromatic hydrocarbon ring in the Z ^1A ring and the Z ^2A ring and the hydrocarbon group in R ¹ to R ³ include a halogen atom, a hydroxyl group, a cyano group, a decyl group, a carboxyl group, a nitro group, and an amine group. , dialkylamino, diarylamino, alkoxy, aryloxy, alkoxycarbonyl, alkylthio, arylthio, trialkylcarbenyl, decyl, allyl, alkyl A sulfonyl group, an alkylsulfamoyl group, a hydrocarbon group which may be substituted by a halogen atom, a heterocyclic group or the like. Among them, a halogen atom or a halogen hydrocarbon group is preferred, a halogen atom or a halogenated C _1-8 hydrocarbon group is more preferred, and a halogen atom or a halogenated C _1-4 alkyl group is further more preferred.

In the cyanine compound of the coloring agent (a1), it is more preferably at least one selected from the group consisting of a compound having a structure represented by each of the following formulas (C1) and (C2) and a group of CI solvent orange 107. .

In the formula (C1), R ^C1 to R ^C6 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms.

In the formula (C2), R ^C7 to R ^C10 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R ^C11 represents a hydrogen atom, a halogen atom or a halogen hydrocarbon group having 1 to 8 carbon atoms. ]

The aliphatic hydrocarbon group having 1 to 8 carbon atoms in R ^C1 to R ^C10 is preferably an alkyl group having 1 to 8 carbon atoms. The alkyl group may be linear or branched. Examples of such an alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a secondary butyl group, a tertiary butyl group, an isobutyl group, and a pentyl group. Tertiary pentyl, hexyl, heptyl, octyl, isooctyl, trioctyl, 2-ethylhexyl and the like.

The aliphatic hydrocarbon group of R ^C1 , R ^C2 , R ^C7 and R ^C8 preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.

The aliphatic hydrocarbon group of R ^C3 to R ^C6 , R ^C9 and R ^C10 preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.

Examples of the halogen atom of R ^C11 include a chlorine atom, a bromine atom, and an iodine atom. Among them, a chlorine atom is preferred.

The hydrocarbon group which is a skeleton of a halogen hydrocarbon group having 1 to 8 carbon atoms in R ^C11 is preferably an aliphatic hydrocarbon group. Specific examples of the aliphatic hydrocarbon group include the same groups as those in R ^C1 to R ^C10 , and among them, an aliphatic hydrocarbon group having 1 to 4 carbon atoms is preferable. The halogen atom in the halogen hydrocarbon group having 1 to 8 carbon atoms of R ^C11 includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. From the viewpoint of heat resistance of the obtained colored composition, it is preferably Fluorine atom. Incidentally, the halogen atom may replace a part or all of the hydrogen atoms of the hydrocarbon group. Specific examples of the halohydrocarbyl group of R ^C11 include a trifluoromethyl group and the like.

Examples of the structure represented by the above formula (C1) include the structures shown by the following formulas (C1-1) to (C1-3), and the structure represented by the above formula (C2), for example, The structures and the like shown by the following formulas (C2-1) to (C2-3) are given.

When the structures represented by the above formulae (C), (C1) and (C2) are cationic, the compound having such a structure has a counter anion to make the whole electrically neutral. Examples of the counter anion include a halide ion, a boron anion, a phosphorus anion, a carboxylate anion, a sulfate anion, an organic sulfonate anion, a nitrogen anion, and a methylation. An anion, a perchlorate ion or the like of a transition metal complex having an azo compound in a ligand or a ligand.

Examples of the halide ion include a fluoride ion, a chloride ion, a bromide ion, and an iodide ion.

Examples of the boron anion include inorganic boron anions such as BF ₄ ^- and B (CN) ₄ , and [0038] of JP-A-2012-173399, and the specification of US Patent Application Publication No. 2008/0275224. Boron anion and the like described in paragraph 0014.

Examples of the phosphorus anion include phosphorus anions such as HPO ₄ ^2- , PO ₄ ^3- , and PF ₆ ^- , and [0037] of JP-A-2012-173399, and U.S. Patent Application Publication No. 2008/0275224 The phosphorus anion described in paragraph [0019] of the specification.

Examples of the carboxylate anion include CH ₃ COO ⁻ , C ₂ H ₅ COO ⁻ , C ₆ H ₅ COO ⁻ , and the like, and those described in JP-A-2009-265641 and JP-A-2008-096680 Carboxylate anion.

Examples of the sulfate anion include a sulfate anion and a sulfite anion.

Examples of the organic sulfonate anion include an alkylsulfonate anion such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid or nonafluorobutanesulfonic acid; benzenesulfonic acid, benzenedisulfonate ion, and p-toluenesulfonate; An arylsulfonate anion such as an acid, p-trifluoromethanesulfonic acid, pentafluorobenzenesulfonic acid, naphthalenesulfonic acid or naphthalene disulfonate; and 2-(meth)acryloxy-1,1,2, 2-tetrafluoroethanesulfonic acid, 2-(4-ethylene Benzyloxy)-1,1,2,2-tetrafluoroethanesulfonic acid, the organic matter described in Table 1 of JP-A-2011-070172, and Table 1 of JP-A-2014-080519 Sulfonate anion and the like.

Examples of the nitrogen anion include [(CN) ₂ N] ^- , [(FSO ₂ ) ₂ N] ^- , [(FSO ₂ ) N(CF ₃ SO ₂ )] ^- , [(CF ₃ SO ₂ ) ₂ N] ^- , [(FSO ₂ )N(CF ₃ CF ₂ SO ₂ )] ^- , [(FSO ₂ )N{(CF ₃ ) ₂ CFSO ₂ }] ^- , [(FSO ₂ )N(CF ₃ CF ^{_{2 CF 2 SO 2)] -}} , [(FSO 2) N (CF 3 CF 2 CF 2 CF 2 SO 2)] -, [(FSO 2) N {(CF 3) 2 CFCF 2 SO 2}] -, [(FSO ₂ )N{CF ₃ CF ₂ (CF ₃ )CFSO ₂ }] ^- , [(FSO ₂ )N{(CF ₃ ) ₃ CSO ₂ }] ^- and the like, and US Patent Application Publication No. 2008/0275224 The nitrogen anions described in paragraph [0039] of JP-A-2011-173803, JP-A-2011-116803, and JP-A-2011-173399.

Examples of the methide anion include (CF ₃ SO ₂ ) ₃ C ^- , (CF ₃ CF ₂ SO ₂ ) ₃ C ^- , [(CF ₃ ) ₂ CFSO ₂ ] ₃ C ^- , (CF ₃ CF). _{2 CF 2 SO 2) 3 C} -, (CF 3 CF 2 CF 2 CF 2 SO 2) 3 C -, [(CF 3) 2 CFCF 2 SO 2] 3 C -, [CF 3 CF 2 (CF 3) CFSO ₂ ] ₃ C ^- , [(CF ₃ ) ₃ CSO ₂ ] ₃ C ^- , (FSO ₂ ) ₃ C ^- and the like.

The anion of the transition metal complex having an azo compound in the above-mentioned ligand is described in paragraphs [0048] to [0062] of JP-A-2009-163226 and JP-A-2012-212089. The azo metal complex anion, the anion portion of the salt described in paragraphs [0053] to [0063] of JP-A-2012-214718, and the paragraphs [0049] to [0054] of JP-A-2012-214719 An anion described in the anion portion of the salt described.

The counter anion in the compound having the structure represented by the above formulas (C), (C1) and (C2) is preferably a halide ion, a boron anion, a nitrogen anion, a methide anion, or a ligand in the above. An anion or a perchlorate ion of a transition metal complex having an azo compound.

[Colorant (a2)]

The coloring agent (a2) in the present invention is selected from the group consisting of a pyridone azo compound, a dibenzopyranyl compound, an azomethine compound, a quinophthalone compound, a coumarin compound, and a pyrazole. A ketone compound, a compound having a structure represented by the above formula (M1), a compound having a structure represented by the above formula (M2), and at least one compound selected from the group consisting of CI basic yellow 11.

-pyridone azo compound -

As the pyridone azo compound in the coloring agent (a2) of the present invention, for example, a compound described in JP-A-2012-194200 can be used. The pyridone azo compound is preferably a compound represented by the following formula (P).

[In the formula (P), Z represents a substituted or unsubstituted aromatic hydrocarbon group, and R ^P1 represents a hydrogen atom, a cyano group, an aminomethyl fluorenyl group, an N-substituted aminomethyl fluorenyl group, a hydrocarbon group, and a carbon number of 3 to 20 a heterocyclic group, an alkoxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 30 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, or a fluorene having 2 to 20 carbon atoms. An aliphatic sulfonyl group having 1 to 30 carbon atoms or an arylsulfonyl group having 6 to 30 carbon atoms, and R ^P2 represents a hydrogen atom, a cyano group, an aminomethyl fluorenyl group, and an N-substituted amino group A mercapto group, an amsulfoxonyl group, a sulfo group, an amine group or a hydrocarbon group, and R ^P3 represents a hydrogen atom, a carboxyl group, a trifluoromethyl group, or a hydrocarbon group having 1 to 10 carbon atoms. ]

The aromatic hydrocarbon group in Z may, for example, be an aryl group, and specifically, a group similar to the aromatic hydrocarbon group in R ¹ to R ³ and R ¹¹ to R ¹⁴ may be mentioned. Among them, a phenyl group or a naphthyl group is preferred.

The aromatic hydrocarbon group preferably has a substituent. Examples of the substituent include a halogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, and a nitrate. A base group, a carboxyl group, a sulfo group, an amsulfoxonyl group, an aminomethylmercapto group, an N-substituted amisulpht group, an alkoxycarbonyl group or the like. When having a sulfo group as a substituent, the sulfo group may be in the form of a salt. The cation at this time may be, for example, a sodium ion, a potassium ion, an ammonium ion or the like. Further, the alkoxycarbonyl group may have an oxygen atom between the C-C bonds of the alkyl group. In addition, when the position and the number of the substituent are arbitrary, and when it has two or more of these substituents, this substituent may be the same or different.

Z in the above formula (P) preferably has an alkyl group selected from a halogen atom, a carbon number of 1 to 4, an alkoxy group having 1 to 4 carbon atoms, a sulfo group, and an N-substituted amisulphuric acid. a phenyl group having 1 or 2 substituents in the group of a nitro group, a nitro group, an alkoxycarbonyl group and a sodium salt type sulfo group, or a naphthyl group substituted by 1 or 2 sulfo groups, further preferably having A phenyl group of an N-substituted aminomercapto group. Here, as the halogen atom, a chlorine atom is preferred. The "sodium salt type sulfo group" means a -SO ₃ Na group.

Examples of the N-substituted substituent in the N-substituted sulfonamide group include an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. An organic group having a heterocyclic structure and having 4 to 8 carbon atoms. Among them, an aliphatic hydrocarbon group having 1 to 16 carbon atoms is preferable, an alkyl group having 4 to 16 carbon atoms is more preferable, and an alkyl group having 4 to 12 carbon atoms is more preferable. Incidentally, the alkyl group may be linear or branched. Further, the alkoxycarbonyl group has preferably 2 to 10 carbon atoms, more preferably 2 to 7. The alkyl group in the alkoxycarbonyl group may be linear or branched. Specific examples of the alkoxycarbonyl group include an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, and a methoxy group. Propyloxycarbonyl and the like.

Specific examples of Z, for example, are as follows: 4-sulfophenyl, 3-sulfo-4-chlorophenyl, 2-sulfo-3-tolylmethyl, 2-sulfo-3-methoxy Phenyl, 3-sulfophenyl, 3-chloro-4-sulfophenyl, 2-sulfophenyl, 2,5-disulfophenyl, 4-(N-dodecylsulfonamide Phenyl, 4,8-disulfonaphthalen-1-yl, 4-(N-pentylsulfamoyl)phenyl, 4-(N-(3-phenyl-1-methylpropyl) Acesulfonyl)phenyl, 4-(N-(2-ethylhexyl)sulfamoyl)phenyl, 2-(N-(2-ethylhexyl)sulfamoyl)phenyl, 4 -(N-methyl-N-n-octylsulfonyl)phenyl, 4-(N-phenyl-N-n-octylsulfonyl)phenyl, 4-nitro-2-(N -(2-ethylhexyl)ammonsulfonyl)phenyl, 2-chloro-4-(N-(2-ethylhexyl)ammonsulfonyl)phenyl, 2-methyl-5-(N- (2-ethylhexyl)ammonsulfonyl)phenyl, 4-(N-(n-octyl)ammonia Sulfhydryl)phenyl, 3-(N-(n-octyl)sulfamoyl)phenyl, 2-methoxy-5-(N-(n-octyl)sulfamoyl)phenyl, 2 -Methoxy-5-(N-(2-ethylhexyl)ammonsulfonyl)phenyl, 4-(N-(1,5-dimethylhexyl)sulfamoyl)phenyl, 4- (N-(1,1,3-trimethylbutyl)ammonsulfonyl)phenyl, 4-(N-(n-propyl)sulfamoyl)phenyl, 4-(N,N-double (2-methoxyethyl)ammonsulfonyl)phenyl, n-nitro-4-chlorophenyl, 3-nitro-4-chlorophenyl, 2-sodium salt sulfophenyl, 1 - sulfonaphthalen-1-yl, 4-(N-(tetrahydrofuran-2-ylmethyl)sulfamoyl)phenyl, 4-(N-(4-sodium salt sulfophenyl) amsulfoxane Phenyl, 4-chlorophenyl, 4-((N-(2-N,N-dimethylamino)ethyl)sulfamoyl)phenyl, 4-(N-(2-( 2-methoxyethoxy)ethyl)sulfamoyl)phenyl, 4-((N-2-methoxy-1-methylethyl)sulfamoyl)phenyl, 4-(( N-(1-isopropylpentyl)ammonsulfonyl)phenyl, 2,3-bis(methoxyethoxycarbonyl)phenyl, 3,4-bis(methoxyethoxycarbonyl) Phenyl and the like.

Examples of the N-substituted group in the N-substituted aminomethyl indenyl group in R ^P1 include an alkyl group having 1 to 12 carbon atoms.

Examples of the hydrocarbon group in R ^P1 include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and their specific structures are the same as those described for the hydrocarbon groups of R ¹ to R ³ and R ¹¹ to R ¹⁴ . In particular, the hydrocarbon group in R ^P1 is preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, more preferably 1 carbon atom. Further, the alkyl group of ~8 is more preferably an alkyl group having 1 to 4 carbon atoms. Incidentally, the alkyl group may be linear or branched, and may be substituted with a hydroxyl group.

The heterocyclic group in R ^P1 may be, for example, a monocyclic hetero ring or a polycyclic hetero ring. The heterocyclic group may be an unsaturated ring or a saturated ring, and may have two or more kinds of hetero atoms (for example, a nitrogen atom, an oxygen atom, or a sulfur atom) of the same type or different types in the ring. The heterocyclic group is preferably a heterocyclic group having 3 to 10 carbon atoms, and specific examples thereof include a pyrrolidinyl group, a pyrazolinyl group, a piperidinyl group, a piperidino group, and a piperidyl group. Base, high piper base, Olinyl group, Alicyclic heterocyclic group such as phenyloyl group, pyridyl group, pyridyl Base, pyrimidinyl, oxime Base, quinolyl, isoquinolyl, anthracene Base Orolinyl, thiophenanthryl, furyl, pyridyl Base, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, An aromatic heterocyclic group such as an azolyl group, a fluorenyl group, a carbazolyl group, a benzimidazolyl group or a fluorenyl group.

The alkoxycarbonyl group in R ^P1 preferably has 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms. Specific examples thereof include the same groups as the alkoxycarbonyl group in the substituent of Z.

The number of carbon atoms of the aryloxycarbonyl group in R ^P1 is preferably from 7 to 11. Specific examples thereof include a phenoxycarbonyl group and a naphthyloxycarbonyl group.

The alkoxyalkyl group in R ^P1 is preferably a C _1-12 alkoxy group substituted by a C _1-12 alkyl group. As a specific example, an ethoxyethyl group is mentioned, for example.

The aliphatic sulfonyl group in R ^P1 is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and specific examples thereof include a methylsulfonyl group, an ethylsulfonyl group, and a hexylsulfonium group. Base, mercaptosulfonyl, tetradecylsulfonyl, tert-dodecylsulfonyl, octadecylsulfonyl and the like.

The arylsulfonyl group in R ^P1 is preferably an arylsulfonyl group having 6 to 14 carbon atoms. Specific examples thereof include a phenylsulfonyl group and a naphthylsulfonyl group.

In particular, R ^{P1 is} preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms.

Examples of the N-substituted group in the N-substituted aminomethyl fluorenyl group in R ^P2 include an alkyl group having 1 to 12 carbon atoms.

The hydrocarbon group in R ^P2 and R ^P3 is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms. . Incidentally, the alkyl group may be linear or branched.

Among them, as R ^P2 , a cyano group is preferred. Further, R ^{P3 is} preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms. Incidentally, the alkyl group may be linear or branched.

Among the compounds represented by the above formula (P), a compound represented by the following formula (P1) is particularly preferred.

In the formula (P1), R ^P4 represents an aliphatic hydrocarbon group having 1 to 16 carbon atoms, and R ^P5 and R ^P6 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms. ]

The aliphatic hydrocarbon group of R ^P4 in the above formula (P1) is preferably an alkyl group having 4 to 12 carbon atoms, and the alkyl group may be linear or branched, and preferably branched.

The aliphatic hydrocarbon group having 1 to 8 carbon atoms in R ^P5 and R ^P6 is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be a linear chain. The shape may also be branched.

Specific examples of the compound represented by the above formula (P1) include compounds represented by the following formulas (P1-1) and (P1-2).

-dibenzopyranyl compound -

For the dibenzopipel-based compound in the coloring agent (a2) of the present invention, for example, a compound represented by the formulas (A1) to (A6) described in the examples of JP-A-2013-100463 can be used. The compounds described in paragraphs [0038] to [0038] of JP-A-2012-181505, and paragraphs [0036] to [0038] of JP-A-2013-007032. The dibenzopipelan compound is preferably a compound having a structure represented by the following formula (X).

[In the formula (X), R ^X1 to R ^X4 each independently represent a hydrogen atom, R ⁰¹ or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms, and R ^X5 and R ^X6 each independently represent a hydrogen atom. Or an alkyl group having 1 to 8 carbon atoms, and R ^X7 represents -SO ₃ -, -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁰¹ , -SO ₃ R ⁰¹ , -SO ₂ NHR ⁰² , -SO ₂ NR ⁰² R ⁰³ or a group having a polymerizable unsaturated group, r represents an integer of 0 to 5, and when r is an integer of 2 or more, a plurality of R ^X7 may be the same or different.

R ⁰¹ represents a saturated hydrocarbon group having 1 to 10 carbon atoms which may have a linking group containing an atom other than a carbon atom, a hydrogen atom or a halogen atom, or may have a bond containing an atom other than a carbon atom, a hydrogen atom or a halogen atom. The group has a carbon number of 1 to 10 halogenated saturated hydrocarbon group, and R ⁰² and R ⁰³ each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted ring having 3 to 30 carbon atoms. An alkyl group, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 10 carbon atoms, and R ⁰² and R ⁰³ may be bonded to each other to form a substitution or An unsubstituted heterocyclic group having 1 to 10 carbon atoms.

M represents a sodium atom or a potassium atom. ]

In the structure represented by the above formula (X), various resonance structures exist. However, as long as one of the limit structures is a structure represented by the above formula (X), it is understood to belong to the structure represented by the above formula (X).

The aromatic hydrocarbon group in R ^X1 to R ^X4 is preferably an aryl group having 6 to 10 carbon atoms, and more preferably a phenyl group or a naphthyl group.

The saturated hydrocarbon group which is a skeleton of a saturated hydrocarbon group and a halogenated saturated hydrocarbon group of R ⁰¹ may have a linear form, a branched form, and a cyclic form, and may have a crosslinked structure. Examples of the saturated hydrocarbon group include a saturated aliphatic hydrocarbon group and a saturated alicyclic hydrocarbon group. Among them, an aliphatic hydrocarbon group having 1 to 8 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred. More preferably, it is an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group. Examples of the halogen of the halogenated saturated hydrocarbon group include a chlorine atom, a bromine atom, and an iodine atom. Among them, a chlorine atom is preferred. Incidentally, the halogen atom may replace a part or all of the hydrogen atoms of the saturated hydrocarbon group.

Further, the saturated hydrocarbon group and the halogenated saturated hydrocarbon group of R ⁰¹ may have a linking group containing an atom other than a carbon atom, a hydrogen atom or a halogen atom between CC bonds which become a saturated hydrocarbon group of the skeleton. Examples of the linking group include -O-, -S-, -CO-, -COO-, -CONH-, -SO ₂ -, -NR'- (wherein R' is a hydrogen atom or a carbon atom 1~8 alkyl groups).

As the aromatic hydrocarbon group in R ⁰² and R ⁰³ , a phenyl group or a naphthyl group is preferred. Further, specific examples of the heterocyclic group in which R ⁰² and R ⁰³ are bonded to each other, and the aromatic heterocyclic group in R ⁰² and R ⁰³ include a heterocyclic group and an aromatic heterocyclic ring in R ^P1 , respectively. The same group of groups. In particular, R ⁰² and R ^{03 are} preferably an alkyl group having 4 to 10 carbon atoms, more preferably an alkyl group having 4 to 8 carbon atoms, and the alkyl group may be linear or branched. However, it is preferably branched.

Examples of the substituent in the aromatic hydrocarbon group of R ^X1 to R ^X4 include a halogen atom, R ⁰¹ , -OH, -OR ⁰¹ , -SO ₃ H, -SO ₃ M, -CO ₂ H, and -CO _{2 .} R ⁰¹ , -SO ₃ R ⁰¹ , -SO ₂ NHR ⁰² or -SO ₂ NR ⁰² R ⁰³ and the like.

Examples of the substituent in the aromatic hydrocarbon group and the aromatic heterocyclic group of R ⁰² and R ⁰³ include a halogen atom, -OH, R ⁰¹ , -OR ⁰¹ , -NO ₂ , -CH=CH ₂ , -CH=CHR ⁰¹ and the like.

Examples of the substituent in the linear alkyl group and the cycloalkyl group of R ⁰² and R ⁰³ include a halogen atom, -OH, -W, -CH=CH ₂ , -CH=CHR ⁰¹ and the like.

Examples of the substituent in the heterocyclic group in which R ⁰² and R ⁰³ are bonded to each other include -R ⁰¹ , -OH, -W and the like.

The above -W is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 10 carbon atoms. Examples of the substituent in the aromatic hydrocarbon group and the aromatic heterocyclic group of -W include a halogen atom, -OH, R ⁰¹ , -OR ⁰¹ , -NO ₂ , -CH=CH ₂ , -CH=. CHR ⁰¹ and so on.

In addition, the substitution position and number of these substituents are arbitrary, and when it has two or more substituents, this substituent may be the same or different. Further, in all of the above, R ⁰¹ to R ⁰³ are each the same meaning as the content defined in the formula (X).

R ^X1 to R ^X4 in the above formula (X) are preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an N-substituted carbon number of 6 to 12. Sulfosylaryl or a sulfoaryl group having 6 to 12 carbon atoms. Specific examples thereof include a hydrogen atom, a methyl group, an ethyl group, a xylyl group, an N-substituted amisulphtyl xylyl group, a sulfoxylyl group, and the like.

R ^X5 and R ^X6 in the above formula (X) are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Specifically, it is a hydrogen atom, a methyl group, etc., for example.

R ^X7 in the above formula (X) is preferably a carboxyl group, an alkoxycarbonyl group having 2 to 6 carbon atoms, an N-substituted sulfonamide group, a sulfo group, or a group having a polymerizable unsaturated group. Specific examples thereof include a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, an N-substituted amisulpht group, a sulfo group and the like. The N-substituted group in the N-substituted sulfonamide group in the above formula (X) may, for example, be a linear or branched alkyl group having 4 to 10 carbon atoms.

In the group having a polymerizable unsaturated group in R ^X7 , examples of the polymerizable unsaturated group include a (meth)acryl fluorenyl group, a vinyl aryl group, a vinyloxy group, an allyl group and the like. It is preferably a (meth) acrylonitrile group. A preferred specific example of the group having a polymerizable unsaturated group is a group represented by the following formula (1x) or (2x).

In the formulae (1x) and (2x), R ^X8 and R ^X9 each independently represent a hydrogen atom or a methyl group.

Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a substituted or unsubstituted alkanediyl group having 1 to 12 carbon atoms.

Z ^X represents a -CO- group or a -COO-(*) group (wherein * represents a bonding site with Y ² ).

Q ^X represents a divalent alicyclic hydrocarbon group.

P ¹ represents an integer from 0 to 12.

p ² and p ³ each independently represent an integer of 0-6. ]

As R ^X8 and R ^X9 , a hydrogen atom and a methyl group are preferably a methyl group.

Examples of the alkanediyl group having 1 to 12 carbon atoms in Y ¹ to Y ⁴ include a methylene group, an ethylidene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, and a propane. -1,2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1 ,4-diyl, pentane-1,2-diyl, pentane-1,3-diyl, pentane-1,4-diyl, pentane-1,5-diyl, hexane-1 , 5-diyl, hexane-1,6-diyl, octane-1,8-diyl, decane-1,10-diyl, etc., wherein an alkane having 2 to 8 carbon atoms is preferred. The dibasic group is more preferably an alkanediyl group having 2 to 6 carbon atoms.

Examples of the substituent of the alkanediyl group include a hydroxyl group, a halogen atom, a (meth)acryloxy group, and a phenoxy group. Among them, a hydroxyl group is preferred.

The divalent alicyclic hydrocarbon group in Q ^X is preferably a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, more preferably a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms. Incidentally, the alicyclic hydrocarbon group may be saturated or unsaturated, and may be a 2 to 4 ring crosslinked cyclic hydrocarbon group. Specific examples thereof include a monocyclic hydrocarbon ring group such as a cyclocyclopropyl group, a cyclobutylene group, a cyclopentylene group, a cyclocyclobutenyl group, a cyclopentylene group, or a cyclohexene group. , 4-Adam Base, 2,5-sub-drop Base A crosslinked cyclic hydrocarbon ring group such as a 1,5-adamantyl group or a 2,6-adamantyl group.

p ^{1 is} preferably an integer of 0 to 3, and p ² and p ³ preferably each independently represent an integer of 0 to 3.

The structure represented by the above formula (X) is, for example, a structure represented by each of the following formulae (X-1) to (X-16).

[In the formula (X-7) to (X-9), R ^c is 2-ethylhexyl. ]

When the structure represented by the above formula (X) is cationic, the compound having such a structure has a counter anion to make the whole electrically neutral. Further, when the structure represented by the above formula (X) is anionic, the compound having such a structure has a counter cation so that the whole becomes electrically neutral.

As the counter anion, a counter anion which is the same as the counter anion described as a counter anion when the structure shown by each of the above formulas (C), (C1) and (C2) is cationic can be used.

Examples of the counter cation include a proton, a metal cation, a phosphonium cation, and the like.

Examples of the metal cation include monovalent metal cations such as lithium ions, sodium ions, potassium ions, cesium ions, and cesium ions; and divalent metal cations such as magnesium ions, calcium ions, strontium ions, and cesium ions.

Examples of the phosphonium cation include an ammonium cation, a phosphonium cation, and the like. Examples of the ammonium cation include tetramethylammonium, tetraethylammonium, monostearyltrimethylammonium, distearyldimethylammonium, tristea monomethylammonium, and cetyl group. Trimethylammonium, trioctylmethylammonium, dioctyldimethylammonium, monolauryltrimethylammonium, dilauryldimethylammonium, trilaurylmethylammonium, triamylbenzylammonium, Trihexylbenzylammonium, trioctylbenzylammonium, trilaurylbenzylammonium, benzyldimethylstearylammonium, benzyldimethyloctylammonium, di-C _14-18 alkyldimethylammonium The resin having an ammonium-cationic group in the side chain described in JP-A-2012-32770, and the above-mentioned phosphonium cation include, for example, methyltrioctylfluorene, octyltributylphosphonium, and ten. Aryltrialkylsulfonium such as dialkyltributylphosphonium, cetyltributylphosphonium, dihexyldioctylfluorene, etc., aryltrialkylsulfonium such as benzyltributylphosphonium, dibutyldiphenylphosphonium An alkyltriphenylphosphonium such as a dialkyldiarylsulfonium or a butyltriphenylphosphonium or a tetraarylphosphonium such as a benzyltriphenylphosphonium.

-Azomethine compounds -

The azo methine-based compound in the coloring agent (a2) of the present invention may be, for example, a compound described in JP-A-2011-219655, and a compound described in JP-A-2013-145258. The azomethine-based compound is preferably a compound having a structure represented by the following formula (A).

[In the formula (A), R ^A1 to R ^A4 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms, R ^A5 represents a hydrogen atom, or may have a carbon atom, a hydrogen atom or a halogen atom. The linking group of the atom has an aliphatic hydrocarbon group having 1 to 8 carbon atoms. ]

The aliphatic hydrocarbon group having 1 to 8 carbon atoms of R ^A1 to R ^A4 in the above formula (A) is preferably an alkyl group having 1 to 8 carbon atoms. The alkyl group may be linear or branched. Examples of such an alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a secondary butyl group, a tertiary butyl group, an isobutyl group, and a pentyl group. Tertiary pentyl, hexyl, heptyl, octyl, isooctyl, trioctyl, 2-ethylhexyl and the like. The number of carbon atoms in the aliphatic hydrocarbon group of R ^A1 to R ^A4 is preferably from 1 to 6, more preferably from 1 to 4.

The aliphatic hydrocarbon group having 1 to 8 carbon atoms of R ^A5 in the above formula (A) is the same as the group described for the aliphatic hydrocarbon group having 1 to 8 carbon atoms of R ^A1 to R ^A4 , but may have A linking group containing an atom other than a carbon atom, a hydrogen atom or a halogen atom may be bonded to the phenyl group via the above-mentioned linking group. Examples of the linking group at this time include -O-, -S-, -CO-, -COO-, -CONH-, -SO ₂ -, etc., among which -O-, -CO- are preferred. Or -COO-, more preferably -O- or -COO-. The orientation of these linking groups is not required. As R ^A5, alkyl carbon atoms, or most preferably 1 to 8 carbon atoms, an alkoxy group having 1 to 8. The number of carbon atoms in the aliphatic hydrocarbon group of R ^A5 is preferably from 1 to 6. In addition, examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group.

When the structure represented by the above formula (A) is cationic, the compound having such a structure has a counter anion to make the whole electrically neutral. The counter anion is the same counter anion as the counter anion described for the counter anion when the structure shown by each of the above formulas (C), (C1), and (C2) is cationic. Among them, a nitrogen anion, a halide ion, an organic sulfonate anion, a boron anion or the like is preferable, and particularly preferably [(CF ₃ SO ₂ ) ₂ N] ^- .

Specific examples of the compound having the structure represented by the above formula (A) include compounds represented by the following formulas (A-1) to (A-3).

-Quinone compound -

Examples of the quinophthalone compound in the color former (a2) of the present invention The compound represented by the formula (2) described in JP-A-2006-126649, JP-A-2006-126649, JP-A-2006-126649, and JP-A-2006-126649, The compound represented by the formula (1) described in JP-A-2010-250291, and the compound represented by the formula (1) described in JP-A-2013-209614. The quinacridone compound is preferably a compound represented by the following formula (Q).

[In the formula (Q), R ^Q1 represents a halogen atom, an alkoxy group, a substituted or unsubstituted phenoxy group, a thioalkoxy group, a substituted or unsubstituted thiophenoxy group, or a substituted or unsubstituted carbon. a hydrocarbon group having 1 to 20 atoms, and R ^Q2 represents a halogen atom, an alkoxy group, a thioalkoxy group, a substituted or unsubstituted amino group, a mercapto group, a mercaptoamine group, an alkoxy alkoxy group, an alkoxy group. a carbonyl group, a phenoxycarbonyl group, an aminomethyl fluorenyl group, an N-substituted aminomethyl fluorenyl group, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.

p represents an integer of 0 to 3, and when p is an integer of 2 or more, a plurality of R ^Q1s may be the same or different.

q represents an integer of 0 to 4, and when q is an integer of 2 or more, a plurality of R ^Q2s may be the same or different. ]

Examples of the halogen atom in R ^Q1 and R ^Q2 include a chlorine atom, a bromine atom, and an iodine atom.

The alkoxy group in R ^Q1 and R ^Q2 is preferably an alkoxy group having 1 to 8 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms.

^Examples of the hydrocarbon group in R ^Q1 and R ^Q2 include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and specific examples thereof are given for the hydrocarbon groups of R ¹ to R ³ and R ¹¹ to R ¹⁴ . The same group. Among them, an aliphatic hydrocarbon group is preferred, an alkyl group having 1 to 12 carbon atoms is more preferred, a more preferred alkyl group having 1 to 8 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms. Particularly preferred are methyl, ethyl, propyl, isopropyl, butyl.

The alkoxyalkoxy group in R ^Q2 is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably an alkoxyalkoxy group having 2 to 5 carbon atoms. Specific examples thereof include a methoxyethoxy group, an ethoxyethoxy group, a n-propoxyethoxy group, and an ethoxypropoxy group.

The alkoxycarbonyl group in R ^Q2 is preferably an alkoxycarbonyl group having 1 to 9 carbon atoms, more preferably an alkoxycarbonyl group having 1 to 5 carbon atoms. Specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, and an octyloxycarbonyl group.

The N-position substituent in the amine group and the N-substituted aminomethyl fluorenyl group in R ^Q2 is, for example, preferably an alkyl group having 1 to 8 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms. . Further, examples of the substituent of the phenoxy group, the thiophenoxy group, and the hydrocarbon group include the same groups as the substituent of the hydrocarbon group in R ¹ to R ³ .

p and q are preferably 0 or 1. When p is 1, R ^{Q1 is} preferably an alkyl group having 1 to 12 carbon atoms. When q is 1, R ^{Q2 is} preferably an N-substituted aminomethyl fluorenyl group, and as the N-substituted group, an alkyl group having 1 to 8 carbon atoms is preferable.

Specific examples of the compound represented by the above formula (Q) include a compound represented by (Q1) and the like.

- Coumarin compounds -

For example, the compound described in Example 4 of JP-A-4-179955, and the formula described in JP-A-2013-151668 can be used as the coumarin compound in the coloring agent (a2) of the present invention. 1) The compound represented by the formula (1) described in JP-A-2013-231165, and the compound represented by the formula (1) described in JP-A-2014-044419. The coumarin compound is preferably a compound represented by the following formula (Cou).

[In the formula (Cou), R ^u1 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and R ^u2 and R ^u3 each independently represent a halogen atom, an alkoxy group, a substituted or unsubstituted amino group. Or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, s represents an integer of 0 to 3, and when s is an integer of 2 or more, a plurality of R ^u2 may be the same or different.

t represents an integer of 0 to 4, and when t is an integer of 2 or more, a plurality of R ^u3 may be the same or different. ]

^Examples of the hydrocarbon group in R ^u1 to R ^u3 include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Among them, an alkyl group having 1 to 8 carbon atoms is preferable, and more preferably a carbon number is 1 to 1. 4 alkyl groups. In addition, examples of the substituent of the hydrocarbon group include the same groups as the substituent of the hydrocarbon group in R ¹ to R ³ .

Examples of the halogen atom in R ^u2 and R ^u3 include a chlorine atom, a bromine atom, and an iodine atom.

The alkoxy group in R ^u2 and R ^u3 is preferably an alkoxy group having 1 to 8 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms.

The amine group in R ^u2 and R ^u3 preferably has a substituent, and as the substituent at the N position, an alkyl group having 1 to 8 carbon atoms is preferred, and an alkyl group having 1 to 4 carbon atoms is more preferred.

s is preferably 1, in which case R ^{u2 is} preferably a substituted amine group, more preferably a dialkyl substituted amine group, still more preferably a bis (C _1-8 alkyl) substituted amine group. t is preferably 0.

In a preferred ^embodiment , R ^u1 is a hydrogen atom, s is 1 and R ^u2 is a substituted amine group, and t is 0. In a more preferred manner, R ^u1 is a hydrogen atom, s is 1 and R ^u2 is a dialkyl substitution. Amine group, t is 0.

Specific examples of the compound represented by the above formula (Cou) include compounds represented by (Cou-1) and (Cou-2), and the like.

-pyrazolone-based compound-

For the pyrazolone-based compound in the coloring agent (a2) of the present invention, for example, a compound represented by the formula (1) described in JP-A-2006-016564, and JP-A-2006-063171 can be used. The compound represented by the formula (1). The pyrazolone compound is preferably a compound represented by the following formula (Pzo).

[In the formula (Pzo), R ^Z1 and R ^Z3 each independently represent an alkyl group or an aryl group, and R ^Z2 represents an alkyl group. ]

The alkyl group in R ^Z1 , R ^Z2 and R ^Z3 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably 1 to 8 carbon atoms. Alkyl. The alkyl group may be linear or branched.

The aryl group in R ^Z1 and R ^Z3 is preferably a monocyclic or bicyclic aryl group having 6 to 10 carbon atoms, more preferably a phenyl group, a benzyl group, an o-tolyl group, an m-tolyl group or a p-toluene group. Base, xylyl, naphthyl.

Specific examples of the compound represented by the above formula (Pzo) include compounds represented by (Pzo-1) to (Pzo-10).

- a compound having the structure represented by formula (M1) -

The compound having a structure represented by the formula (M1) is the following compound.

In the formula (M1), R ^M1 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and R ^M2 represents an alkanediyl group having 1 to 8 carbon atoms. R ^M3 and R ^M4 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms. ]

The aliphatic hydrocarbon group having 1 to 8 carbon atoms of R ^M1 is preferably an alkyl group having 1 to 8 carbon atoms. The alkyl group may be linear or branched. Examples of such an alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a secondary butyl group, a tertiary butyl group, an isobutyl group, and a pentyl group. Tertiary pentyl, hexyl, heptyl, octyl, isooctyl, trioctyl, 2-ethylhexyl and the like. The number of carbon atoms in the aliphatic hydrocarbon group of R ^M1 is preferably from 1 to 6, more preferably from 1 to 4.

The alicyclic hydrocarbon group having 3 to 20 carbon atoms of R ^M1 is preferably an alicyclic hydrocarbon group having 3 to 12 carbon atoms. Specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclododecyl group, and a lower portion. base, Base, adamantyl, bicyclooctyl, and the like.

Examples of the alkanediyl group having 1 to 8 carbon atoms of R ^M2 include a methylene group, an ethylidene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, and a propane-1. 2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4- Diyl, pentane-1,4-diyl, pentane-1,5-diyl, hexane-1,5-diyl, hexane-1,6-diyl, octane-1,8- Second base and so on. Among them, an alkanediyl group having 1 to 6 carbon atoms is preferable, and an alkanediyl group having 1 to 4 carbon atoms is more preferable.

The aliphatic hydrocarbon group having 1 to 8 carbon atoms of R ^M3 and R ^{M4 is} the same as the group described for the aliphatic hydrocarbon group having 1 to 8 carbon atoms of R ^M1 , and preferably has 1 to 6 carbon atoms. The alkyl group is more preferably an alkyl group having 1 to 4 carbon atoms.

Specific examples of the compound represented by the above formula (M1) include a compound represented by the following formula (M1-1).

- a compound having the structure represented by the formula (M2) -

The compound having a structure represented by the formula (M2) is the following compound.

[In the formula (M2), R ^M5 represents a cyano group, an aminomethyl fluorenyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylaminocarbonyl group, or a benzimidazolyl group, and R ^M6 represents a hydrogen atom, an alkylcarbonyl group, Or a trialkylcarbinyl group, R ^M7 and R ^M8 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and R ^M7 and R ^M8 may be bonded to each other to form a nitrogen-containing group. Heterocyclic. ]

The alkoxycarbonyl group in R ^M5 preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 2 to 7 carbon atoms. The alkyl group of the alkoxycarbonyl group may be linear or branched. Specific examples thereof include an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, and a 2-ethylhexyloxycarbonyl group.

The aryloxycarbonyl group in R ^M5 preferably has 7 to 11 carbon atoms, and specific examples thereof include a phenoxycarbonyl group and a naphthyloxycarbonyl group.

The arylaminocarbonyl group in R ^M5 preferably has 7 to 11 carbon atoms, and specific examples thereof include a phenylaminocarbonyl group and a naphthylaminocarbonyl group.

The alkylcarbonyl group in R ^M6 preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 2 to 7 carbon atoms. The alkyl group in the alkylcarbonyl group may be linear or branched. Specific examples thereof include a methylcarbonyl group, an ethylcarbonyl group, a propylcarbonyl group, and a butylcarbonyl group.

The alkyl group of the trialkylcarbenyl group in R ^M6 preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms. The alkyl group of the trialkylcarbenyl group may be linear or branched, and the three alkyl groups may be the same or different. Specific examples thereof include a trimethylmethane alkyl group and a triethylmethane alkyl group.

The alkyl group in R ^M7 and R ^M8 preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms. The alkyl group may be linear or branched. Specific examples thereof include the same groups as those exemplified for R ¹ to R ³ and R ¹¹ to R ¹⁴ .

^Examples of the aryl group in R ^M7 and R ^M8 include the same groups as the aromatic hydrocarbon groups in R ¹ to R ³ and R ¹¹ to R ¹⁴ . Among them, a phenyl group or a naphthyl group is preferred.

Examples of the substituent of the alkyl group and the aryl group in R ^M7 and R ^M8 include a halogen atom, a hydroxyl group, a cyano group, a decyl group, a carboxyl group, a nitro group, an alkoxy group and the like.

The nitrogen-containing hetero ring which is formed by bonding R ^M7 and R ^{M8 to} each other is preferably a heterocyclic group having 3 to 10 carbon atoms, and specific examples thereof include the same groups as those exemplified in R ^P1 . group. Among them, preferably Olinyl group, A nitrogen-containing alicyclic heterocyclic group such as a phenyl group.

Specific examples of the compound represented by the above formula (M2) include compounds represented by the following formulas (M2-1) to (M2-6).

The C.I. Basic Yellow 11 in the coloring agent (a2) of the present invention is a compound represented by the following formula (M3).

In the present invention, a specific dye such as a coloring agent (a1) and a coloring agent (a2) is used in combination as the (A) coloring agent. Further, the coloring composition containing such a coloring agent (A) can be preferably used for forming a red cured film, and is particularly preferably used for forming a red pixel of a display element or a solid-state image sensor.

[other colorants]

The coloring agent (A) in the coloring composition of the present invention must contain the coloring agent (a1) and the coloring agent (a2) as described above, but other coloring agents may be optionally contained.

As the other coloring agent usable herein, for example, a dye other than the coloring agent (a1) and the coloring agent (a2) and a pigment can be used. However, in order to obtain a pixel having high luminance and color purity, it is preferable to use it as an organic pigment and an organic dye as the other coloring agent, and it is more preferable to use an organic pigment.

As the above-mentioned organic pigment, for example, a compound belonging to a pigment in a color index (C.I.; issued by The Society of Dyers and Colourists) can be cited. In addition, as a preferable pigment, the Japanese Laid-Open Patent Publication No. 2001-081348, JP-A-2010-026334, and the Japanese The lakes described in JP-A-2010-237304, JP-A-2010-237384, JP-A-2010-237569, JP-A-2011-006602, JP-A-2011-145346, and the like Pigment; CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 264, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Blue 15:6, CI Pigment Blue 80, CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 211, CI Pigment Yellow 215, CI Organic pigments other than lake pigments such as Pigment Orange 38 and CI Pigment Violet 23. As the above lake pigment, preferred are a triarylmethane-based lake pigment, a dibenzopyran-based lake pigment, and an azo-based lake pigment, more preferably a triarylmethane-based lake pigment and dibenzopyran. It is a lake pigment.

The colored composition of the present invention is preferably used to form a red cured film. At this time, as another coloring agent, a red pigment and a red dye are preferable.

When a pigment is used as the other coloring agent, it may be used after one or more kinds of treatments selected from the group consisting of refining and surface modification by a known method; a known dispersing agent and dispersing aid may be used in combination. Examples of the known dispersant include a polyurethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, and a polyoxyethylene alkylphenyl ether dispersant. a polyethylene glycol diester dispersant, a sorbitan fatty acid ester dispersant, a polyester dispersant, an acrylic dispersant, or the like; As a well-known dispersing adjuvant, a pigment derivative etc. are mentioned.

[(A) Composition of colorant]

In the coloring agent (A) of the coloring composition of the present invention, the use ratio of the coloring agent (a1) is preferably from 10 to 90% by mass based on the total mass of the coloring agent (a1) and the coloring agent (a2). Good is 25 to 80% by mass, and particularly preferably 40 to 70% by mass.

The coloring agent (a2) may be selected from the group consisting of the above pyridone azo compound, dibenzopyran type compound, azomethine type compound, quinophthalone type compound, coumarin type compound, and pyrazolone type. a compound, a compound having a structure represented by the above formula (M1), a compound having a structure represented by the above formula (M2), and at least one compound selected from the group consisting of CI basic yellow 11, but preferably used only One of them.

In the coloring composition of the present invention, the coloring agent (A) contains a pigment as a further coloring agent in addition to the coloring agent (a1) and the coloring agent (a2), and is used as a ratio of the pigment to the coloring ratio of (A). The total mass of the agent is preferably 50% by mass or less, more preferably 30% by mass or less, particularly preferably 10% by mass or less, and most preferably no pigment is used.

<(B) Adhesive Resin>

The (B) binder resin contained in the colored composition of the present invention is not particularly limited, but is preferably a resin having an acidic functional group. The acidic functional group may, for example, be a carboxyl group or a phenolic hydroxyl group, and is preferably a carboxyl group.

The (B) binder resin in the present invention is particularly preferably: (b1) an ethylenically unsaturated monomer having a carboxyl group (hereinafter referred to as "unsaturated monomer (b1)") and (b2) a copolymer of another ethylenically unsaturated monomer copolymerizable with the unsaturated monomer (b1) (hereinafter referred to as "unsaturated monomer (b2)"), or a polymerizable unsaturated bond and a carboxyl group Polymer.

Examples of the unsaturated monomer (b1) include (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2-(methyl) propylene methoxyethyl ester], and ω-carboxyl polymerization. As the caprolactone mono(meth)acrylate, p-vinylbenzoic acid or the like, at least one selected from the group consisting of them can be used.

Examples of the unsaturated monomer (b2) include an N-position-substituted maleimide, an aromatic vinyl compound, a (meth) acrylate, and a vinyl ether, and have a single terminal at the polymer molecular chain. A (methyl) acrylonitrile-based macromonomer or the like. Specific examples of the above-mentioned N-position substituted maleimine include, for example, N-phenylmaleimide, N-cyclohexylmaleimide, and the like; as the above aromatic vinyl compound For example, styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, decene, etc.; as the above (meth)acrylic acid Examples of the ester include methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and (methyl). ) allyl acrylate, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (methyl) Acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, (a) Acrylic Ester, tricyclo [5.1.02 ^2,6 ]decane-8-yl ester, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, (meth)acrylic acid 4 -Hydroxyphenyl ester, ethylene oxide modified (meth) acrylate of p-cumylphenol, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[(meth)acryloxymethyl]oxetane, 3-[(meth)acryloxymethyl]-3-ethyloxetane, etc.; as the above vinyl Examples of the ether include cyclohexyl vinyl ether and Vinyl ether, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxy Heterocyclic butane and the like. Examples of the polymer in the macromonomer having a mono(meth)acryl fluorenyl group at the terminal of the polymer molecular chain include polystyrene, poly(methyl) methacrylate, and poly(methyl). N-butyl acrylate, polyoxyalkylene, and the like.

These unsaturated monomers (b2) can be used individually or in mixture of 2 or more types.

Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include JP-A-7-140654, JP-A-8-259876, and JP-A-10-10. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Copolymers, etc.

The copolymerization ratio of the unsaturated monomer (b1) in the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, A coloring composition excellent in alkali developability and storage stability can be obtained.

The polymerizable unsaturated bond in the polymer having a polymerizable unsaturated bond and a carboxyl group is preferably a side chain of the polymer. Specific examples of such a polymer include, for example, JP-A-H05-19467, JP-A-H06-230212, JP-A-H07-207211, JP-A-H09-325494, and Japan A copolymer or the like disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei.

In the (B) binder resin of the present invention, the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (elution solvent: tetrahydrofuran, hereinafter referred to as "GPC") is preferably 1,000. ~100000, more preferably 3000~50000. In such a manner, heat resistance, film properties, electrical properties, pattern shape, and resolution of the formed colored cured film can be further improved. (B) The ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. The above Mn is a polystyrene-equivalent number average molecular weight measured by GPC.

The (B) binder resin as described above can be produced by a known method. For example, the structure, Mw, Mw/Mn, etc. can be controlled by the method disclosed in Japanese Laid-Open Patent Publication No. 2003-222717, JP-A-2006-259680, and International Publication No. 07/029871. The range is synthesized on the side.

The (B) binder resin in the present invention may be used singly or in combination of two or more.

Content ratio of (B) binder resin in the coloring composition of the present invention The content is preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass, still more preferably 50 to 350 parts by mass, even more preferably 100 to 250 parts by mass, per 100 parts by mass of the (A) colorant. By setting the content ratio of the (B) binder resin to the above range, the storage stability and alkali developability of the obtained coloring element and the chromaticity characteristics of the formed colored cured film can be further improved.

<(C) Polymerizable Compound>

The (C) polymerizable compound contained in the colored composition of the present invention is a compound having two or more polymerizable groups in the molecule. Here, examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group.

As the (C) polymerizable compound in the present invention, a compound having two or more (meth)acryl fluorenyl groups in the molecule or a compound having two or more N-alkoxymethylamino groups in the molecule is preferably used.

Specific examples of the compound having two or more (meth) acrylonitrile groups in the molecule include, for example, a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid. A polyfunctional urethane (meth) acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, a polyfunctional group having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group with an acid anhydride (Meth) acrylate, caprolactone-modified polyfunctional (meth) acrylate, alkylene oxide-modified polyfunctional (meth) acrylate, and the like.

Examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; glycerin, trimethylolpropane, and neopentyl alcohol; new A trivalent or higher aliphatic polyhydroxy compound such as pentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane bis(meth)acrylate, and pentaerythritol tri(meth)acrylic acid. Ester, dipentaerythritol penta (meth) acrylate, glycerin dimethacrylate, and the like. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include acid anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride; and pyromellitic acid II. A tetrabasic acid dianhydride such as an anhydride, biphenyltetracarboxylic dianhydride or benzophenone tetracarboxylic dianhydride.

The compound described in paragraphs [0015] to [0018] of JP-A-11-44955 is exemplified as the above-mentioned caprolactone-modified polyfunctional (meth) acrylate. As the above polyalkylene oxide-modified polyfunctional (meth) acrylate, for example, at least one modified bisphenol A bis(meth)acrylic acid selected from the group consisting of ethylene oxide and propylene oxide may be mentioned. An ester, modified by at least one selected from the group consisting of ethylene oxide and propylene oxide, tris(meth)acrylate isocyanurate, modified from at least one selected from the group consisting of ethylene oxide and propylene oxide a trimethylolpropane tri(meth) acrylate having at least one modified pentaerythritol tri(meth) acrylate selected from the group consisting of ethylene oxide and propylene oxide, selected from the group consisting of At least one modified neopentyltetrakis(meth)acrylate of oxyethane and propylene oxide, and dipentaerythritol modified by at least one selected from the group consisting of ethylene oxide and propylene oxide An alcohol penta (meth) acrylate, at least one modified pentaerythritol hexa(meth) acrylate selected from the group consisting of ethylene oxide and propylene oxide.

On the other hand, examples of the compound having two or more N-alkoxymethylamino groups in the molecule include a compound having a melamine structure, a benzoguanamine structure or a urea structure. Here, the melamine structure means having one or more three The chemical structure of the ring as a basic skeleton, the benzoguanamine structure means having more than one phenyl substitution three The chemical structure of the ring as a basic skeleton is a concept comprising melamine, benzoguanamine and their condensates. Specific examples of the compound having two or more N-alkoxymethylamino groups in the molecule include N, N, N', N', N", N"-hexa(alkoxymethyl). Melamine, N,N,N',N'-tetrakis(alkoxymethyl)benzoguanamine, N,N,N',N'-tetrakis(alkoxymethyl)glycolil, and the like.

In the (C) polymerizable compound of the present invention, a preferred compound group is a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid. Ester-modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate having carboxyl group, N, N, N', N', N ", N"-hexa(alkoxymethyl)melamine and N,N,N',N'-tetrakis(alkoxymethyl)benzoguanamine. The formed colored cured product is excellent in high strength and smooth in surface smoothness, and it is difficult to cause floating impurities and film residue on the substrate of the unexposed portion and the light shielding layer, and the trivalent or higher aliphatic polyhydroxy compound is Among the polyfunctional (meth) acrylates obtained by the reaction of (meth)acrylic acid, trimethylolpropane triacrylate, neopentyl alcohol triacrylate, dipentaerythritol pentaacrylate, and new are particularly preferred. Pentaerythritol hexaacrylate; in a polyfunctional (meth) acrylate having a carboxyl group, particularly preferably obtained by reacting pentaerythritol triacrylate with succinic anhydride A compound and a compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride.

The (C) polymerizable compound in the invention may be used singly or in combination of two or more.

The content ratio of the (C) polymerizable compound in the coloring composition of the present invention is preferably 10 to 1000 parts by mass, more preferably 20 to 700 parts by mass, still more preferably 100% by mass based on 100 parts by mass of the (A) coloring agent. ~500 parts by mass, particularly preferably 200 to 400 parts by mass. By setting the use ratio of the (C) polymerizable compound to the above range, the alkali developability and the curability of the colored composition can be further improved.

<(D) Photopolymerization Initiator>

The coloring composition of the present invention may contain a photopolymerization initiator. The (D) photopolymerization initiator contained in the colored composition of the present invention is an active material which causes polymerization of the (C) polymerizable compound by irradiation of visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like. compound of.

The (D) photopolymerization initiator in the present invention is preferably selected from the group consisting of a biimidazole-based compound, a thioxanthone-based compound, an acetophenone-based compound, and three. At least one of the group of the compound and the O-mercapto lanthanide compound. Examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2. '-Bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-three Chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole;etc.; as the thioxanthone-based compound, for example, thioxanthone or 2-chlorothioxanthone , 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2, 4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, etc.; as the acetophenone-based compound, for example, 2-methyl-1-[4-(methylthio)benzene Base]-2- Olinone propan-1-one, 2-benzyl-2-dimethylamino-1-(4- Oleinophenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Olostinophenyl)butan-1-one and the like. As the above three a compound, preferably a three having a halogenated methyl group The compound may, for example, be 2,4,6-tris(trichloromethyl)-all. 2-methyl-4,6-bis(trichloromethyl)-all three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-all three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-all three 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-all three , 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-all three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-all three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-all three , 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-all three Wait. Examples of the above O-fluorenyl fluorene-based compound include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzamide), 1-[9 -ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethanone 1-(O-acetamidine), 1-[9-ethyl-6-( 2-methyl-4-tetrahydrofuranylmethoxybenzylidene)-9H-indazol-3-yl]-ethanone 1-(O-acetamidine), 1-[9-ethyl-6- {2-Methyl-4-(2,2-dimethyl-1,3-dioxolyl)methoxybenzylidenyl}-9H-indazol-3-yl]-ethanone 1-(O-acetamidine) and the like.

When a biimidazole-based compound is used as the (D) photopolymerization initiator in the present invention, it is preferred to use the biimidazole-based compound and the hydrogen donor in combination from the viewpoint of improving light sensitivity. Here, the "hydrogen donor" is a compound capable of supplying a hydrogen atom to a radical generated by a biimidazole compound by light irradiation. Examples of such a hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzoene. A thiol-based hydrogen donor such as azole; and an amine-based hydrogen donor such as 4,4'-bis(dimethylamino)benzophenone or 4,4'-bis(diethylamino)benzophenone. These hydrogen donors may be used singly or in combination of two or more kinds. However, at least one thiol-based hydrogen donor and at least one amine-based hydrogen donor are preferably used in combination from the viewpoint of greatly improving high sensitivity.

On the other hand, as the (D) photopolymerization initiator in the present invention, a photopolymerization initiator other than the biimidazole-based compound is preferably used, and a thioxanthone-based compound, an acetophenone-based compound, and the like are preferably used. When at least one of the group of the compound and the O-mercapto fluorene compound is used, these photopolymerization initiators can be used together with the sensitizer. Examples of such a sensitizer include 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone, and 4-diethylamine. Acetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis(4-diethyl) Aminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethylamino)chalcone, etc. At least one selected from the group consisting of is used.

The content ratio of the (D) photopolymerization initiator in the colored composition of the present invention is preferably 0.01 to 120 parts by mass, more preferably 1 to 100 parts by mass, per 100 parts by mass of the (C) polymerizable compound. By setting the content ratio of the (D) photopolymerization initiator to the above range, the coloring composition can be made more excellent in curability, which is preferable.

When a biimidazole compound is used as the (D) photopolymerization initiator, and the biimidazole compound is used in combination with a hydrogen donor, it is used as the hydrogen donor. The ratio is preferably 40 parts by mass or less, more preferably 0.01 to 40 parts by mass, still more preferably 1 to 30 parts by mass, even more preferably 2 to 20 parts by mass, per 100 parts by mass of the (C) polymerizable compound.

<Other additives>

The coloring composition of the present invention contains the (A) coloring agent, the (B) binder resin, and the (C) polymerizable compound as described above, and is preferably a liquid composition prepared by mixing these components in a solvent to be described later. . However, in addition to these components, the coloring composition of the present invention may be blended with other additives.

Examples of such other additives include a filler, a polymer compound, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomeration agent, a residue improving agent, and a developability improving agent. Specific examples of the filler include, for example, glass and alumina, and examples of the polymer compound include polyvinyl alcohol and poly(fluoroalkyl acrylate); Examples of the agent include a fluorine-based surfactant and a lanthanoid surfactant; and examples of the adhesion promoter include vinyl trimethoxy decane, vinyl triethoxy decane, and vinyl tris(2). -methoxyethoxy)decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-amino Propyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2- (3,4-Epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyl Trimethoxy decane, 3-methacryloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, etc.; as the above antioxidant, for example, 2,2-thiobis (4- Methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, etc.; as the ultraviolet absorber, for example, 2-(3-tris-butyl-5-methyl-2) - hydroxyphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, etc., as the anti-agglomeration agent, for example, sodium polyacrylate, etc., and the residue improvement agent is, for example, C Diacid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3 -Amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, etc.; as the developability improver, for example, succinic acid mono 2-(meth)acryloxyethyl ester], phthalic acid mono [2-(methyl) propylene methoxyethyl ester], ω-carboxy polycaprolactone mono (meth) acrylate, and the like.

<solvent>

The coloring composition of the present invention is preferably prepared by mixing (A) a colorant, (B) a binder resin, and (C) a polymerizable compound as described above in a solvent, and optionally using (D) photopolymerization. A liquid composition of an initiator and other additives.

The solvent used in the coloring composition of the present invention is preferably selected from the group consisting of the components (A) to (C) and optionally used (D) photopolymerization initiators, other additives. Dissolved or dispersed, and does not react with these ingredients, with moderate volatility.

As such a solvent, for example, (poly)alkylene glycol Monoalkyl ethers, other ethers, alkyl lactates, (cyclo)alkyl alcohols, keto alcohols, (poly)alkylene glycol monoalkyl ether acetates, ketones, diacetates Further, at least one selected from the group consisting of alkoxycarboxylates, other esters, aromatic hydrocarbons, guanamines, and decylamines can be used. Specific examples of the (poly)alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, and ethylene glycol. N-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol single Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol Monomethyl ether, tripropylene glycol monoethyl ether, etc.; examples of the other ethers include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, and the like; Examples of the alkyl lactate include methyl lactate and ethyl lactate; and examples of the (cyclo)alkyl alcohols include methanol, ethanol, propanol, butanol, isopropanol, and isobutanol. , tertiary butanol, octanol, 2-ethylhexanol, cyclohexanol, etc.; as the above ketone alcohols, for example, dipropylene Examples of the (poly)alkylene glycol monoalkyl ether acetates include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and diethylene glycol monomethyl ether. Acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3 -methyl-3-methoxybutyl Examples of the ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; and examples of the diacetate include propylene glycol diethyl hydride. An acid ester, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate or the like; and examples of the alkoxycarboxylic acid esters include 3-methoxypropionic acid Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl Examples of the other esters include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, and isoamyl acetate. n-Butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate Ethyl acetate, ethyl 2-oxobutyrate, etc., and examples of the aromatic hydrocarbons include toluene and xylene; and examples of the guanamines include N,N-dimethyl Carbenamide, N,N-dimethylacetamide, etc.; Amides within the above-mentioned, for example, include N- methylpyrrolidinone and the like.

Among these solvents, from the viewpoint of ensuring good solubility, coatability, and the like, it is preferred to use a solvent selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether. Acid ester, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethyl Diol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butanediol diacetate, 1,6-hexanediol Acetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl Propionate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate and pyruvate At least one of the groups of esters.

The ratio of use of the solvent in the colored composition of the present invention is not particularly limited, and the solid content concentration of the colored composition (in the colored composition) is from the viewpoint of ensuring good dispersibility, stability, and coatability of the colored composition. The ratio of the total concentration of the components other than the solvent to the total amount of the colored composition is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass.

<Method for Preparing Colored Composition>

The colored composition of the present invention can be produced by an appropriate method. For example, the method disclosed in JP-A-2008-58642, JP-A-2010-132874, and the like can be mentioned.

Specifically, for example, a method of preparing a solution containing (A) a colorant, and the components of (B) to (C) and optionally using (D) a photopolymerization initiator, other components, are prepared in advance. mixing. The previously prepared coupler solution and the mixed composition can be separately used after being filtered using a filter having an appropriate pore diameter.

<Method of Forming Colored Cured Film>

Coloring can be formed using the colored composition of the present invention as described above Hardened film. The colored cured film of the present invention is a concept including a pixel of each color used in a display element and a solid-state image sensor, a black matrix, a black spacer, and the like.

When forming a colored cured film using the colored composition of the present invention, it is preferred to use any of the following methods.

The first method is to apply the colored composition of the present invention on a substrate to form a coating film, and then irradiate at least a part of the coating film to develop light, preferably further heating (post-baking); the second method It is preferable to apply a coloring composition of the present invention to a pattern on a substrate to form a coating film by an inkjet method, and to illuminate the coating film arbitrarily, preferably by further heating (post-baking).

In any of the above methods, a color-developing film which is a pixel of each color is sequentially formed by using three colors of red, green, and blue or coloring compositions of cyan, magenta, and yellow, and a color filter can be formed; A black colored cured film can be formed by using a black colored composition to form a black matrix or a black spacer.

Examples of the substrate include a substrate made of glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidimide, polyimine or the like. If necessary, appropriate pretreatment such as a reagent (for example, a decane coupling agent) treatment, a plasma treatment, an ion plating treatment, a sputtering treatment, a treatment by a gas phase reaction method, a treatment by a vacuum vapor deposition method, or the like may be performed on these substrates. .

Preferably, a black matrix is formed on the substrate used in the coloring composition of the present invention in order to form a pixel of the color filter. Sub-pixel area. The black matrix may be a film of a metal (for example, chromium or the like) having a desired pattern, a colored cured film formed of a colored composition, or the like. The patterned metal thin film can be formed, for example, by applying photolithography to a metal thin film formed on a substrate by a sputtering method, a vapor deposition method, or the like. The patterned colored cured film formed of the colored composition can be formed by the same method as the present invention using a black colored composition. In the second method using the inkjet method, in addition to the light-shielding function, the black matrix functions as a barrier for preventing color mixing of the respective color components ejected by the inkjet method. Therefore, the black matrix at this time preferably has a film thickness of a certain thickness or more. Therefore, the black matrix at this time is preferably a black cured film formed using a black colored composition.

As the substrate used in the formation of the black matrix of the coloring composition of the present invention, a substrate in which a black matrix in which pixel regions are divided is preferably formed.

Further, the substrate used in the formation of the black spacer in the coloring composition of the present invention is preferably a substrate on which both a black matrix and a pixel which divide the pixel region are formed.

In the first method, examples of the method of applying the colored composition on the substrate include a spray method, a roll coating method, a spin coating method (spin coating method), and a slit die coating method (slit coating method). , bar coating method, etc. Among them, a spin coating method or a slit die coating method is preferred.

After coating by the above-described method or the inkjet method, in order to form a coating film, a method of removing the solvent by heating (prebaking) the colored composition after coating is preferably used. The prebaking conditions are preferably carried out at 70 to 110 ° C under reduced pressure for about 1 to 10 minutes. As the degree of vacuum, It is preferable to set so that the arrival pressure (absolute pressure) becomes 50 to 200 Pa.

The thickness of the coating film is preferably from 0.6 to 12 μm, more preferably from 1.2 to 10 μm, as the thickness after solvent removal.

Examples of the light source used for light irradiation of the formed coating film include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, and a low pressure mercury lamp. Such as light source, or argon ion laser, YAG laser, XeCl excimer laser, nitrogen laser, ultraviolet LED and so on. As the light to be irradiated, light having a bright line in the range of 190 to 450 nm is preferable. The amount of light irradiation is preferably from 10 to 10,000 J/m ² , more preferably from 50 to 5,000 J/m ² .

The above development is carried out using an alkali developer. The unexposed portion in the coating film is removed by development treatment to form a pattern-like coating film. As the alkali developing solution, for example, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-diazabicyclo-[5.4.0] is preferably used. An aqueous solution of -7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene or the like. In the aqueous solution, a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added in an appropriate range as needed.

As the developing method, for example, a shower developing method, a spray developing method, a dipping (impregnation) developing method, a spin coating immersion (water puddle) developing method, or the like can be used. The development conditions are preferably 5 to 300 seconds at normal temperature. The developed coating film is preferably washed with water.

The post-baking described above can be carried out, for example, at a temperature of 180 to 280 ° C for, for example, 10 to 60 minutes.

The film thickness of the colored cured film formed as described above is as follows according to the use thereof.

Pixel: preferably 0.5 to 5 μm, more preferably 1 to 3 μm

Black matrix: preferably 0.5 to 10 μm, more preferably 0.8 to 5 μm

Black spacer: preferably 0.5 to 10 μm, more preferably 1 to 7 μm

The pixel pattern obtained by forming the pixels of the respective colors as described above is formed thereon as a protective film, and then a transparent conductive film and a spacer are sequentially formed, whereby the color filter can be used as a display element.

<display element>

The display element in the present invention includes a colored cured film selected from at least one selected from the group consisting of a pixel formed as described above and a color filter, a black matrix, and a black spacer. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.

As the color liquid crystal display element, a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, an IPS (In-Planes Switching) type, and a VA (Vertical Orientation) can be applied. A well-known liquid crystal mode such as a Vertical Alignment type or an OCB (Optically Compensated Birefringence) type.

The above color liquid crystal display element may be of a transmissive type or a reflective type, and may have a liquid crystal cell of a suitable structure. The configuration of the liquid crystal cell is, for example, a configuration in which a driving substrate on which a thin film transistor (TFT) is disposed and a counter substrate on which a color filter is formed are used as a pair, and a liquid crystal layer is sandwiched between the pair of substrates; a substrate having both a thin film transistor (TFT) and a color filter A substrate in which an ITO (tin-doped indium oxide) electrode is formed is used as a pair, and a structure of a liquid crystal layer is sandwiched between the pair of substrates.

The color liquid crystal display device further includes a backlight unit in addition to the liquid crystal cell. Examples of the light source in the backlight unit include a cold cathode fluorescent tube, a white LED, and the like.

The organic EL display element can have a suitable structure, and for example, a structure disclosed in Japanese Laid-Open Patent Publication No. Hei 11-307242 can be used.

The electronic paper may have a suitable structure, and for example, a structure disclosed in Japanese Laid-Open Patent Publication No. 2007-41169 may be employed.

[Examples]

Hereinafter, embodiments of the present invention will be further specifically described by way of examples. However, the invention is not limited to the following examples.

<(B) Synthesis of binder resin>

Synthesis Example 1

100 parts by mass of propylene glycol monomethyl ether acetate was placed in a flask equipped with a cooling tube and a stirrer, and nitrogen substitution was performed. After heating to 80 ° C, 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, and 5 parts by mass of benzyl methacrylate were added dropwise at this temperature for 1 hour. Parts, 15 parts by mass of 2-hydroxyethyl methacrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, and mono(2-propenyloxy) succinate A mixed solution of 15 parts by mass of ethyl ester and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was maintained at a temperature of 80 ° C, and polymerization was carried out for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and polymerization was further carried out for 1 hour to obtain a solution containing 33% by mass of the binder resin (B1). The Mw of the binder resin (B1) is 12200, Mn is 6500.

<Preparation and evaluation of coloring composition>

Example 1

(1) Preparation of coloring composition

A coloring composition having a solid concentration of 20% by mass is prepared by mixing the following materials, and (A) a coloring agent: 5% by mass of the following formula (C1-1-1) as a coloring agent (a1) 23.4 parts by mass of a cyclohexanone solution of the compound and 16.6 parts by mass of a cyclohexanone solution containing 5% by mass of a compound represented by the above formula (P1-1) as a coloring agent (a2), as (B) a binder resin: 26.3 parts by mass of a solution (solid content concentration: 33% by mass) containing the binder resin (B1) obtained in the above Synthesis Example 1, as (C) polymerizable compound: M-402 (trade name, manufactured by Toago Seisakusho Co., Ltd.) a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 9.9 parts by mass as (D) photopolymerization initiator: 2-benzyl-2-dimethylamino-1-(4) - 1.8 parts by mass of phenyl phenyl) butan-1-one (trade name "IRGACURE 369", manufactured by BASF Corporation), as a fluorine-based surfactant: Megafac F-554 (trade name, manufactured by DIC) 0.05 mass And as a solvent: propylene glycol monomethyl ether acetate.

(2) Evaluation of chromaticity characteristics

The colored composition prepared above was applied onto a glass substrate by a spin coater, and then prebaked on a hot plate at 80 ° C for 10 minutes to form a coating film. The same operation was carried out by changing the rotation speed of the spin coater to form three coating films having different film thicknesses.

After the coating film formed as described above was allowed to cool to room temperature, light including bright lines of wavelengths of 365 nm, 405 nm, and 436 nm was irradiated to the entire surface of each of the coating films at an irradiation amount of 2000 J/cm ² without interposing the mask. To each of the substrates after the irradiation, an alkali developing solution composed of a 0.04 mass% potassium hydroxide solution at 23 ° C was used, and a shower development was performed for 90 seconds under the conditions of a nozzle diameter of 1 mm and a developing pressure of 1 kg/cm ² . Next, each of the developed substrates was washed with ultrapure water, air-dried, and post-baked in a clean oven at 200 ° C for 30 minutes to form three red cured films.

For the three cured films, a color analyzer (Model: "MCPD2000" manufactured by Otsuka Electronics Co., Ltd.) was used to measure the chromaticity coordinate value (x, y) and the stimulus in the CIE color system using a C light source and a 2 degree field of view. Value (Y). From the obtained measurement results, the chromaticity coordinate value (y) and the stimulation value (Y) at the chromaticity coordinate value x=0.661 were obtained. These values are shown in Table 1. The larger the value of the stimulation value (Y), the higher the brightness.

(3) Foreign body evaluation

The colored composition (S-1) which was allowed to stand at 5 ° C for 3 days was applied to a 10 cm × 10 cm soda glass substrate having a SiO ₂ film on the surface of which sodium ions were eluted by using a slit die coater, and then 90. The hot plate at °C was prebaked for 4 minutes to form a coating film having a film thickness of 2.5 μm after prebaking. When the obtained substrate was observed with an optical microscope, it was evaluated as "○" when no foreign matter was observed on the coating film, and "△" was evaluated if the number of foreign matter on the coating film was one to ten. When the number of foreign matter generation on the coating film was 11 or more, it was evaluated as "X". The evaluation results are shown in Table 1.

Examples 2 to 19 and Comparative Examples 1 to 11

In the "(1) Preparation of colored composition" of the above-mentioned Example 1, a cyclohexanone solution containing 5 mass% of the dye of the type shown in Table 1 was mixed and used in the amount (parts by mass) shown in Table 1, respectively. In the same manner as in Example 1, a colored composition was prepared and evaluated (the total amount of the coloring agent solution used and the total amount of the coloring agent contained in the solution were fixed to 40 parts by mass and 2 parts by mass, respectively).

The evaluation results are shown in Table 1.

The abbreviations of the coloring agents in the coloring agent column of Table 1 have the following meanings.

<Colorant (a1)>

C1-1-1: a compound represented by the following formula (C1-1-1)

C1-2-1: a compound represented by the following formula (C1-2-1) (C.I. Basic Red 12)

C1-3-1: a compound represented by the following formula (C1-3-1)

C2-1-1: a compound represented by the following formula (C2-1-1)

C2-2-1: a compound represented by the following formula (C2-2-1)

SO-107: C.I. Solvent Orange 107

<Colorant (a2)>

P1-1: a compound represented by the above formula (P1-1) (pyridone azo compound)

P1-2: a compound represented by the above formula (P1-2) (pyridone azo compound)

A-1: a compound represented by the above formula (A-1) (azomethine compound)

A-2: a compound represented by the above formula (A-2) (azomethine compound)

A-3: a compound represented by the above formula (A-3) (azomethine compound)

Q1: a compound represented by the following formula (Q1) (C.I. Solvent Yellow 114)

M1-1: a compound represented by the above formula (M1-1) (C.I. Solvent Yellow 179)

M2: a compound represented by the following formula (M2-1)

M3: a compound represented by the above formula (M3) (C.I. Basic Yellow 11)

X-1-1: a compound represented by the following formula (X-1-1) (dibenzopyran-based compound)

X-1-2: a compound represented by the following formula (X-1-2) (dibenzopyran-based compound)

X-2-1: a compound represented by the following formula (X-2-1) (dibenzopyranyl compound)

Cou-1: a compound represented by the following formula (Cou-1) (coumarin compound described in Example 4 of JP-A-4-179955)

Cou-2: a compound represented by the following formula (Cou-2) (C.I. Disperse yellow 82, coumarin compound)

Pzo-1: a compound represented by the above formula (Pzo-1) (pyrazolone compound)

<Other colorants>

R-1: a compound represented by the following formula (R-1) (C.I. Acid Yellow 19, azo compound)

R-2: a compound represented by the following formula (R-2)

R-3: a compound represented by the following formula (R-3) (C.I. Acid Orange 56, azo compound)

Y150: C.I. Pigment Yellow 150

Claims (11)

A coloring composition comprising (A) a coloring agent, (B) a binder resin, and (C) a coloring composition of a polymerizable compound, wherein the (A) coloring agent comprises: (a1) a cyanine system The compound and (a2) are selected from the group consisting of pyridinone azo compounds, dibenzopipelan compounds, azomethine compounds, quinophthalone compounds, coumarin compounds, pyrazolone compounds, a compound having a structure represented by the following formula (M1), a compound having a structure represented by the following formula (M2), and at least one compound selected from the group consisting of CI basic yellow 11 In the formula (M1), R ^M1 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and R ^M2 represents an alkanediyl group having 1 to 8 carbon atoms. R ^M3 and R ^M4 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms. In the formula (M2), R ^M5 represents a cyano group, an aminomethyl fluorenyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylaminocarbonyl group or a benzimidazolyl group, and R ^M6 represents a hydrogen atom, an alkylcarbonyl group or a trioxane. The benzyl group, R ^M7 and R ^M8 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and R ^M7 and R ^M8 may be bonded to each other to form a nitrogen-containing hetero ring. The coloring composition of claim 1, wherein the pyridone azo compound is a compound represented by the following formula (P), and the dibenzopyran-based compound has a structure represented by the following formula (X) The azomethine-based compound is a compound having a structure represented by the following formula (A), and the quinacridone-based compound is a compound having a structure represented by the following formula (Q), and the coumarin The priming compound is a compound having a structure represented by the following formula (Cou), and the pyrazolone compound is a compound having a structure represented by the following formula (Pzo). In the formula (P), Z represents a substituted or unsubstituted aromatic hydrocarbon group, and R ^P1 represents a hydrogen atom, a cyano group, an aminomethyl fluorenyl group, an N-substituted aminomethyl fluorenyl group, a hydrocarbon group, and a carbon number of 3 to 20 a heterocyclic group, an alkoxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 30 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, or a fluorenyl group having 2 to 20 carbon atoms An aliphatic sulfonyl group having 1 to 30 carbon atoms or an arylsulfonyl group having 6 to 30 carbon atoms, and R ^P2 represents a hydrogen atom, a cyano group, an aminomethyl fluorenyl group, and an N-substituted amino formazan group. a group, a sulfonamide group, a sulfo group, an amine group, or a hydrocarbon group, and R ^P3 represents a hydrogen atom, a carboxyl group, a trifluoromethyl group, or a hydrocarbon group having 1 to 10 carbon atoms; In the formula (X), R ^X1 to R ^X4 each independently represent a hydrogen atom, R ⁰¹ or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms, and R ^X5 and R ^X6 each independently represent a hydrogen atom or An alkyl group having 1 to 8 carbon atoms, and R ^X7 represents -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁰¹ , -SO ₃ R ⁰¹ , -SO ₂ NHR ⁰² -SO ₂ NR ⁰² R ⁰³ or a group having a polymerizable unsaturated group, r represents an integer of 0 to 5, and when r is an integer of 2 or more, a plurality of R ^{X7 are the} same or different, and R ⁰¹ represents or a saturated hydrocarbon group having 1 to 10 carbon atoms which does not have a linking group, or a halogenated saturated hydrocarbon group having 1 to 10 carbon atoms with or without a linking group, the linking group containing a carbon atom, a hydrogen atom or a halogen atom Other than the atom, R ⁰² and R ⁰³ each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted carbon. An aromatic hydrocarbon group having 6 to 10 atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 10 carbon atoms, and R ⁰² and R ⁰³ may be bonded to each other to form a substituted or unsubstituted carbon atom number 1~ a heterocyclic group of 10, M represents a sodium atom or a potassium atom, In the formula (A), R ^A1 to R ^A4 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R ^A5 represents a hydrogen atom or has 1 to 8 carbon atoms with or without a linking group. An aliphatic hydrocarbon group having an atom other than a carbon atom, a hydrogen atom or a halogen atom, In the formula (Q), R ^Q1 represents a halogen atom, an alkoxy group, a substituted or unsubstituted phenoxy group, a thioalkoxy group, a substituted or unsubstituted thiophenoxy group, or a substituted or unsubstituted carbon atom. a hydrocarbon group of 1 to 20, R ^Q2 represents a halogen atom, an alkoxy group, a thioalkoxy group, a substituted or unsubstituted amino group, a mercapto group, a mercaptoamine group, an alkoxy alkoxy group, an alkoxycarbonyl group a phenoxycarbonyl group, an aminomethyl fluorenyl group, an N-substituted aminomethyl fluorenyl group, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, p represents an integer of 0 to 3, and p is an integer of 2 or more , the same or different and a plurality of R ^Q1, q represents an integer of 0 to 4, q is an integer of 2 or more, same or different, a plurality of R ^Q2, In the formula (Cou), R ^u1 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and R ^u2 and R ^u3 each independently represent a halogen atom, an alkoxy group, a substituted or unsubstituted amino group, Or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, s represents an integer of 0 to 3, and when s is an integer of 2 or more, a plurality of R ^{u2 are the} same or different, t represents an integer of 0 to 4, and t is 2 When the above integer is used, multiple R ^{u3 are the} same or different, In the formula (Pzo), R ^Z1 and R ^Z3 each independently represent an alkyl group or an aryl group, and R ^Z2 represents an alkyl group. The coloring composition of claim 2, wherein the compound represented by the formula (P) is a compound represented by the following formula (P1), In the formula (P1), R ^P4 represents an aliphatic hydrocarbon group having 1 to 16 carbon atoms, and R ^P5 and R ^P6 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms. The colored composition of claim 1 or 2, wherein the (a1) cyanine compound is at least 1 selected from the group consisting of a compound having a structure represented by the following formula (C) and a CI solvent orange 107. Kind, In the formula (C), R ¹ to R ³ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group, and the Z ^1A ring and the Z ^2A ring each independently represent a substituted or unsubstituted aromatic hydrocarbon ring. Q ¹ and Q ² each independently represent -O-, -S- or -CR ¹³ R ¹⁴ -, and R ¹¹ to R ¹⁴ each independently represent a substituted or unsubstituted hydrocarbon group. The colored composition of claim 1 or 2, wherein the (a1) cyanine compound is selected from the group consisting of a compound having a structure represented by each of the following formulas (C1) and (C2) and a CI solvent orange 107 group. At least one of the groups, In the formula (C1), R ^C1 to R ^C6 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms, and in the formula (C2), R ^C7 to R ^C10 each independently represent a hydrogen atom or a carbon atom. 1 to 8 of an aliphatic hydrocarbon group, and R ^C11 represents a hydrogen atom, a halogen atom, or a halogen hydrocarbon group having 1 to 8 carbon atoms. The colored composition of claim 1 or 2, wherein the use ratio of the pigment is 10% by mass or less based on the total mass of the (A) colorant. The colored composition of claim 4, wherein the use ratio of the pigment is 10% by mass or less based on the total mass of the (A) colorant. A colored composition as claimed in claim 1 or 2 for forming a red cured film. The colored composition of claim 8, wherein the red cured film is a red pixel. A colored cured film comprising: (a1) a cyanine compound, and (a2) selected from the group consisting of a pyridone azo compound, a dibenzopyran compound, an azomethine compound, and quinine An anthrone-based compound, a coumarin-based compound, a pyrazolone-based compound, a compound having a structure represented by the following formula (M1), a compound having a structure represented by the following formula (M2), and a CI basic yellow compound At least one compound in the group of 11, In the formula (M1), R ^M1 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and R ^M2 represents an alkanediyl group having 1 to 8 carbon atoms, and R ^M3 and R ^M4 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having a carbon number of 1 to 8, In the formula (M2), R ^M5 represents a cyano group, an aminomethyl fluorenyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylaminocarbonyl group or a benzimidazolyl group, and R ^M6 represents a hydrogen atom, an alkylcarbonyl group or a trioxane. The benzyl group, R ^M7 and R ^M8 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and R ^M7 and R ^M8 may be bonded to each other to form a nitrogen-containing hetero ring. A display element characterized by having a colored cured film as claimed in claim 10.