TWI676657B - Coloring composition, coloring cured film, and display element - Google Patents

Abstract

The present invention provides a coloring composition containing a cyanine dye as a colorant and having good storage stability.

It contains (A) a colorant, (B) a binder resin, and (C) a polymerizable compound, and (A) a colorant contains a compound having a structure represented by the following formula (1) and a compound having the following formula (2) The content of the compound having a structure represented by the following formula (2) is 0.001 based on the total content of the compound having the structure represented by the following formula (1) and the compound having the structure represented by the following formula (2). Above mass%.

[式(1)、(2)中，環Z¹、環Z²、環Z³和環Z⁴相互獨立地表示經取代或未經取代的雜環，R¹~R⁶相互獨立地表示氫原子、鹵素原子、或者經取代或未經取代的烴基。其中，R¹、R²、R⁴和R⁵存在多個時，可以相同也可以不同。p表示1或2，p為1時q表示2以上的整數，p為2時q表示3以上的整數]。

[In formulae (1) and (2), ring Z ¹ , ring Z ² , ring Z ³ and ring Z ⁴ each independently represent a substituted or unsubstituted heterocyclic ring, and R ¹ to R ⁶ each independently represent hydrogen Atom, halogen atom, or substituted or unsubstituted hydrocarbon group. However, when there are multiple R ¹ , R ² , R ⁴ and R ⁵ , they may be the same or different. p is 1 or 2, q is an integer of 2 or more when p is 1, and q is an integer of 3 or more when p is 2].

Description

Colored composition, colored cured film and display element

The present invention relates to a coloring composition, a coloring cured film, and a display element, and more specifically, to a color liquid crystal display element, a solid-state imaging element, an organic EL display element, an electronic paper, and the like for forming a transmissive or reflective type. A coloring composition for a coloring cured film used in the present invention, a coloring cured film formed using the coloring composition, and a display element including the coloring cured film.

When manufacturing a color filter using a colored radiation-sensitive composition, it is known to apply a pigment-dispersed colored radiation-sensitive composition to a substrate and dry it, and then irradiate the dried coating film with radiation to have a desired pattern shape ( Hereinafter, it is referred to as "exposure"), and a method of obtaining pixels of each color by performing development (for example, refer to Patent Documents 1 to 2). A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed is also known (for example, refer to Patent Document 3). A method of obtaining pixels of each color by an inkjet method using a pigment-dispersed colored resin composition is also known (for example, refer to Patent Document 4).

For a coloring composition for forming a coloring cured film, the use of a dye as a colorant has been studied for the purpose of forming a coloring cured film with higher brightness. For example, Patent Document 5 reports that a coating film having excellent brightness is obtained by using a cyanine dye as a colorant.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2-144502

[Patent Document 2] Japanese Unexamined Patent Publication No. 3-52201

[Patent Document 3] Japanese Unexamined Patent Publication No. 6-35188

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

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

However, according to the study by the present inventors, it is known that the storage stability of the colored composition may be insufficient for a colored composition containing a cyanine dye as a colorant.

Therefore, an object of the present invention is to provide a coloring composition containing a cyanine dye as a colorant, which is excellent in storage stability, and capable of forming a coloring cured film with high brightness. Another object of the present invention is to provide a colored cured film formed using the colored composition and a display element including the colored cured film.

The present inventors have conducted intensive studies, and as a result, found that the above-mentioned problems can be solved by using at least two kinds of cyanine compounds as colorants and controlling their content ratios.

That is, the present invention provides a coloring composition which is a coloring composition containing (A) a coloring agent, (B) a binder resin, and (C) a polymerizable compound, and (A) the coloring agent containing the following formula (1) A compound having a structure represented by the formula and a compound having a structure represented by the following formula (2) have the following formula (2) The content of the compound having the structure represented is 0.001% by mass or more with respect to the total content of the compound having the structure represented by the following formula (1) and the compound having the structure represented by the following formula (2).

The present invention also provides a coloring agent containing a compound having a structure represented by the following formula (1) and a compound having a structure represented by the following formula (2), and a compound having a structure represented by the following formula (2) The content is 0.001% by mass or more based on the total content of the compound having a structure represented by the following formula (1) and the compound having a structure represented by the following formula (2).

[In formula (1), ring Z ¹ and ring Z ² independently represent a substituted or unsubstituted heterocyclic ring.

p represents 1 or 2. When p is 2, a plurality of R ¹ and R ² may be the same or different.

R ¹ to R ³ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group. ]

[In formula (2), ring Z ³ and ring Z ⁴ independently represent a substituted or unsubstituted heterocyclic ring.

When p is 1, q represents an integer of 2 or more, and when p is 2, q represents an integer of 3 or more.

R ⁴ to R ⁶ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group. Among them, a plurality of R ⁴ and R ⁵ may be the same or different. ]

The present invention also provides a colored cured film formed using the colored composition and a display element including the colored cured film. Here, the "colored cured film" refers to pixels of each color, a black matrix, a black spacer, and the like used in a display element and a solid-state imaging element.

The coloring composition of the present invention has good storage stability. In addition, by using the coloring composition of the present invention, a coloring cured film with high brightness can be formed.

Therefore, the coloring composition of the present invention is extremely suitable for producing display elements such as color liquid crystal display elements, organic EL display elements, electronic paper, and solid-state imaging elements such as CMOS image sensors.

[Form of Implementing Invention]

Hereinafter, the present invention will be described in detail.

Coloring composition

Hereinafter, the constituent components of the coloring composition of the present invention will be described in detail.

-(A) Colorant-

The colored composition of the present invention contains a compound having a structure represented by the following formula (1) (hereinafter, also referred to as "compound (1)") and a compound having the following formula A compound having a structure represented by (2) (hereinafter, also referred to as "compound (2)") is used as (A) a colorant.

[In formula (1), ring Z ¹ and ring Z ² independently represent a substituted or unsubstituted heterocyclic ring.

p represents 1 or 2. When p is 2, a plurality of R ¹ and R ² may be the same or different.

R ¹ to R ³ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group. ]

[In formula (2), ring Z ³ and ring Z ⁴ independently represent a substituted or unsubstituted heterocyclic ring.

When p is 1, q represents an integer of 2 or more, and when p is 2, q represents an integer of 3 or more.

R ⁴ to R ⁶ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group. A plurality of R ⁴ and R ⁵ may be the same or different. ]

啉環、硫代

啉環、哌啶環、哌

環、高哌

環、四氫嘧啶環等含氮脂環式雜環；吡啶環、吡

環、嘧啶環、嗒

環、喹啉環、異喹啉環、酞

環、喹

啉環、咪唑環、吡唑環、三唑環、四唑環、噻唑環、苯并噻唑環、

唑環、吲哚環、吲唑環、苯并咪唑環、苯并

唑、鄰苯二甲醯亞胺環等含氮芳香族雜環；噻吩環、呋喃環、嘌呤環等其它的芳香族雜環。其中，較佳為含氮芳香族雜環，更佳為吲哚環、苯并

唑環、苯并噻唑環，進一步更佳為吲哚環。 The heterocyclic ring in ring Z ¹ to ring Z ⁴ may be a monocyclic heterocyclic ring or a polycyclic heterocyclic ring. The heterocyclic ring may be an unsaturated ring or a saturated ring, and the ring may have two or more heteroatoms (for example, a nitrogen atom, an oxygen atom, and a sulfur atom) of the same or different kinds. Examples include a pyrrolidine ring, a pyrazoline ring,

Porphyrin ring, thio

Porphyrin ring, piperidine ring, piperidine

Ring, homopipe

Ring, tetrahydropyrimidine ring and other nitrogen-containing alicyclic heterocyclic rings; pyridine ring, pyridine

Ring, pyrimidine ring, da

Ring, quinoline ring, isoquinoline ring, phthalate

Ring, quine

Phthaloline ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, benzothiazole ring,

Azole ring, indole ring, indazole ring, benzimidazole ring, benzo

Nitrogen-containing aromatic heterocyclic rings such as azole, phthalimide ring, and other aromatic heterocyclic rings such as thiophene ring, furan ring, and purine ring. Among them, preferred are nitrogen-containing aromatic heterocycles, more preferred are indole rings and benzo

An azole ring and a benzothiazole ring are further more preferably an indole ring.

p represents 1 or 2, and p is preferably 1.

When p is 1, q represents an integer of 2 or more, but 2 or 3 is preferable, and 2 is more preferable. When p is 2, q represents an integer of 3 or more, but is preferably 3.

As a combination of p and q, p is preferably 1 and q is 2 or more, more preferably p is 1 and q is 2.

Examples of the halogen atom in R ¹ to R ⁶ include a fluorine atom, a chlorine atom, and a bromine atom.

Examples of the hydrocarbon group in R ¹ to R ⁶ 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 1 to 30, more preferably 1 to 24, and particularly preferably 1 to 20. These aliphatic hydrocarbon groups may be linear or branched. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, hexyl, heptyl, and octyl. Base, nonyl, decyl, undecyl, 1-methyldecyl, dodecyl, 1-methyldodecyl, 1-ethyldecyl, tridecyl, tetradecyl , Dodecyl, pentadecyl, 1-heptyl octyl, hexadecyl, octadecyl, behenyl-1-yl, behenyl-1-yl, behenyl Trialkyl-1-yl, behenate-1-yl and the like. Examples of alkenyl include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 1,3-butadienyl, 1-pentenyl, 2- Pentenyl, 1-hexenyl, 2-ethyl-2-butenyl, 2-octenyl, (4-vinyl) -5-hexenyl, 2-decenyl, and the like. Examples of the alkynyl group include ethynyl, 1-propynyl, 1-butynyl, 1-pentynyl, 3-pentynyl, 1-hexynyl, and 2-ethyl-2- 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 fused polycyclic hydrocarbon group, a bridged cyclic hydrocarbon group, a spirocyclic hydrocarbon group, and a cyclic terpene alkenyl group. More specific examples include cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, third butyl cyclohexyl, cycloheptyl, and cyclooctyl; rings such as 1-cyclohexenyl Alkenyl; tricyclic decyl, decahydro-2-naphthyl, adamantyl and other fused polycyclic hydrocarbon groups; tricyclic [5.2.1.0 ^2,6 ] decane-8-yl, pentacyclopentadecyl, Isobornyl, dicyclopentenyl, tricyclopentenyl and other bridged hydrocarbon groups; a monovalent group obtained by removing one hydrogen atom from spiro [3,4] heptane and spiro [3,4] octane Isospirocyclic hydrocarbon groups; cyclic terpene olefin groups such as monovalent groups obtained by removing one hydrogen atom from mentane, thujane, pinane, and the like. Among the above cycloalkyl and cycloalkenyl groups, the number of carbon atoms is more preferably 3 to 12.

The aromatic hydrocarbon group is preferably an aromatic group having 6 to 20 carbon atoms. The aromatic hydrocarbon group is more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms. Examples of the aromatic hydrocarbon group include an aryl group. Here, the "aryl group" in the present specification means a monocyclic to tricyclic aromatic hydrocarbon group, and specific examples include a phenyl group, a benzyl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, and a xylyl group. , Naphthyl, anthracenyl, phenanthryl, fluorenyl, 9-fluorenyl and the like.

Examples of the substituent of the heterocyclic ring of ring Z ¹ to ring Z ⁴ and the hydrocarbon group of R ¹ to R ⁶ include a halogen atom, a hydroxyl group, a cyano group, a methylamino group, a carboxyl group, a nitro group, an amine group, and a dialkylamine. Base, diarylamino, alkoxy, aryloxy, alkoxycarbonyl, alkylthio, arylthio, trialkylsilyl, mercapto, allyl, alkylsulfonyl, Alkylaminesulfonyl, aliphatic hydrocarbon, heterocyclic, aromatic hydrocarbon, and the like.

The compound having a structure represented by the formula (1) is preferably a compound having a structure represented by the following formula (1A) (hereinafter, also referred to as "compound (1A)". In addition, the compound having a structure represented by the formula (2) A compound having a structure represented by the following formula (2A) (hereinafter, also referred to as "compound (2A)") is preferred.

[In the formula (1A), R ¹ to R ³ have the same meanings as described above.

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

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

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

[In formula (2A), q, R ⁴ to R ⁶ have the same meanings as described above.

Ring Z ^3A and ring Z ^4A independently of one another represent a substituted or unsubstituted aromatic hydrocarbon ring.

Q ³ and Q ⁴ independently represent -O-, -S-, or -CR ²³ R ^24- .

R ²¹ to R ²⁴ each independently represent a substituted or unsubstituted hydrocarbon group. ]

As the aromatic hydrocarbon ring in ring Z ^1A to ring Z ^4A , an aromatic hydrocarbon ring having 6 to 20 carbon atoms is preferred, an aromatic hydrocarbon ring having 6 to 10 carbon atoms is more preferred, and a benzene ring is particularly preferred. .

R ¹ to R ^{6 are} preferably a hydrogen atom.

q is preferably 2.

Q ¹ and Q ^{2 are} preferably -O-, -CR ¹³ R ^14- . The hydrocarbon group in R ¹³ and R ¹⁴ is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. 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.

Q ³ and Q ^{4 are} preferably -O- and -CR ²³ R ^24- . The hydrocarbon group in R ²³ and R ²⁴ is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. 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.

^Examples of the hydrocarbon group in R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Specific examples include the same examples as those exemplified for the hydrocarbon group of R ¹ to R ⁶ . Among them, as the hydrocarbon group in R ¹¹ to R ¹² and R ²¹ to R ²² , an aliphatic hydrocarbon group is preferable, and an alkyl group is more preferable. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 8, and particularly preferably 1 to 6.

When the structure represented by formula (1) and the structure represented by formula (2) are cationic, a compound having this structure may have an anion in order to be electrically neutral. Examples of the anion include a halogen ion, a boron anion, a phosphate anion, a carboxylic acid anion, a sulfate anion, an organic sulfonic acid anion, a nitrogen anion, a methylate anion, and a transition metal complex having an azo compound in a ligand Anions, etc.

Examples of the halogen ion include fluoride ion, chloride ion, bromide ion, and iodide ion. Examples of the boron anion, phosphate anion, and nitrogen anion include the ions described in paragraphs [0037] to [0039] of JP 2012-173399. Examples of the carboxylic acid anion include carboxylic acid anions described in Japanese Patent Application Laid-Open No. 2009-265641 and Japanese Patent Application Laid-Open No. 2008-096680. Examples of the sulfate anion include a sulfate anion and a sulfite anion. Examples of the organic sulfonic acid anion include Japanese Patent Application Publication No. 2012-173399, International Publication No. 2011/037195, International Publication No. 2011/162217, Japanese Patent No. 3376221, and Japanese Patent Application No. 2011-070172. An organic sulfonic acid anion described in the publication. Examples of the methylate anion include Japanese Patent Application Laid-Open The methylate anion described in 2011-145540, US Patent No. 5,554,664, Japanese Patent Application Laid-Open No. 2005-309408, Japanese Patent Application Laid-Open No. 2004-085657, Japanese Patent Application No. 2010-505787, and the like.

Examples of the anion of the transition metal complex having an azo compound in the ligand include the anions described in Japanese Patent Application Laid-Open No. 2009-163226 and Japanese Patent Application Laid-Open No. 2012-212089.

Among these anions, a boron anion, a nitrogen anion, and an anion of a transition metal complex having an azo compound in a ligand are preferable, and a boron anion and a nitrogen anion are more preferable.

Specific examples of the boron anion, and examples thereof include ^{_{BF 4 -, (CF 3)}} 4 B -, (CF 3) 3 BF -, (CF 3) 2 BF 2 -, (CF 3) BF 3 -, (C ^{_{2 F 5) 4 B -,}} (C 2 F 5) 3 BF -, (C 2 F 5) BF 3 -, (C 2 F 5) 2 BF 2 -, (CF 3) (C 2 F 5) 2 ^{_{BF -, (C 6 F 5}} ) 4 B -, [(CF 3) 2 C 6 H 3] 4 B -, (CF 3 C 6 H 4) 4 B -, (C 6 F 5) 2 BF 2 - _{, (C 6 F 5) BF} 3 -, (C 6 H 3 F 2) 4 B -, B (CN) 4 -, B (CN) F 3 -, B (CN) 2 F 2 -, B (CN ^{_{) 3 F -, (CF 3}} ) 3 B (CN) -, (CF 3) 2 B (CN) 2 -, (C 2 F 5) 3 B (CN) -, (C 2 F 5) 2 B ( ^{_{CN) 2 -, (nC 3}} F 7) 3 B (CN) -, (nC 4 F 9) 3 B (CN) -, (nC 4 F 9) 2 B (CN) 2 -, (nC 6 F 13 ^{_{) 3 B (CN) -,}} (CHF 2) 3 B (CN) -, (CHF 2) 2 B (CN) 2 -, (CH 2 CF 3) 3 B (CN) -, (CH 2 CF 3) ^{_{2 B (CN) 2 -,}} (CH 2 C 2 F 5) 3 B (CN) -, (CH 2 C 2 F 5) 2 B (CN) 2 -, (CH 2 CH 2 C 3 F 7) 2 ^{_{B (CN) 2 -, (}} nC 3 F 7 CH 2) 2 B (CN) 2 -, (C 6 H 5) 3 B (CN) -, tetrakis (pentafluorophenyl) borate anion.

Specific examples of the nitrogen anion include [(CN) ₂ N] ^- , [(FSO ₂ ) ₂ N] ^- , [(FSO ₂ ) N (CF ₃ SO ₂ )] ^- , [(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}] -, [(CF 3 SO 2) 2 N] - and the like.

In the coloring composition of the present invention, the content of the compound (2) needs to be 0.001% by mass or more with respect to the total content of the compound (1) and the compound (2). The present inventors have inferred that the compound (1) has low solubility in a solvent and is easily crystallized to become a foreign substance, so that the storage stability of the colored composition is poor. Furthermore, it is estimated that by containing the compound (2) in a predetermined amount or more together with the compound (1), the crystallization of the compound (1) can be prevented and the storage stability of the colored composition can be improved. From the viewpoint of further improving the storage stability, the content of the compound (2) is preferably 0.003 mass% or more, more preferably 0.005 mass% or more, and even more preferably relative to the total content of the compound (1) and the compound (2). It is 0.008 mass% or more, and particularly preferably 0.01 mass% or more. In addition, from the viewpoint of forming a colored hardened film with higher brightness, it is preferably 1% by mass or less, more preferably 0.4% by mass or less, still more preferably 0.1% by mass or less, still more preferably 0.09% by mass or less, more It is more preferably 0.08 mass% or less, and still more preferably 0.07 mass% or less. The content of the compound (2) is preferably 0.001 to 1% by mass, more preferably 0.003 to 0.4% by mass, and still more preferably 0.005 to 0.1% by mass, more than the total content of the compounds (1) and (2). It is more preferably 0.01 to 0.1% by mass, and particularly preferably 0.01 to 0.08% by mass.

The coloring composition of the present invention may further contain a coloring agent (hereinafter, also referred to as "other coloring agent") other than the compound (1) and the compound (2). Other colorants are not particularly limited, and colors and materials can be appropriately selected according to the application, and colors other than compound (1) and compound (2) can be selected. Both materials and dyes can be used. Among these, in the meaning of obtaining a colored hardened film with high brightness and color purity, organic pigments and organic dyes are preferred.

系色澱顏料、偶氮系色澱顏料，更佳為三芳基甲烷系色澱顏料和

系色澱顏料。 Examples of the organic pigment include compounds classified as pigments in the color index (issued by The Society of Dyers and Colourists). Among them, CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 179, 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 129, 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 Pigment Orange 38, CI Pigment Purple 23, etc. In addition, Japanese Patent Laid-Open No. 2001-081348, Japanese Patent Laid-Open No. 2010-026334, Japanese Patent Laid-Open No. 2010-191304, Japanese Patent Laid-Open No. 2010-237384, and Japanese Patent Laid-Open No. 2010-237569 are also preferred. Lake pigments described in Japanese Patent Application Laid-Open No. 2011-006602, Japanese Patent Application Laid-Open No. 2011-145346, etc., and brominated diketopyrrolopyrrolopyrrole pigments represented by Formula (Ic) in Japanese Patent Application No. 2011-523433. . Among the lake pigments, triarylmethane-based lake pigments,

Based lake pigments and azo based lake pigments, more preferably triarylmethane based lake pigments and

Department of lake pigments.

In the present invention, when a pigment is used as another coloring agent, the pigment may be purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. In addition, the pigment may be used by modifying the surface of its particles with a resin as necessary. As a resin for modifying the particle surface of a pigment, for example, Examples thereof include a vehicle resin described in Japanese Patent Application Laid-Open No. 2001-108817, and various commercially available resins for dispersing pigments. As a method for coating the carbon black surface, for example, the methods described in Japanese Patent Application Laid-Open No. 9-71733, Japanese Patent Application Laid-Open No. 9-95625, Japanese Patent Application Laid-Open No. 9-124969, and the like can be used. An organic pigment can be used by miniaturizing the primary particles by a so-called salt mill. As a method of salt milling, for example, the method disclosed in Japanese Patent Application Laid-Open No. 8-179111 can be adopted.

In the present invention, when a pigment is used as another coloring agent, it may further contain a known dispersant and a dispersing assistant. Examples of well-known dispersants include a polyurethane-based dispersant, a polyethyleneimine-based dispersant, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene alkylphenyl ether-based dispersant, Polyethylene glycol diester-based dispersant, sorbitan fatty acid ester-based dispersant, polyester-based dispersant, acrylic-based dispersant, etc. Examples of the dispersion aid include pigment derivatives.

Such a dispersant is commercially available. For example, as the acrylic dispersant, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (the above is BYK-Chemie (BYK)) ), And examples of the polyurethane-based dispersant include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182, Disperbyk-2164 (the above is BYK-Chemie (Manufactured by BYK), Solsperse 76500 (manufactured by Lubrizol), as the polyethyleneimine-based dispersant, Solsperse 24000 (manufactured by Lubrizol), and polyester-based dispersant include Adisper PB821, Adisper PB822, Adisper PB880, Adisper PB881 (above are manufactured by Ajinomoto Fine-Techno), in addition to BYK-LPN21324 (non-volatile content of 40% by mass) (BYK-Chemie (BYK))制) and so on.

Examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and a sulfonic acid derivative of quinophthalone.

The other coloring agents in the present invention can be used alone or in combination of two or more.

The coloring composition of the present invention is preferably used to form a red pixel or a green pixel.

When used for forming a red pixel, it is preferable that the (A) colorant contains a red pigment, a red dye, a purple pigment, a purple dye, a yellow pigment, a yellow dye, and a red pigment selected from the compound (1) together with the compound (1) At least one of the orange pigments is used as another coloring agent. When forming a green pixel, it is preferable that the (A) colorant contains at least one selected from the group consisting of a green pigment, a green dye, a yellow pigment, and a yellow dye other than the compound (1) together with the compound (1). Colorants.

The red pigment is preferably a diketopyrrolopyrrole pigment of C.I. Pigment Red 177, C.I. Pigment Red 254, C.I. Pigment Red 264, and Japanese Patent Publication No. 2011-523433 as represented by formula (Ic). The purple pigment is preferably C.I. Pigment Violet 23. As said yellow pigment, C.I. pigment yellow 129, C.I. pigment yellow 138, C.I. pigment yellow 139, C.I. pigment yellow 150, and C.I. pigment yellow 185 are preferable. As said orange pigment, C.I. pigment orange 38 is preferable. As the green pigment, C.I. pigment is preferred. Phthalocyanine pigments such as Feed Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58 and the like.

系染料。 As said red dye and purple dye, it is preferable

Department of dyes.

From the viewpoint of forming a pixel that is excellent in chromaticity characteristics even at a low exposure level and is less prone to defects, or a black matrix and black spacer that are excellent in light shielding properties, the content of (A) the colorant in the solid content of the coloring composition is usually It is 5 to 70 mass%, preferably 10 to 60 mass%, and more preferably 15 to 40 mass%. The solid content is a component other than the solvent mentioned later.

When other coloring agents are used, the content of the other coloring agents is preferably 99% by mass or less, and more preferably 95 parts by mass or less, based on the total content of the colorants. The lower limit value is not particularly limited as long as it is 0.01% by mass or more.

-(B) Binder resin-

Although it does not specifically limit as (B) binder resin in this invention, It is preferable that it is a resin which has an acidic functional group, such as a carboxyl group and a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter, also referred to as a “carboxyl-containing polymer”) is preferred, and for example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter, also referred to as “unsaturated” A copolymer of the monomer (b1) ") and another copolymerizable ethylenically unsaturated monomer (hereinafter, also referred to as" unsaturated monomer (b2) ").

Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinate mono [2- (meth) acryloxyethyl] ester, and ω-carboxyl. Polycaprolactone mono (meth) acrylate, p-vinylbenzoic acid and the like.

These unsaturated monomers (b1) can be used individually or in mixture of 2 or more types.

基苯酚的環氧乙烷改性(甲基)丙烯酸酯、(甲基)丙烯酸縮水甘油酯、3,4-環氧環己基甲基(甲基)丙烯酸酯、(甲基)丙烯酸3,4-環氧三環[5.2.1.0^2,6]癸烷-8-基酯、(甲基)丙烯酸3,4-環氧三環[5.2.1.0^2,6]癸烷-9-基酯、3-[(甲基)丙烯醯氧基甲基]氧雜環丁烷、3-[(甲基)丙烯醯氧基甲基]-3-乙基氧雜環丁烷之類的(甲基)丙烯酸酯；如環己基乙烯基醚、異冰片基乙烯基醚、三 環[5.2.1.0^2,6]癸烷-8-基乙烯基醚、五環十五烷基乙烯基醚、3-(乙烯基氧甲基)-3-乙基氧雜環丁烷之類的乙烯基醚；在如聚苯乙烯、聚(甲基)丙烯酸甲酯、聚(甲基)丙烯酸正丁酯、聚矽氧烷之類的聚合物分子鏈的末端具有單(甲基)丙烯醯基的大分子單體等。 Examples of the unsaturated monomer (b2) include N-substituted maleimine such as N-phenylmaleimide and N-cyclohexylmaleimide; Aromatic vinyl compounds such as styrene, α-methylstyrene, vinyl toluene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinyl benzyl glycidyl ether, and pinene; Such as methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, Benzyl (meth) acrylate, polyethylene glycol (polymerization degree 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) methyl ether (meth) 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, isobornyl (meth) acrylate, Tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, (meth) acrylic acid 4-hydroxyphenyl ester, para

Ethylene oxide modified (meth) acrylate of phenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, 3,4 (meth) acrylate -Epoxy tricyclo [5.2.1.0 ^2,6 ] decane-8-yl ester, (meth) acrylic 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9-yl ester, 3-[(Meth) propenyloxymethyl] oxetane, 3-[(meth) propenyloxymethyl] -3-ethyloxetane and the like (methyl ) Acrylic esters; such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclic [5.2.1.0 ^2,6 ] decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3- (Vinyloxymethyl) -3-ethyloxetane; vinyl ethers such as polystyrene, poly (meth) acrylate, poly (meth) acrylate, poly (meth) acrylate A macromonomer having a mono (meth) acrylfluorenyl group at the end of a polymer molecular chain such as a siloxane.

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

Among these unsaturated monomers (b2), it is preferred to include, for example, an ethylenically unsaturated monomer having an epoxyethyl group, an ethylenically unsaturated monomer having an oxetanyl group, and an ethylenically unsaturated group having a tetrahydrofuran group. The ethylenically unsaturated monomer having a cyclic ether structure having 2 to 4 carbon atoms, such as a monomer, more preferably contains an ethylenically unsaturated monomer having an ethylene oxide group. As the ethylenically unsaturated monomer having an epoxy ethyl group, 3,4-epoxycyclohexyl methyl (meth) acrylate and 3,4-epoxy tricyclic (meth) acrylate are preferred [5.2.1.0] ^2,6 ] decane-8-yl ester, 3,4-epoxytricyclo (meth) acrylic acid [5.2.1.0 ^2,6 ] decane-9-yl ester.

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

Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, Japanese Patent Application Laid-Open No. 7-140654, Japanese Patent Application Laid-Open No. 8-259876, and Japanese Patent Laid-Open No. 10- 31308 Published in the Gazette, Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-174224, Japanese Patent Laid-Open No. 11-258415, Japanese Patent Laid-Open No. 2000-56118, Japanese Patent Laid-Open No. 2004-101728, etc. Copolymer.

In addition, in the present invention, for example, Japanese Patent Laid-Open No. 5-19467, Japanese Patent Laid-Open No. 6-230212, Japanese Patent Laid-Open No. 7-207211, Japanese Patent Laid-Open No. 9-325494, and Japanese Patent Laid-Open No. A carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acrylfluorenyl group in a side chain disclosed in Japanese Unexamined Patent Application Publication No. 11-140144, Japanese Laid-Open Patent Publication No. 2008-181095, and the like is used as a binder resin.

The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter, omitted as GPC) of the binder resin in the present invention (eluting solvent: tetrahydrofuran) is usually 1,000 to 100,000, preferably 3,000. ~ 50,000. By adopting this method, the residual film rate, pattern shape, heat resistance, electrical characteristics, and resolution of the film can be further improved, and the generation of dry foreign matter during coating can be suppressed at a high level.

In addition, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin in the present invention is preferably 1.0 to 5.0, and more preferably 1.0 to 3.0. In addition, Mn here means the number average molecular weight of polystyrene conversion measured by GPC (eluting solvent: tetrahydrofuran).

The binder resin in the present invention can be produced by a known method, and can also be controlled by a method disclosed in, for example, Japanese Patent Laid-Open No. 2003-222717, Japanese Patent Laid-Open No. 2006-259680, and International Publication No. 07/029871. Its structure, Mw, Mw / Mn.

In this invention, a binder resin can be used individually or in mixture of 2 or more types.

In the present invention, the content of the (B) binder resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, and more preferably 50 to 200 parts by mass relative to 100 parts by mass of the colorant (A). More preferably, it is 80 to 150 parts by mass. By adopting this method, it is possible to further improve the alkali developability, the storage stability of the colored composition, the pattern shape, and the chromaticity characteristics.

-(C) polymerizable compound-

The polymerizable compound in the present invention means a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an epoxyethyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the polymerizable compound is preferably a compound having two or more (meth) acrylfluorenyl groups or a compound having two or more N-alkoxymethylamino groups.

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

Here, as the aliphatic polyhydroxy compound, for example, a binary one such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol can be mentioned. Aliphatic polyhydroxy compounds; such as glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol and the like. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and Pentaerythritol penta (meth) acrylate, glycerol dimethacrylate and the like. Examples of the polyfunctional isocyanate include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and the like. Examples of the acid anhydride include dibasic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, and pyromellitic dicarboxylic acid. Tetracarboxylic dianhydride such as anhydride, biphenyltetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride.

Examples of the polyfunctional (meth) acrylate modified with caprolactone include compounds described in paragraphs [0015] to [0018] of Japanese Patent Application Laid-Open No. 11-44955. Examples of the polyfunctional (meth) acrylate modified with the alkylene oxide include bisphenol A di (meth) acrylate modified with at least one selected from the group consisting of ethylene oxide and propylene oxide. Isocyanuric acid tri (meth) acrylate modified with at least one kind selected from ethylene oxide and propylene oxide, and modified with at least one kind selected from ethylene oxide and propylene oxide Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide, selected from ethylene oxide and At least one modified pentaerythritol tetra (meth) acrylate in propylene oxide, at least one modified dipentaerythritol penta (meth) acrylate selected from ethylene oxide and propylene oxide, At least one modified dipentarate selected from ethylene oxide and propylene oxide Tetraol hexa (meth) acrylate and the like.

環或者苯基取代三

環作為基本骨架的化學結構，亦包括三聚氰胺、苯并胍胺或者它們的縮合物的概念。作為具有2個以上的N-烷氧基甲基胺基的化合物的具體例，可舉出N,N,N’,N’,N”,N”-六(烷氧基甲基)三聚氰胺、N,N,N’,N’-四(烷氧基甲基)苯并胍胺、N,N,N’,N’-四(烷氧基甲基)甘脲等。 Examples of the compound having two or more N-alkoxymethylamine groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. In addition, a melamine structure and a benzoguanamine structure mean that it has 1 or more

Ring or phenyl substituted tri

The chemical structure of the ring as the basic skeleton also includes the concept of melamine, benzoguanamine, or their condensates. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ', N', N ", N" -hexa (alkoxymethyl) melamine, N, N, N ', N'-tetrakis (alkoxymethyl) benzoguanamine, N, N, N', N'-tetrakis (alkoxymethyl) glycolurea and the like.

Among these polymerizable compounds, polyfunctional (meth) acrylates obtained by reacting a ternary or higher aliphatic polyhydroxy compound with (meth) acrylic acid, and polyfunctional (methyl) modified with caprolactone are preferred. ) Acrylic esters, polyfunctional urethane (meth) acrylates, polyfunctional (meth) acrylates with carboxyl groups, N, N, N ', N', N ", N" -hexa (alkoxy) Methyl) melamine, N, N, N ', N'-tetrakis (alkoxymethyl) benzoguanamine. From the viewpoints of high strength of the colored layer, excellent surface smoothness of the colored layer, and less likely to cause dirt, film residue, etc. on the substrate of the unexposed portion and the light-shielding layer, the ternary or higher aliphatic polyhydroxy compound and Among the polyfunctional (meth) acrylates obtained by the (meth) acrylic acid reaction, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are particularly preferred. Among the carboxyl polyfunctional (meth) acrylates, particularly preferred are compounds obtained by reacting pentaerythritol triacrylate with succinic anhydride, and dipentaerythritol pentaacrylate and succinic acid. A compound obtained by the reaction of dianhydride.

In the present invention, the (C) polymerizable compound may be used alone or in combination of two or more.

The content of the (C) polymerizable compound in the present invention is preferably from 10 to 1,000 parts by mass, more preferably from 20 to 700 parts by mass, and even more preferably from 50 to 500 parts by mass relative to 100 parts by mass of the (A) colorant. , And even more preferably 80 to 250 parts by mass. In addition, the content of the polymerizable compound (C) is preferably 50 to 300 parts by mass, more preferably 70 to 200 parts by mass, and still more preferably 100 to 150 parts by mass with respect to 100 parts by mass of the binder resin (B). By adopting this method, it is possible to further improve the hardenability and the alkali developability, and to suppress the occurrence of dirt, film residue, and the like on the substrate or the light-shielding layer of the unexposed portion at a high level.

-(D) Photopolymerization initiator-

The coloring composition of the present invention may contain a photopolymerization initiator. This makes it possible to impart radiation sensitivity to the colored composition. The photopolymerization initiator used in the present invention is a compound that generates an active species that can initiate the polymerization of the polymerizable compound by exposure to radiation such as visible light, ultraviolet rays, extreme ultraviolet rays, electron beams, and X-rays.

化合物、O-醯肟化合物、鎓鹽化合物、苯偶姻化合物、二苯甲酮化合物、α-二酮化合物、多環醌化合物、重氮化合物、醯亞胺磺酸酯化合物等。 Examples of such a photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a biimidazole compound, and

Compounds, O-hydrazine compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polycyclic quinone compounds, diazonium compounds, sulfonium iminosulfonate compounds, and the like.

化合物、O-醯肟化合物中的至少1種。 In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator is preferably selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, and

At least one of a compound and an O-hydroxime compound.

Among the preferred photopolymerization initiators in the present invention, examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone. Ketone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyl Thioxanthone and so on.

啉代丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-

啉并苯基)丁烷-1-酮、2-(4-甲基苄基)-2-(二甲基胺基)-1-(4-

啉并苯基)丁烷-1-酮等。 Moreover, as a specific example of the said acetophenone compound, 2-methyl-1- [4- (methylthio) phenyl] -2-

Porphyrin-1-one, 2-benzyl-2-dimethylamino-1- (4-

Phenolinophenyl) butane-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-

Phenolino) butane-1-one and the like.

Specific examples of the biimidazole 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-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like.

唑等硫醇供氫體，4,4’-雙(二甲基胺基)二苯甲酮、4,4’-雙(二乙基胺基)二苯甲酮等胺供氫體。本發明中，供氫體可以單獨使用或者混合2種以上使用，但從能夠進一步改善靈敏 度的觀點考慮，較佳為將1種以上的硫醇供氫體和1種以上的胺供氫體組合使用。 In addition, when using a biimidazole compound as a photoinitiator, it is preferable to use a hydrogen donor together from a viewpoint which can improve sensitivity. The "hydrogen donor" as used herein refers to a compound capable of supplying a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzo

Thiol hydrogen donors such as azoles, amine hydrogen donors such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone. In the present invention, the hydrogen donor may be used alone or in combination of two or more, but from the viewpoint of further improving the sensitivity, it is preferable to combine one or more thiol hydrogen donors and one or more amine hydrogen donors. use.

化合物的具體例，可舉出2,4,6-三(三氯甲基)-s-三

、2-甲基-4,6-雙(三氯甲基)-s-三

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

、2-[2-(呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-s-三

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

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

、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-s-三

、2-(4-乙氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三

、2-(4-正丁氧基苯基)-4,6-雙(三氯甲基)-s-三

等具有鹵代甲基的三

化合物。 In addition, as the above three

Specific examples of the compound include 2,4,6-tris (trichloromethyl) -s-tri

, 2-methyl-4,6-bis (trichloromethyl) -s-tri

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

, 2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -s-tri

, 2- [2- (4-Diethylamino-2-methylphenyl) vinyl] -4,6-bis (trichloromethyl) -s-tri

, 2- [2- (3,4-dimethoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -s-tri

, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-tri

, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-tri

, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-tri

Halomethyl

Compound.

Specific examples of the O-fluorenoxime compound include 1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzoxime), 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -ethanone 1- (O-acetamoxime), 1- [9-ethyl-6 -(2-methyl-4-tetrahydrofurylmethoxybenzyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetamoxime), 1- [9-ethyl- 6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolane) methoxybenzylidene} -9H-carbazol-3-yl] -ethanone 1- (O-acetamoxime) and the like. As commercially available products of O-hydrazine compounds, NCI-831, NCI-930 (the above are manufactured by ADEKA Co., Ltd.), DFI-020, DFI-091 (the above are manufactured by Daitochemix Co., Ltd.), etc. can also be used.

In the present invention, when a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound is used, a sensitizer may be used in combination. Examples of such a sensitizer include 4,4'-bis (dimethylamino) benzophenone. 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminophenylacetone, 4-dimethylaminobenzoate ethyl Ester, 2-dimethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- ( 4-diethylaminobenzyl) coumarin, 4- (diethylamino) chalcone and the like.

In the present invention, the content of the (D) photopolymerization initiator is preferably 0.01 to 120 parts by mass, more preferably 1 to 100 parts by mass, and still more preferably 5 to 50 parts by mass relative to 100 parts by mass of the polymerizable compound (C). Mass parts, particularly preferably 10 to 30 mass parts. By adopting this method, it is possible to further improve the hardenability and the film characteristics.

-(E) Solvent-

The coloring composition of the present invention contains the above components (A) to (C) and other components optionally added, and is usually prepared as a liquid composition by blending a solvent.

As the (E) solvent, as long as the components (A) to (C) and other components constituting the coloring composition are dispersed or dissolved, and do not react with these components, and have appropriate volatility, they can be appropriately selected and used.

Examples of such solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethylene glycol. Monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether (Poly) alkylene diene, 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, and tripropylene glycol monoethyl ether Alcohol monoalkyl ethers; Alkyl lactates such as methyl lactate and ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tertiary butanol, octanol, 2-ethylhexanol, cyclohexanol Iso (cyclo) alkyl alcohols; keto alcohols such as diacetone alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol Alcohol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methyl (Poly) alkylene glycol monoalkyl ether acetates such as oxybutyl acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc. Ethers; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; propylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate Diacetates such as esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethoxy Alkoxy carboxylic acid esters such as ethyl acetate, 3-methyl-3-methoxybutyl propionate; acetic acid Ester, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, butyl Isopropyl ester, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, ethyl 2-oxobutanoate, etc. Esters; Toluene, xylene and other aromatic hydrocarbons; N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and other amines or lactams Wait.

Among these solvents, (poly) alkylene glycol monoalkyl ethers, alkyl lactate, and (poly) alkylene glycol mono are preferred from the viewpoints of solubility, pigment dispersibility, and coatability. Alkyl ether acetates, other ethers, ketones, diacetates, alkoxycarboxylic acid esters, and other esters. Particularly preferred are propylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethylene glycol monomethyl ether. Ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, 3- Methyl ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, isobutyl acetate, n-pentyl formate, acetic acid Isoamyl, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, and the like.

In this invention, a solvent can be used individually or in mixture of 2 or more types.

(E) The content of the solvent is not particularly limited, and the total concentration of each component other than the solvent of the coloring composition is preferably an amount of 5 to 50% by mass, and more preferably an amount of 10 to 40% by mass. By using this method, a coloring agent dispersion liquid having good dispersibility and stability and a coloring composition having good coatability and stability can be obtained.

-additive-

The coloring composition of the present invention may further contain various additives as necessary.

Examples of the additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); and fluorine Surfactants, silicone surfactants and other surfactants; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, N- (2-amine Ethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane Equal adhesion promoter; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, pentaerythritol tetra [3- (3,5-di Third butyl-4-hydroxyphenyl) propionate], 3,9-bis [2- [3- (3-third butyl-4-hydroxy-5-methylphenyl) -propanyloxy Group] -1,1-dimethylethyl] -2,4,8,10-tetraoxa-spiro [5.5] undecane, thiodiethylidenebis [3- (3,5-di Tertiary butyl-4-hydroxyphenyl) propionate] and other antioxidants; 2- (3-third 5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones and other UV absorbers; anti-flocculants such as sodium polyacrylate; malonic acid, adipic acid , Itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1, Residue improving agents such as 2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol; succinic acid mono [2- (meth) propenyloxyethyl] Esters, developing agents such as mono [2- (meth) acryloxyethyl] phthalate, omega-carboxy polycaprolactone mono (meth) acrylate, and the like.

In addition, when both the dye and the pigment are used as the colorant in the coloring composition of the present invention, as disclosed in Japanese Patent Application Laid-Open No. 2010-132874, a preparation method can be adopted in which a dye solution is passed through After the first filter, the dye solution passing through the first filter is mixed with a separately prepared pigment dispersion liquid, etc., so that the resulting colored composition is prepared through the second filter. In addition, the following preparation method can be adopted: the dye, the above components (B) to (C), and other components used as necessary are dissolved in a solvent, so that the obtained solution passes through the first filter, and then passes through the first filter. The solution was mixed with a separately prepared pigment dispersion, and the resulting colored composition was prepared through a second filter. In addition, the following preparation method can also be adopted: After passing the dye solution through the first filter, the dye solution passing through the first filter is mixed with the above components (B) to (C) and other components used as required. Dissolve, pass the obtained solution through the second filter, and then mix the solution passed through the second filter with a separately prepared pigment dispersion liquid, so that the obtained colored composition is prepared through the third filter.

Colored hardened film and its forming method

The coloring cured film of the present invention is formed using the coloring composition of the present invention, and specifically refers to pixels, black matrices, black spacers, and the like constituting a color filter.

Hereinafter, a colored curing film used in a color filter constituting a display element and a solid-state imaging element and a method for forming the same will be described.

As a method of manufacturing a color filter, the following method is mentioned first. First, a light-shielding layer (black matrix) is formed on the surface of the substrate so that a portion where a pixel is formed is divided as necessary. Next, the liquid composition of the radiation-sensitive coloring composition of the present invention, such as red, is applied to the substrate, and then pre-baking is performed to evaporate the solvent to form a coating film. Next, after exposing this coating film with a photomask, it develops using an alkaline developing solution, and the unexposed part of a coating film is melt | dissolved and removed. After that, after passing This is baked to form a pixel array in which red pixel patterns (colored cured films) are arranged in a predetermined arrangement.

Next, using the respective radiation-sensitive coloring composition of green or blue, coating, pre-baking, exposing, developing, and post-baking of each of the radiation-sensitive coloring compositions are performed in the same manner as described above to sequentially form green pixels on the same substrate. Array and blue pixel array. As a result, a color filter in which pixel arrays of three primary colors of red, green, and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above order.

The black matrix may be formed using a photolithography method to form a thin metal film such as chromium formed by sputtering or vapor deposition into a desired pattern, or a radiation-sensitive coloring composition in which a black colorant is dispersed and the pixel is formed The situation is the same.

Examples of the substrate used when forming a color filter include glass, silicon, polycarbonate, polyester, aromatic polyamine, polyimide, polyimide, and the like.

In addition, these substrates may be subjected to an appropriate pretreatment such as a reagent treatment using a silane coupling agent, plasma treatment, ion plating, sputtering, vapor phase reaction method, vacuum evaporation, etc. as necessary.

When the radiation-sensitive colored composition is coated on the substrate, a suitable method such as a spray coating method, a roll coating method, a spin coating method, a slit die coating method (slit coating method), or a rod coating method can be used. The coating method is particularly preferably a spin coating method or a slit die coating method.

Pre-baking is usually performed by combining reduced pressure drying and heat drying. Drying under reduced pressure is usually performed to 50 to 200 Pa. In addition, heating and drying conditions Usually it is about 70 ~ 110 ℃, about 1 ~ 10 minutes.

The coating thickness is 0.6 to 8 μm, and preferably 1.2 to 5 μm, based on the film thickness after drying.

Examples of the light source for forming radiation used when at least one selected from a pixel and a black matrix include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and medium-pressure mercury lamps , Low-pressure mercury lamp and other lamp light sources, argon ion laser, YAG laser, XeCl excimer laser, nitrogen laser and other laser light sources. As the light source for exposure, an ultraviolet LED may be used. Radiation having a wavelength in the range of 190 to 450 nm is preferred.

The radiation exposure is generally preferably 10 to 10,000 J / m ² .

In addition, as the alkaline developer, for example, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4 .0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene and other aqueous solutions.

An appropriate amount of a water-soluble organic solvent such as methanol, ethanol, or a surfactant may be added to the alkaline developer. In addition, after alkaline development, it wash | cleans with water normally.

As the development treatment method, a spray development method, a spray development method, a dip development method, a puddle development method, or the like can be applied. The developing conditions are preferably 5 to 300 seconds at room temperature.

Post-baking conditions are usually 180 ~ 280 ° C, about 10 ~ 60 minutes.

The film thickness of the pixel formed in this way is usually 0.5 to 5 μm, preferably 1 ~ 3μm.

In addition, as a second method of manufacturing a color filter, a method of obtaining pixels of each color by an inkjet method disclosed in Japanese Patent Application Laid-Open No. 7-318723, Japanese Patent Application Laid-Open No. 2000-310706, and the like can be adopted. In this method, first, a partition wall also having a light shielding function is formed on the surface of the substrate. Next, a liquid composition such as a red thermosetting coloring composition is ejected by a spraying device in the formed partition wall, followed by pre-baking to evaporate the solvent. Next, after exposing this coating film as needed, it hardens by post-baking, and a blue pixel pattern is formed.

Next, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate using the respective thermosetting colored compositions of green or blue on the same substrate as described above. Thus, a color filter having pixel patterns of three primary colors of red, green, and blue arranged on the substrate was obtained. However, in the present invention, the order of forming pixels of each color is not limited to the order described above.

It should be noted that the partition wall not only performs a light-shielding function, but also functions to prevent the thermosetting colored composition of each color ejected into the partition area from mixing colors. Therefore, the film thickness is larger than that of the black matrix used in the first method. For thick. Therefore, the partition wall is usually formed using a black radiation-sensitive composition.

The substrate used for forming the color filter, the radiation light source, and the pre-baking and post-baking methods and conditions are the same as those in the first method described above. The film thickness of the pixel formed by the inkjet method is equal to the height of the partition wall.

After forming a protective film on the pixel pattern obtained in this manner as needed, a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to make a color filter. The spacer is usually formed using a radiation-sensitive composition, but a spacer (black spacer) having a light-shielding property may be formed. In this case, a radiation-sensitive coloring composition in which a black coloring agent is dispersed is used, but the coloring composition of the present invention is also suitable for forming the black spacer.

The radiation-sensitive coloring composition of the present invention can be suitably used to form a colored hardened film of any of the pixels, black matrices, and black spacers used in the color filter described above.

The color filter including the colored hardened film of the present invention thus formed has extremely high brightness and color purity, and is therefore extremely useful in color liquid crystal display elements, color image pickup tube elements, color sensors, organic EL display elements, electronic paper, and the like. it works. In addition, the display element mentioned later may be provided with at least one coloring cured film formed using the radiation-sensitive coloring composition of this invention.

Display element

The display element of the present invention includes the colored cured film of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.

The color liquid crystal display element provided with the colored curing film of the present invention may be a transmissive type or a reflective type, and an appropriate structure may be adopted. For example, a structure in which a color filter is formed on a substrate different from a driving substrate on which a thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. In addition, you can also use A structure in which a substrate on which a color filter is formed on a surface of a driving substrate on which a thin film transistor (TFT) is arranged and a substrate on which an ITO (tin-doped indium oxide) electrode is formed are opposed to each other via a liquid crystal layer. The latter structure has the advantage of being able to significantly increase the aperture ratio and obtain a bright and high-definition liquid crystal display element. In the latter configuration, the black matrix and the black spacer may be formed on either the substrate side on which the color filter is formed and the substrate side on which the ITO electrode is formed.

The color liquid crystal display element provided with the colored hardened film of the present invention includes a cold cathode fluorescent tube (CCFL: Cold Cathode Fluorescent Lamp) and a backlight unit using a white LED as a light source. Examples of the white LED include a white LED that combines red LED, green LED, and blue LED to obtain white light by mixing colors, a white LED that combines blue LED, red LED, and green phosphor to obtain white light by mixing colors, and blue Color LED, red light-emitting phosphor and green light-emitting phosphor are mixed to obtain a white LED with white light, and blue LED and YAG-based phosphor are mixed to obtain a white LED with white light. A combination of blue LED and orange light-emitting phosphor A white LED is obtained by mixing a light body and a green light-emitting phosphor to obtain white light by combining colors, and a white LED having a white light by combining colors of ultraviolet LED, red light-emitting phosphor, green light-emitting phosphor, and blue light-emitting phosphor.

The color liquid crystal display element provided with the colored hardened film of the present invention may be a TN (Twisted Nematic) type, a STN (Super Twisted Nematic) type, or an IPS (In-Planes Switching) type. VA (Vertical Alignment) type, OCB (Optically Compensated Birefringence), light Learn the appropriate liquid crystal mode such as compensated bend alignment.

Moreover, the organic EL display element provided with the colored hardening film of this invention can take an appropriate structure, For example, the structure disclosed by Unexamined-Japanese-Patent No. 11-307242 is mentioned.

Moreover, the electronic paper provided with the colored hardened film of this invention can take an appropriate structure, For example, the structure disclosed by Unexamined-Japanese-Patent No. 2007-41169 is mentioned.

[Example]

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

<Synthesis of colorant>

Synthesis Example 1

In a 300 mL eggplant-shaped flask equipped with a stirrer, 9.7 g of 2,3,3-trimethylindoline, 25.9 g of 1-iodomethane, and 85 mL of acetonitrile were added, and the mixture was stirred with heating under reflux for 10 hours. After cooling to room temperature, the reaction solution was added to 425 mL of diisopropyl ether, ice-cooled, and left to stand for 30 minutes. Thereafter, the precipitate was filtered off with suction filtration, and the obtained solid was dried under reduced pressure to obtain 16.1 g of a pale pink solid. It was confirmed by ¹ H-NMR and MS spectrum analysis that the obtained solid was the compound (A1) represented by the above formula.

Synthesis Example 2

A 100 mL eggplant-shaped flask equipped with a stirrer was charged with 8.1 g of the compound (A1) obtained in Synthesis Example 1, 12.0 g of ethyl orthoformate, and 24 mL of pyridine, and stirred at 120 ° C. for 5 hours. After cooling to room temperature, the reaction solution was concentrated under reduced pressure using a rotary evaporator. Then, 20 mL of acetone was added, and it stirred at 40 degreeC for 30 minutes. Then, it was added to 200 mL of diisopropyl ether, ice-cooled, and left still for 30 minutes. Then, the precipitate was filtered by suction filtration, and the obtained solid was dried under reduced pressure to obtain 6.3 g of a red-purple solid. By ¹ H-NMR and LC-MS analysis, it was confirmed that the obtained solid was a mixture of the compound represented by the formula (A2-1) and the compound represented by the formula (A2-2). This compound was used as a colorant (A-2).

Synthesis Example 3

The colorant (A-2) was recrystallized by the following method. That is, a 300 mL eggplant-shaped flask equipped with a stir bar was charged with 5.0 g of the coloring agent (A-2) obtained in Synthesis Example 2 and 100 g of ion-exchanged water containing 10% by mass of ethanol, and stirred at 80 ° C. for 2 hours. After that, the solution was cooled and left to stand at 5 ° C overnight. The precipitate was filtered off with suction filtration, and the obtained solid was dried under reduced pressure to obtain 4.6 g of a red-purple solid. This compound was used as a colorant (A-3).

Synthesis Example 4

The colorant (A-3) was recrystallized by the following method. That is, A 300 mL eggplant-shaped flask with a stir bar was charged with 5.0 g of the coloring agent (A-3) obtained in Synthesis Example 3 and 100 g of ion-exchanged water containing 10% by mass of ethanol, and stirred at 80 ° C. for 2 hours. After that, the solution was cooled and left to stand at 5 ° C overnight. The precipitate was filtered off with suction filtration, and the obtained solid was dried under reduced pressure to obtain 4.3 g of a red-purple solid. This compound was used as a colorant (A-4).

Synthesis Example 5

A 300 mL eggplant-shaped flask equipped with a stir bar was charged with 3.0 g of the coloring agent (A-2) obtained in Synthesis Example 2, lithium bistrifluoromethanesulfonimide 2.7 g, 24 mL of acetonitrile, 36 mL of ethyl acetate, and ions. Exchange 30 mL of water and stir for 2 hours. Thereafter, the aqueous layer was separated and removed, and the organic layer was washed three times with 30 mL of ion-exchanged water. Subsequently, the organic layer was concentrated under reduced pressure on a rotary evaporator, and dried under vacuum at 50 ° C. overnight to obtain 4.0 g of a dark red solid. By ¹ H-NMR and LC-MS analysis, it was confirmed that the obtained solid was a mixture of the compound represented by the formula (A5-1) and the compound represented by the formula (A5-2). This compound was used as a colorant (A-5).

Synthesis Example 6

In Synthesis Example 5, except that the colorant (A-3) was used in place of the colorant (A-2), the same reaction operation as in Synthesis Example 5 was performed to obtain the compound represented by the above formula (A5-1) and the above A mixture of compounds represented by formula (A5-2). The obtained compound was used as a colorant (A-6).

Synthesis Example 7

In Synthesis Example 5, except that the colorant (A-4) was used in place of the colorant (A-2), the same reaction operation as in Synthesis Example 5 was performed to obtain the compound represented by the above formula (A5-1) and the above A mixture of compounds represented by formula (A5-2). The obtained compound was used as a colorant (A-7).

Synthesis Example 8

In Synthesis Example 5, 2.4 g of p- (vinylphenyl) trifluoromethanesulfonyliminic acid triethylamine salt was used instead of 2.7 g of lithium bistrifluoromethanesulfonyliminide, and Synthesis Example 5 was performed. The same reaction operation. By ¹ H-NMR and LC-MS analysis, it was confirmed that the obtained solid was a mixture of the compound represented by the formula (A8-1) and the compound represented by the formula (A8-2). The obtained compound was used as a colorant (A-8).

Synthesis Example 9

In Synthesis Example 8, except that the colorant (A-3) was used instead of the colorant (A-2), the same reaction operation as in Synthesis Example 8 was performed to obtain the compound represented by the above formula (A8-1) and the above A mixture of compounds represented by formula (A8-2). The obtained compound was used as a colorant (A-9).

Synthesis Example 10

In Synthesis Example 8, except that the colorant (A-4) was used instead of the colorant (A-2), the same reaction operation as in Synthesis Example 8 was performed to obtain the compound represented by the above formula (A8-1) and the above A mixture of compounds represented by formula (A8-2). The obtained compound was used as a colorant (A-10).

Synthesis Example 11

In Synthesis Example 1, except that 30.9 g of 1-iodopropane was used instead of 25.9 g of 1-iodomethane, the same reaction operation as in Synthesis Example 1 was performed to obtain a compound (A11) represented by the above formula.

Synthesis Example 12

In Synthesis Example 2, the same reaction operation as in Synthesis Example 2 was performed except that 8.8 g of the compound (A11) obtained in Synthesis Example 11 was used instead of 8.1 g of the compound (A1). Analysis by ¹ H-NMR and LC-MS confirmed that the obtained compound was a mixture of the compound represented by the above formula (A12-1) and the compound represented by the above formula (A12-2). This compound was used as a colorant (A-12).

Synthesis Example 13

In Synthesis Example 3, the same recrystallization operation as in Synthesis Example 3 was performed except that 5 g of the colorant (A-12) was used instead of 5 g of the colorant (A-2). The obtained compound was used as a colorant (A-13).

Synthesis Example 14

In Synthesis Example 4, the same recrystallization operation as in Synthesis Example 4 was performed except that 5 g of the colorant (A-13) was used instead of 5 g of the colorant (A-3). The obtained compound was used as a colorant (A-14).

Synthesis Example 15

In Synthesis Example 5, the same reaction operation as in Synthesis Example 5 was performed except that 3.3 g of the colorant (A-12) was used instead of 3.0 g of the colorant (A-2). A mixture of the compound represented by the formula (A15-1) and the compound represented by the formula (A15-2) is obtained. The obtained compound was used as a colorant (A-15).

Synthesis Example 16

In Synthesis Example 5, except that 3.3 g of the colorant (A-13) was used instead of 3.0 g of the colorant (A-2), the same reaction operation as in Synthesis Example 5 was performed to obtain the formula (A15-1) A mixture of a compound of the present invention and a compound represented by the above formula (A15-2). The obtained compound was used as a colorant (A-16).

Synthesis Example 17

In Synthesis Example 5, except that 3.3 g of the colorant (A-14) was used instead of 3.0 g of the colorant (A-2), the same reaction operation as in Synthesis Example 5 was performed to obtain the formula (A15-1) A mixture of a compound of the present invention and a compound represented by the above formula (A15-2). The obtained compound was used as a colorant (A-17).

Confirmation of purity

Prepare acetonitrile solutions (colorant concentration 1000ppm) of colorants (A-5) ~ (A-10) and (A-15) ~ (A-17) respectively, and use high-performance liquid chromatography to perform purity analysis using the following analysis conditions. Quantitative. The concentration of the compound (2), that is, the compound having the structure represented by the formula (2) in each colorant was measured, and the content of the compound (2) relative to the total content of the compound (1) and the compound (2) was calculated. The results are shown in Table 1.

[Analysis conditions]

‧Device: High-performance liquid chromatography [Smartline (PDA SYSTEM) LC SYSTEM, manufactured by KNAUER]

‧Detector: Smartline PDA Detector 2850

‧Solvent: acetonitrile / 0.1% trifluoroacetic acid aqueous solution = 7/3 (v / v) mixed solvent

‧Column: CAPCELLPAK C18 MG (5μ150x4.6mm, made by Shiseido)

‧Column oven setting temperature: 40 ℃

‧Sample injection volume: 10 μL

‧Flow: 0.5mL / min

Table 1 shows that the concentration of the compound (2) in the colorants (A-7), (A-10), and (A-17) is lower than the detection limit in high-performance liquid chromatography.

<Preparation of Pigment Dispersion>

Preparation Example 1

15 parts by mass of CI Pigment Red 254 was used as a colorant, 12.5 parts by mass (solid content concentration of 40% by mass) of BYK-LPN21116 (manufactured by BYK-Chemie (BYK)) was used as a dispersant, and 72.5 parts by mass of a solvent was used. Propylene glycol monomethyl ether acetate was processed with a bead mill to prepare a pigment dispersion liquid (a-1).

<Preparation of colorant solution>

Preparation Example 2

10 parts by mass of the colorant (A-5) and 90 parts by mass of the propylene glycol monomethyl ether were mixed to prepare a colorant solution (A-5).

Preparation Examples 3 ~ 10

In Preparation Example 2, except that the kind of the colorant was changed as shown in Table 2, the colorant solutions (A-6) ~ (A-10) and (A-15) ~ ( A-17).

<(B) Synthesis of Binder Resin>

Synthesis Example 18

100 parts by mass of propylene glycol monomethyl ether acetate was charged into a flask equipped with a cooling tube and a stirrer, and nitrogen replacement was performed. Heat to 80 ° C, and add 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, and methyl at this temperature dropwise over 1 hour. 15 parts by mass of 2-hydroxyethyl acrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, and mono (2-propenyloxyethyl) succinate A mixed solution of 15 parts by mass and 6 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) was polymerized while maintaining the temperature for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and polymerization was further performed for 1 hour, thereby obtaining a binder resin solution (B1) (solid content concentration: 33% by mass). The obtained binder resin had Mw of 12,200 and Mn of 6,500.

Synthesis Example 19

According to the method described in Synthesis Example 6 of Japanese Patent Application Laid-Open No. 2013-203955, a solution containing a resin having the following structural unit was obtained. Next, propylene glycol monomethyl ether acetate was added to adjust the solid content concentration to 33% by mass to obtain a binder resin solution (B2) (solid content concentration: 33% by mass).

Preparation of colored composition

Example 1

啉并苯基)丁烷-1-酮(商品名IRGACURE 369，Ciba Specialty Chemicals公司製)1.8質量份和NCI-930(ADEKA股份有限公司製)0.1質量份、作為氟系界面活性劑的MEGAFAC F-554(DIC股份有限公司製)0.05質量份以及作為溶劑的丙二醇單甲醚乙酸酯混合，製備固體成分濃度為20質量%的著色組成物(S-1)。 (A) 30.5 parts by mass of the pigment dispersion liquid (a-1), 23.0 parts by mass of the colorant solution (A-5), and 26.3 parts by mass of the binder resin solution (B1) as the (B) binder resin. 9.9 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate as a polymerizable compound (manufactured by Nippon Kayaku Co., Ltd. under the trade name KAYARAD DPHA) and 2-benzyl as a photopolymerization initiator -2-dimethylamino-1- (4-

MEGAFAC F as a fluorosurfactant, 1.8 parts by mass of phosphono) butane-1-one (trade name IRGACURE 369, manufactured by Ciba Specialty Chemicals) and 0.1 part by mass of NCI-930 (made by ADEKA Corporation) -554 (manufactured by DIC Corporation) was mixed with propylene glycol monomethyl ether acetate as a solvent to prepare a colored composition (S-1) having a solid content concentration of 20% by mass.

Evaluation of chromaticity characteristics

The obtained colored composition was applied on a glass substrate using a spin coater, and then pre-baked with a hot plate at 80 ° C. for 10 minutes to form a coating film. By changing the rotation speed of the spin coater, three coating films having different film thicknesses were formed by the same operation.

Next, after these substrates were cooled to room temperature, each coating film was exposed to radiation including wavelengths of 365 nm, 405 nm, and 436 nm using a high-pressure mercury lamp without a photomask at an exposure amount of 2,000 J / m ² . Thereafter, a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. was sprayed onto these substrates at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm), and spray-developed for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and then post-baked in a dust-free oven at 200 ° C. for 30 minutes to form a colored hardened film for evaluation.

A color analyzer (MCPD2000, manufactured by Otsuka Electronics Co., Ltd.) was used for the obtained three colored hardened films, and the chromaticity coordinate values (x, y) and stimulus values (in the CIE color system) were measured in a C light source and a 2 degree field of view. Y). Based on the measurement results, the chromaticity coordinate value x and the stimulus value (Y) when the fineness coordinate value y = 0.329 is obtained. The evaluation results are shown in Table 3. In addition, it can be said that the higher the stimulus value (Y), the higher the brightness.

Foreign body evaluation

Using a spin coater, a 10 cm × 10 cm soda-lime glass substrate having a SiO ₂ film preventing the elution of sodium ions was applied to a colored composition (S-1) at 5 ° C. for 3 days, and then heated at 90 ° C. The board was pre-baked for 4 minutes to form a coating film having a film thickness of 2.5 μm after the pre-baking. Observe the obtained substrate with an optical microscope. If no foreign matter is observed on the coating film, it will be marked as "○". If the number of foreign matter on the coating film is between 1 and 10, it will be marked as "△". When the number of foreign matter observed on the coating film was 11 or more, it was described as "×". The evaluation results are shown in Table 3. In addition, the less foreign matter, the more excellent the storage stability of a coloring composition.

Examples 2 to 4 and Comparative Examples 1 and 2

A coloring composition was prepared in the same manner as in Example 1 except that the type of the colorant solution was changed as shown in Table 3. Then, it evaluated similarly to Example 1. The results are shown in Table 3.

Examples 5, 6 and Comparative Example 3

In Example 1, the coloring composition was prepared in the same manner as in Example 1 except that the types of the colorant solution and the binder resin were changed as shown in Table 3. Then, it evaluated similarly to Example 1. The results are shown in Table 3.

Claims (6)

A coloring composition comprising (A) a colorant, (B) a binder resin, and (C) a polymerizable compound, and (A) a colorant containing a compound having a structure represented by the following formula (1) And the content of the compound having the structure represented by the following formula (2) and the compound having the structure represented by the following formula (2) with respect to the compound having the structure represented by the following formula (1) and the content of the compound having the following formula (2) The total content of the compound of the structure represented by) is 0.001 to 1% by mass, In formula (1), ring Z ¹ and ring Z ² independently of each other represent a substituted or unsubstituted heterocyclic ring, and p represents 1 or 2, wherein when p is 2, a plurality of R ¹ and R ² may be present. The same may be different, and R ¹ to R ³ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group, In formula (2), ring Z ³ and ring Z ⁴ independently represent a substituted or unsubstituted heterocyclic ring, when p is 1, q represents an integer of 2 or more, when p is 2, q represents an integer of 3 or more, and R ⁴ to R ⁶ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group, and a plurality of R ⁴ and R ⁵ may be the same or different. The coloring composition according to claim 1, which is used to form a red pixel or a green pixel. The colored composition according to claim 1 or 2, wherein the compound having the structure represented by the formula (1) is a compound having the structure represented by the following formula (1A), and the compound having the structure represented by the formula (2) The compound is a compound having a structure represented by the following formula (2A), In the formula ^{(1A), R R 1 ~} R 3 and requested item 1 ¹ ~ R ^{3 are} the same meaning as the ring Z ^1A and ring Z ^2A each independently represents a substituted or unsubstituted aromatic hydrocarbon ring, Q ¹ and Q ² independently represents -O-, -S- or -CR ¹³ R ^14- , and R ¹¹ to R ¹⁴ independently represent a substituted or unsubstituted hydrocarbon group, In formula (2A), q and R ⁴ to R ⁶ have the same meanings as those of claim 1 and q and R ⁴ to R ^6. Ring Z ^3A and ring Z ^4A independently represent a substituted or unsubstituted aromatic hydrocarbon ring. Q ³ and Q ⁴ independently represent -O-, -S- or -CR ²³ R ^24- , and R ²¹ to R ²⁴ independently represent a substituted or unsubstituted hydrocarbon group. A colored hardened film containing a compound having a structure represented by the following formula (1) and a compound having a structure represented by the following formula (2), and the content of the compound having a structure represented by the following formula (2) is relative to The total content of the compound having a structure represented by the following formula (1) and the compound having a structure represented by the following formula (2) is 0.001 to 1% by mass, In formula (1), ring Z ¹ and ring Z ² independently of each other represent a substituted or unsubstituted heterocyclic ring, and p represents 1 or 2, wherein when p is 2, a plurality of R ¹ and R ² may be present. The same may be different, and R ¹ to R ³ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group, In formula (2), ring Z ³ and ring Z ⁴ independently represent a substituted or unsubstituted heterocyclic ring, when p is 1, q represents an integer of 2 or more, when p is 2, q represents an integer of 3 or more, and R ⁴ to R ⁶ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group, and a plurality of R ⁴ and R ⁵ may be the same or different. A display element having a colored hardened film as claimed in claim 4. A coloring agent containing a compound having a structure represented by the following formula (1) and a compound having a structure represented by the following formula (2), and the content of the compound having a structure represented by the following formula (2) relative to The total content of the compound having the structure represented by the formula (1) and the compound having the structure represented by the following formula (2) is 0.001 to 1% by mass. In formula (1), ring Z ¹ and ring Z ² independently of each other represent a substituted or unsubstituted heterocyclic ring, and p represents 1 or 2, wherein when p is 2, a plurality of R ¹ and R ² may be present. The same may be different, and R ¹ to R ³ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group, In formula (2), ring Z ³ and ring Z ⁴ independently represent a substituted or unsubstituted heterocyclic ring, when p is 1, q represents an integer of 2 or more, when p is 2, q represents an integer of 3 or more, and R ⁴ to R ⁶ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group, and a plurality of R ⁴ and R ⁵ may be the same or different.