TW201525075A - Coloring composition, coloring hardened film, and display element - Google Patents

Abstract

The present invention is to provide a coloring composition containing a cyanine dye as the coloring agent and having excellent stability, which contains (A) colorant, (B) binder resin, and (C) polymerizable compound, wherein the (A) colorant contains the compound with structure as represented by the below-mentioned formula (I) and the compound with structure as represented by the below-mentioned formula (II), and the content of the compound with structure as represented by the below-mentioned formula (II) relative to the total content of the compound with structure as represented by the below-mentioned formula (I) and the compound with structure as represented by the below-mentioned formula (II) is above 0.001 mass%. [in the formulae (1) and (2), ring Z1, ring Z2, ring Z3, and ring Z4 mutually independently represent substituted or unsubstituted heterocyclic ring. R1 - R6 mutually independently represent hydrogen atom, halogen atom, or substituted or unsubstituted hydrocarbon group, wherein when R1, R2, R4, and R5 are multiply existent, they can be the same or different. P represents 1 or 2, and when p is 1, q represents the integer above 2; when p is 2, q represents integer above 3].

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, and more particularly to a color liquid crystal display element, a solid-state imaging element, an organic EL display element, an electronic paper, etc. for forming in a transmissive or reflective type. The colored composition of the colored cured film used in the coloring cured film formed using the colored composition and a display element including the colored cured film.

When a color filter is produced using a colored radiation-sensitive composition, it is known that a pigment-dispersed colored radiation-sensitive composition is applied onto a substrate and dried, and then the dried coating film is irradiated with radiation to have a desired pattern shape ( Hereinafter, a method of performing development to obtain pixels of respective colors (for example, refer to Patent Documents 1 and 2). Further, a method of forming a black matrix by using a photopolymerizable composition in which carbon black is dispersed is known (for example, refer to Patent Document 3). Further, a method of obtaining a pixel of each color by an inkjet method using a pigment-dispersed colored resin composition is known (for example, see Patent Document 4).

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

[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, according to studies by the present inventors, it has been found that the coloring composition containing a cyanine dye as a coloring agent may have insufficient storage stability of the coloring composition.

Therefore, an object of the present invention is to provide a coloring composition containing a cyanine dye as a coloring agent and having a coloring cured film which is excellent in storage stability and capable of forming high brightness. Further, an 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.

As a result of intensive studies, the present inventors have found that the above problems can be solved by using at least two kinds of cyanine compounds as colorants and controlling the content ratio thereof.

That is, the present invention provides a coloring composition comprising (A) a coloring agent, (B) a binder resin, and (C) a coloring composition of a polymerizable compound, and (A) the coloring agent contains the following formula (1) The compound of the structure shown and the compound having the structure represented by the following formula (2) have the following formula (2) 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% by mass or more.

Furthermore, the present invention 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 total content of the compound with respect to the compound represented by the following formula (1) and the compound represented by the following formula (2) is 0.001% by mass or more.

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

p represents 1 or 2. Wherein, when p is 2, a plurality of R ¹ and R ^{2 present} may be the same or different.

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

[In the formula (2), the ring Z ³ and the ring Z ⁴ independently of each other 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 independently of each other represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group. Among them, a plurality of R ⁴ and R ^{5 present} may be the same or different. ]

Further, the present invention provides a colored cured film formed using the above colored composition and a display element comprising the colored cured film. Here, the "coloring cured film" means a pixel of each color used in a display element or a solid-state image sensor, a black matrix, a black spacer, or the like.

The coloring composition of the present invention has good storage stability. Further, when the colored composition of the present invention is used, a high-color colored cured film can be formed.

Therefore, the coloring composition of the present invention is extremely suitable for producing a solid-state imaging element such as a color liquid crystal display element, an organic EL display element, a display element such as an electronic paper, or a CMOS image sensor.

[Formation of the Invention]

Hereinafter, the present invention will be described in detail.

Coloring composition

Hereinafter, the constituent components of the colored 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 has the following formula The compound of the structure shown in (2) (hereinafter, also referred to as "compound (2)") is (A) a coloring agent.

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

p represents 1 or 2. Wherein, when p is 2, a plurality of R ¹ and R ^{2 present} may be the same or different.

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

[In the formula (2), the ring Z ³ and the ring Z ⁴ independently of each other 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 independently of each other represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group. The plurality of R ⁴ and R ^{5 present} may be the same or different. ]

The heterocyclic ring in the ring Z ¹ to the ring Z ⁴ may be a monocyclic hetero ring or a polycyclic hetero ring. The heterocyclic ring 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 kind or different types in the ring. For example, a pyrrolidine ring, a pyrazoline ring, Porphyrin ring, thio Phenanthene ring, piperidine ring, piperazine Ring, high piper a nitrogen-containing alicyclic heterocyclic ring such as a ring or a tetrahydropyrimidine ring; a pyridine ring or a pyridyl group Ring, pyrimidine ring, anthracene Ring, quinoline ring, isoquinoline ring, anthracene Ring, quin a porphyrin ring, an imidazole ring, a pyrazole ring, a triazole ring, a tetrazole ring, a thiazole ring, a benzothiazole ring, Oxazole ring, anthracene ring, indazole ring, benzimidazole ring, benzo a nitrogen-containing aromatic heterocyclic ring such as an azole or a phthalic acid imine ring; or an aromatic heterocyclic ring such as a thiophene ring, a furan ring or an anthracene ring. Among them, a nitrogen-containing aromatic heterocyclic ring is preferred, and an anthracene ring and a benzo ring are more preferred. The azole ring and the benzothiazole ring are further more preferably an anthracene ring.

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

When p is 1, q represents an integer of 2 or more, but is preferably 2 or 3, more preferably 2. Further, 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 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. Specifically, 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 second butyl group, a third butyl group, a hexyl group, a heptyl group, and a octyl group. Base, fluorenyl, fluorenyl, undecyl, 1-methylindenyl, dodecyl, 1-methyldodecyl, 1-ethylindenyl, tridecyl, tetradecyl , thirty-dodecyl, pentadecyl, 1-heptyloctyl, hexadecyl, octadecyl, eicosyl-1-yl, docosa-1-yl, twentieth Trialkyl-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 bridged 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 t-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, a bridged hydrocarbon group such as isobornyl, dicyclopentenyl or tricyclopentenyl; a monovalent group obtained by removing one hydrogen atom from spiro[3,4]heptane or spiro[3,4]octane The spirocyclic hydrocarbon group; a cyclic terpene group such as a monovalent group obtained by removing one hydrogen atom from menthane, arborane, decane or the like. More preferably, the above cycloalkyl group and cycloalkenyl group have 3 to 12 carbon atoms.

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

Examples of the substituent of the hetero ring of the ring Z ¹ to the ring Z ⁴ and the hydrocarbon group of R ¹ to R ⁶ include a halogen atom, a hydroxyl group, a cyano group, a decyl group, a carboxyl group, a nitro group, an amine group, and a dialkylamine. , diarylamino, alkoxy, aryloxy, alkoxycarbonyl, alkylthio, arylthio, trialkylcarbenyl, decyl, allyl, alkylsulfonyl, An alkylamine sulfonyl group, an aliphatic hydrocarbon group, a heterocyclic group, an aromatic hydrocarbon group or 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)"). Further, a 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.

The ring Z ^1A and the ring Z ^2A independently of each other 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 independently of each other represent a substituted or unsubstituted hydrocarbon group. ]

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

The ring Z ^3A and the ring Z ^4A independently of each other 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 independently of each other represent a substituted or unsubstituted hydrocarbon group. ]

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

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 -. As the hydrocarbon group in R ¹³ and R ¹⁴ , 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.

Q ³ and Q ^{4 are} preferably -O-, -CR ²³ R ²⁴ -. As the hydrocarbon group in R ²³ and R ²⁴ , 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, 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 thereof are the same as those exemplified as the hydrocarbon groups 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 preferred, and an alkyl group is more preferred. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms.

When the structure represented by the formula (1) and the structure represented by the formula (2) are cationic, the compound having such a 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 sulfonate anion, a nitrogen anion, a methide anion, and a transition metal complex having an azo compound in the ligand. Anion, etc.

Examples of the halogen ion include a fluoride ion, a chloride ion, a bromide ion, and an iodide ion. Examples of the boron anion, the phosphate anion, and the nitrogen anion include the ions described in paragraphs [0037] to [0039] of JP-A-2012-173399. Examples of the carboxylic acid anion include a carboxylic acid anion described in JP-A-2009-265641 and JP-A-2008-096680. Examples of the sulfate anion include a sulfate anion, a sulfite anion, and the like. Examples of the organic sulfonic acid anion include JP-A-2012-173399, International Publication No. 2011/037195, International Publication No. 2011/162217, Japanese Patent No. 3372221, and Japanese Patent Application No. 2011-070172. The organic sulfonic acid anion described in the publication. As the methide anion, for example, JP-A A methide anion described in JP-A-2005-505787, JP-A-2005-309657, JP-A-2004-085657, and JP-A-2010-505787.

The anion of the transition metal complex having an azo compound in the ligand is, for example, an anion described in JP-A-2009-212226 and JP-A-2012-212089.

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

Specific examples of the boron anion 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, and the like.

Further, 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 colored composition of the present invention, the content of the compound (2) is required to be 0.001% by mass or more based on the total content of the compound (1) and the compound (2). The present inventors have estimated that the solubility of the compound (1) in a solvent is low, and it is easy to crystallize and become a foreign matter. Therefore, the storage stability of the colored composition is poor. In addition, it is presumed that the compound (1) is contained in a predetermined amount or more together with the compound (1), and 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% by mass or more, more preferably 0.005% by mass or more, and further preferably the total content of the compound (1) and the compound (2). It is 0.008% by mass or more, and particularly preferably 0.01% by mass or more. In addition, from the viewpoint of forming a colored cured film having a higher brightness, it is preferably 1% by mass or less, more preferably 0.4% by mass or less, further preferably 0.1% by mass or less, and still more preferably 0.09% by mass or less. More preferably, it is 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, still more preferably 0.005 to 0.1% by mass, even more preferably the total content of the compound (1) and the compound (2). Further, it is more preferably 0.01 to 0.1% by mass, particularly preferably 0.01 to 0.08% by mass.

The coloring composition of the present invention may further contain a coloring agent other than the compound (1) and the compound (2) (hereinafter also referred to as "another coloring agent"). The other coloring agent is not particularly limited, and a color or a material can be appropriately selected depending on the application, and a color other than the compound (1) and the compound (2) can be selected. Both materials and dyes can be used. Among them, in the meaning of obtaining a colored cured film having high brightness and color purity, an organic pigment or an organic dye is preferred.

As the above-mentioned organic pigment, for example, a compound classified as a pigment in a color index (CI; issued by The Society of Dyers and Colourists) can be cited. Among them, preferred are 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 Violet 23, and the like. In addition, Japanese Laid-Open Patent Publication No. 2001-081348, JP-A-2010-026334, JP-A-2010-191304, JP-A-2010-237384, JP-A-2010-237569 The brominated diketopyrrolopyrrole pigment represented by the formula (Ic) of JP-A-2011- 523 433, Japanese Laid-Open Patent Publication No. 2011-145346, and the like. . Among the lake pigments, preferred are triarylmethane-based lake pigments, a lake pigment, an azo lake pigment, more preferably a triaryl methane lake pigment and It is a lake pigment.

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. Further, the pigment may be used by modifying the surface of the particles with a resin as needed. As a resin that modifies the surface of the particles of the pigment, for example The vehicle resin described in JP-A-2001-108817 or a commercially available resin for dispersing various pigments is exemplified. For the resin coating method of the surface of the carbon black, for example, the method described in JP-A-H09-71733, JP-A-9-95625, and JP-A-9-124969 can be used. Further, the organic pigment can be used by making the primary particles fine by a so-called salt milling. As a method of salt milling, for example, the method disclosed in Japanese Laid-Open Patent Publication No. Hei 8-179111 can be employed.

In the present invention, when a pigment is used as the other coloring agent, it may further contain a well-known dispersing agent and a dispersing aid. 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-based dispersing agent, a sorbitan fatty acid ester-based dispersing agent, a polyester-based dispersing agent, an acrylic dispersing agent, and the like, and examples of the dispersing aid include a pigment derivative.

Such a dispersing agent can be obtained commercially. For example, as an acrylic dispersing agent, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (above BYK-Chemie (BYK)) As a polyurethane dispersant, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182, Disperbyk-2164 (above BYK-Chemie) (BYK), manufactured by Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), and as a polyethyleneimine-based dispersant, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), and a polyester-based dispersant, Adisper PB821, Adisper PB822, Adisper PB880, Adisper PB881 (above is Ajinomoto Fine-Techno), in addition to BYK-LPN21324 (40% by mass non-volatiles) (BYK-Chemie (BYK)) System) and so on.

Further, specific examples of the pigment derivative include sulfonium cyanine, diketopyrrolopyrrole, and a sulfonic acid derivative of quinacridone.

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

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

When forming a red pixel, as the (A) coloring agent, it is preferable to contain, together with the compound (1), a red pigment, a red dye, a violet pigment, a violet dye, a yellow pigment, a yellow dye, and the like selected from the compound (1). At least one of the orange pigments is used as another coloring agent. When the green pixel is formed, as the (A) coloring agent, at least one selected from the group consisting of a green pigment other than the compound (1), a green dye, a yellow pigment, and a yellow dye is preferably contained as the coloring agent (A). Coloring agent.

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

As the above red dye or purple dye, preferably Is a dye.

From the viewpoint of forming a black matrix or a black separator which is excellent in low chromaticity and low in chromaticity characteristics and which is less likely to cause defects, and in the solid content of the colored composition, (A) the content of the colorant is usually It is 5 to 70% by mass, preferably 10 to 60% by mass, more preferably 15 to 40% by mass. Here, the solid component is a component other than the solvent described later.

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

- (B) Adhesive Resin -

The (B) binder resin in the present invention is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. In particular, a polymer having a carboxyl group (hereinafter also referred to as a "carboxyl group-containing polymer") is preferably an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter, also referred to as "unsaturated". A copolymer of a 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, succinic acid mono [2-(methyl) propylene methoxyethyl] ester, and ω-carboxyl group. 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.

In addition, examples of the unsaturated monomer (b2) include an N-position substituted maleimide such as N-phenylmaleimide or N-cyclohexylmaleimide; An aromatic vinyl compound such as styrene, α-methylstyrene, vinyl toluene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, terpene; For example, methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, Benzyl (meth)acrylate, polyethylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2~10) 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[methyl]acrylic acid [5.2.1.0 ^2,6 ]decane-8-yl ester, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, (meth)acrylic acid 4-hydroxyphenyl ester, pair Ethylene oxide modified (meth) acrylate of phenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, (meth) acrylate 3, 4 - epoxy tricyclo [5.2.1.0 ^2,6 ]decane-8-yl ester, (meth)acrylic acid 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-9-yl ester, 3-[(Meth)acryloxymethyl]oxetane, 3-[(meth)acryloxymethyl]-3-ethyloxetane (methyl) Acrylate; such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ]decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3- a vinyl ether such as (vinyloxymethyl)-3-ethyloxetane; in, for example, polystyrene, poly(methyl) methacrylate, poly(methyl) acrylate, poly A macromolecular monomer having a mono(meth)acryl fluorenyl group at the end of the polymer molecular chain such as a decane.

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

Among these unsaturated monomers (b2), preferred are ethylenically unsaturated monomers having an epoxy group, ethylenically unsaturated monomers having an oxetanyl group, and ethylenic unsaturation having a tetrahydrofuranyl 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 epoxy group. As the ethylenically unsaturated monomer having an epoxy group, 3,4-epoxycyclohexylmethyl (meth)acrylate and 3,4-epoxytricyclo(meth)acrylate [5.2.1.0] are preferred. ^2,6 ]decane-8-yl ester, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-9-yl (meth)acrylate.

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 from 5 to 50% by mass, further preferably 10 ~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.

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. No. 31308 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. No. Hei. Copolymer.

In the present invention, for example, Japanese Laid-Open Patent Publication No. Hei 5-19467, JP-A-H06-230212, JP-A-H07-207211, JP-A No. Hei 9-325494, and JP-A No. 9-325494 A carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acrylonitrile group in a side chain disclosed in Japanese Laid-Open Patent Publication No. 2008-181095, or the like, is used as a binder resin.

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

Further, 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 from 1.0 to 5.0, more preferably from 1.0 to 3.0. In addition, the term "Mn" as used herein means a polystyrene-equivalent number average molecular weight measured by GPC (elution solvent: tetrahydrofuran).

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

In the present invention, the binder resin may be used singly or in combination of two or more.

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, more preferably 50 to 200 parts by mass, per 100 parts by mass of the (A) coloring agent. More preferably 80 to 150 parts by mass. By doing so, it is possible to further improve the alkali developability, the storage stability of the colored composition, the pattern shape, and the chromaticity characteristics.

- (C) Polymeric 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 epoxy 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)acryl fluorenyl groups or a compound having two or more N-alkoxymethylamino groups.

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

Here, examples of the aliphatic polyhydroxy compound include a two-membered product such as ethylene glycol, propylene glycol, polyethylene glycol, or polypropylene glycol. An aliphatic polyhydroxy compound; a trihydric or higher aliphatic polyhydroxy compound such as glycerin, trimethylolpropane, pentaerythritol or dipentaerythritol. 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 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, a biphenyltetracarboxylic dianhydride, or a benzophenone tetracarboxylic dianhydride.

In addition, examples of the polyfunctional (meth) acrylate modified by the caprolactone include the compounds described in paragraphs [0015] to [0018] of JP-A-11-44955. The polyfunctional (meth) acrylate modified with the alkylene oxide may, for example, be bisphenol A di(meth)acrylate modified with at least one selected from the group consisting of ethylene oxide and propylene oxide. And at least one modified isocyanuric acid tri(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide, modified by at least one selected from the group consisting of ethylene oxide and propylene oxide Trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate modified by at least one selected from the group consisting of ethylene oxide and propylene oxide, selected from ethylene oxide and At least one modified pentaerythritol tetra(meth)acrylate in propylene oxide, dipentaerythritol penta(meth)acrylate modified by at least one selected from the group consisting of ethylene oxide and propylene oxide At least one modified di-pentazone selected from the group consisting of ethylene oxide and propylene oxide Tetraol hexa(meth) acrylate or the like.

In addition, examples of the compound having two or more N-alkoxymethylamino groups include a compound having a melamine structure, a benzoguanamine structure, and a urea structure. It should be noted that the melamine structure and the benzoguanamine structure refer to having one or more three Ring or phenyl substituted three The chemical structure of the ring as a 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)glycolil and the like.

Among these polymerizable compounds, a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid or a polyfunctional (methyl group) modified with caprolactone is preferred. Acrylate, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate having carboxyl group, N, N, N', N', N", N"-hexa (alkoxy) Methyl) melamine, N, N, N', N'-tetrakis(alkoxymethyl)benzoguanamine. From the viewpoint of high strength of the colored layer, excellent surface smoothness of the colored layer, and difficulty in generation of dirt and film residue on the substrate of the unexposed portion and the light shielding layer, the aliphatic polyhydroxy compound having three or more members is used. Among the polyfunctional (meth) acrylates obtained by the reaction of (meth)acrylic acid, particularly preferred are trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, Among the polyfunctional (meth) acrylates of a carboxyl group, a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, and dipentaerythritol pentaacrylate and a A compound obtained by reacting phenolic anhydride.

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

The content of the (C) polymerizable compound in the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 700 parts by mass, still more preferably 50 to 500 parts by mass, per 100 parts by mass of the (A) coloring agent. Further, it is more preferably 80 to 250 parts by mass. Further, the content of the (C) polymerizable compound is preferably 50 to 300 parts by mass, more preferably 70 to 200 parts by mass, still more preferably 100 to 150 parts by mass, per 100 parts by mass of the (B) binder resin. In this manner, it is possible to further improve the curability and the alkali developability, and to suppress the generation of dirt, film residue, and the like on the substrate of the unexposed portion or the light shielding layer at a high level.

-(D) Photopolymerization Initiator -

The coloring composition of the present invention may contain a photopolymerization initiator. Thereby, it is possible to impart radiation sensitivity to the colored composition. The photopolymerization initiator used in the present invention is a compound which generates an active species which can initiate polymerization of the above polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam or X-ray.

Examples of such a photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a biimidazole compound, and the like. a compound, an O-antimony compound, an onium salt compound, a benzoin compound, a benzophenone compound, an α-diketone compound, a polycyclic anthracene compound, a diazo compound, a quinone sulfinate compound, or the like.

In the present invention, the photopolymerization initiator may be used singly or in combination of two or more. As the photopolymerization initiator, it is preferably selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, and three At least one of a compound and an O-tellurium compound.

In a preferred photopolymerization initiator of the present invention, specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxene. Ketone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyl Ketyl ketone and the like.

Further, specific examples of the acetophenone compound include 2-methyl-1-[4-(methylthio)phenyl]-2- Olinone propan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenyl-phenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Phenidophenyl)butan-1-one and the like.

Further, 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.

In the case where a biimidazole compound is used as the photopolymerization initiator, it is preferred to use a hydrogen donor in combination from the viewpoint of improving sensitivity. The term "hydrogen donor" as used herein refers to a compound capable of supplying a hydrogen atom to a radical generated by a biimidazole compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzoene. An amine hydrogen donor such as a thiol donor hydrogen donor, 4,4'-bis(dimethylamino)benzophenone or 4,4'-bis(diethylamino)benzophenone. In the present invention, the hydrogen donor may be used singly or in combination of two or more. However, from the viewpoint of further improving the sensitivity, it is preferred to combine one or more kinds of thiol hydrogen donors and one or more amine hydrogen donors. use.

In addition, as the above three Specific examples of the compound include 2,4,6-tris(trichloromethyl)-s-three. 2-methyl-4,6-bis(trichloromethyl)-s-three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-three ,2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-three Three with a halogenated methyl group Compound.

Further, specific examples of the O-tellurium 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-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-ethanone 1-(O-acetamidine), 1-[9-ethyl- 6-{2-Methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene}-9H-indazol-3-yl]-ethanone 1-(O-acetamidine) and the like. As a commercial item of the O-oxime compound, NCI-831, NCI-930 (above, ADEKA Co., Ltd.), DFI-020, DFI-091 (manufactured by Daitochemix Co., Ltd.), or the like can be used.

In the present invention, when a photopolymerization initiator other than the biimidazole compound such as an acetophenone compound is used, a sensitizer may be used in combination. As such a sensitizer, for example, 4,4'-bis(dimethylamino)benzophenone can be mentioned. , 4,4'-bis(diethylamino)benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 4-dimethylaminobenzoic acid Ester, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3- 4-Diethylaminobenzimidyl)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, still more preferably 5 to 50 parts by mass based on 100 parts by mass of the (C) polymerizable compound. The mass fraction is particularly preferably 10 to 30 parts by mass. By adopting such an aspect, the curability and the film properties can be further improved.

- (E) Solvent -

The colored composition of the present invention contains the above components (A) to (C) and optionally added other components, and is usually prepared as a liquid composition in combination with a solvent.

The (E) solvent is appropriately selected and used as long as it disperses or dissolves the components (A) to (C) constituting the colored composition and other components, and does not react with these components, and has appropriate volatility.

Examples of such a solvent 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 , 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. Alcohol monoalkyl ethers; Methyl lactate such as methyl lactate or ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tert-butanol, octanol, 2-ethylhexanol, cyclohexanol Ketone alcohols such as (cyclo)alkyl alcohols; diacetone alcohols; 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 Alkyl diol 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 diacetic acid Diacetate such as ester; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethoxylate Alkoxycarboxylates such as ethyl acetate and 3-methyl-3-methoxybutylpropionate; 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 acrylate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutyrate, etc. Esters; aromatic hydrocarbons such as toluene and xylene; decylamines such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or indoleamines Wait.

Among these solvents, from the viewpoints of solubility, pigment dispersibility, coatability, and the like, (poly)alkylene glycol monoalkyl ethers, alkyl lactates, and (poly)alkylene glycols are preferred. Alkyl ether acetates, other ethers, ketones, diacetates, alkoxycarboxylates, other esters, particularly preferably propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl Ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl 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-amyl formate, acetic acid Isoamyl ester, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, and the like.

In the present invention, the solvent may be used singly or in combination of two or more.

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

-additive-

The colored composition of the present invention may further contain various additives as needed.

Examples of the additive include a filler such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); and fluorine. Surfactant, surfactant such as surfactant, ketone surfactant; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2-amine Benzyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxylate Baseline, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Baseline, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane Equal adhesion promoter; 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-t-butylphenol, pentaerythritol tetra[3-(3,5-di Third butyl-4-hydroxyphenyl)propionate], 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propanoxime 1,1-dimethylethyl]-2,4,8,10-tetraoxa-spiro[5.5]undecane, thiodiethylidene bis[3-(3,5-di Antioxidant such as third butyl-4-hydroxyphenyl)propionate; 2-(3-third Ultraviolet absorbers such as 5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and alkoxybenzophenone; antiflocculating agents such as sodium polyacrylate; malonic acid and adipic acid , itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1, Residue improver such as 2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol; succinic acid mono[2-(methyl)acryloxyethyl] A developer improving agent such as an ester, a mono[2-(methyl)acryloxyethyl) phthalate, or an ω-carboxypolycaprolactone mono(meth)acrylate.

Further, when the coloring composition of the present invention uses both a dye and a pigment as a coloring agent, as disclosed in Japanese Laid-Open Patent Publication No. 2010-132874, a preparation method may be employed in which a dye solution is passed. After the first filter, the dye solution passing through the first filter is mixed with a separately prepared pigment dispersion or the like, and the resulting colored composition is prepared by a second filter. In addition, a preparation method may be employed in which a dye, the above components (B) to (C), and other components used as needed are dissolved in a solvent, so that the obtained solution passes through the first filter and passes through the first filter. The solution was mixed with a separately prepared pigment dispersion such that the resulting colored composition was prepared through a second filter. Alternatively, a preparation method may be employed in which the dye solution passing through the first filter is mixed with the components (B) to (C) and other components used as needed after passing the dye solution through the first filter. The solution was dissolved, the resulting solution was passed through a second filter, and the solution passing through the second filter was mixed with the separately prepared pigment dispersion, so that the obtained colored composition was prepared through the third filter.

Colored hardening film and method of forming same

The colored cured film of the present invention is formed using the colored composition of the present invention, and specifically refers to each color pixel, black matrix, black spacer, and the like constituting the color filter.

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

As a method of manufacturing a color filter, the first method is as follows. First, a light shielding layer (black matrix) is formed on the surface of the substrate in such a manner as to divide a portion where pixels are formed. Next, a liquid composition of, for example, a red radiation-sensitive coloring composition of the present invention is applied onto the substrate, and then pre-baked to evaporate the solvent to form a coating film. Next, the coating film was exposed by a photomask, and then developed with an alkali developing solution to dissolve and remove the unexposed portion of the coating film. After that, after passing After baking, a pixel array in which red pixel patterns (colored cured films) are arranged in a predetermined arrangement is formed.

Next, using each of the radiation-sensitive coloring compositions of green or blue, the coating, prebaking, exposure, development, and post-baking of each of the radiation-sensitive coloring compositions are performed in the same manner as described above, and green pixels are sequentially formed on the same substrate. Array and blue pixel array. Thereby, a color filter in which a pixel array of three primary colors of red, green, and blue is disposed on the substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above order.

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

Examples of the substrate used for forming the color filter include glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidimide, and polyimide.

Further, as appropriate, these substrates may be subjected to an appropriate pretreatment such as reagent treatment such as a decane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, or vacuum vapor deposition.

When a radiation-sensitive coloring composition is applied onto a substrate, a spray coating method, a roll coating method, a spin coating method, a slit die coating method (slit coating method), a bar coating method, or the like may be employed. The coating method is particularly preferably a spin coating method or a slit die coating method.

The pre-baking is usually carried out by combining dry-pressure drying and heat drying. Drying under reduced pressure usually proceeds to 50 to 200 Pa. In addition, the conditions of heat drying Usually 70~110 °C, 1~10 minutes or so.

The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, in terms of the film thickness after drying.

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

The exposure amount of the radiation is generally preferably from 10 to 10,000 J/m ² .

Further, as the above alkaline developing solution, for example, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-diazabicyclo-[5.4 is preferred. .0] an aqueous solution of 7-undecene, 1,5-diazabicyclo-[4.3.0]-5-decene.

A water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline developer in an appropriate amount. Incidentally, after alkaline development, water washing is usually performed.

As the development treatment method, a shower 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 from normal temperature to 5 to 300 seconds.

The post-baking conditions are usually 180 to 280 ° C for about 10 to 60 minutes.

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

In addition, as a second method of producing a color filter, a method of obtaining pixels of respective colors by an inkjet method disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2000-310706, and the like. In this method, first, a partition wall which also has a light blocking 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, and then pre-baked to evaporate the solvent. Next, the coating film is exposed as needed, and then cured by post-baking to form a blue pixel pattern.

Next, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate in the same manner as described above using each of the green or blue thermosetting coloring composition. Thereby, a color filter in which pixel patterns of three primary colors of red, green, and blue are arranged on the substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above-described order.

In addition, since the partition wall not only functions as a light-shielding function but also functions to prevent color mixing of the thermosetting coloring compositions of the respective colors discharged into the compartments, the film thickness is thinner than that of the black matrix used in the first method. It is thick. Therefore, the partition walls are usually formed using a black radiation sensitive composition.

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

After forming a protective film as needed on the pixel pattern thus obtained, a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer may be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but a spacer having a light-shielding property (black spacer) may also 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 for forming a colored cured film of any of the color pixels, the black matrix, and the black spacer used in the color filter.

The color filter including the colored cured film of the present invention thus formed has extremely high brightness and color purity, and thus is extremely excellent in a color liquid crystal display element, a color image pickup element, a color sensor, an organic EL display element, an electronic paper, or the like. it works. In addition, the display element which will be described later may be provided with at least one or more colored cured films formed using the radiation-sensitive coloring composition of the present invention.

Display component

The display element of the present invention comprises 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 having the colored cured film of the present invention may be of a transmissive type or a reflective type, and an appropriate structure may be employed. For example, a color filter may be formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is disposed, and the substrate for driving and the substrate on which the color filter is formed may be opposed to each other via the liquid crystal layer. In addition, you can also take A substrate on which a color filter is formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed, 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 an advantage of being able to remarkably 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 one of 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 device including the colored cured 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 in which a combination of a red LED, a green LED, and a blue LED obtains white light by color mixing, and a combination of a blue LED, a red LED, and a green phosphor to obtain white light by color mixing, combined blue The color LED, the red illuminating phosphor and the green illuminating phosphor obtain a white LED of white light by color mixing, and a white LED of white light is obtained by color mixing of the blue LED and the YAG-based phosphor, and the combination of the blue LED and the orange illuminating illuminating The light body and the green light-emitting phosphor obtain a white light white LED by color mixing, and a white LED or the like which combines the ultraviolet light LED, the red light-emitting phosphor, the green light-emitting phosphor, and the blue light-emitting phosphor to obtain white light by color mixing.

The color liquid crystal display element having the colored cured film of the present invention can be TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, or IPS (In-Planes Switching) type. , VA (Vertical Alignment) type, OCB (Optically Compensated Birefringence, light) Appropriate liquid crystal mode such as compensation and bending arrangement.

In addition, the organic EL display element having the colored cured film of the present invention may have a suitable structure, and for example, a structure disclosed in Japanese Laid-Open Patent Publication No. Hei 11-307242.

In addition, the electronic paper provided with the colored cured film of the present invention may have a suitable structure, and for example, the structure disclosed in JP-A-2007-41169 can be cited.

[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 embodiments.

<Synthesis of Colorants>

Synthesis Example 1

To a 300 mL eggplant-shaped flask equipped with a stirrer, 9.7 g of 2,3,3-trimethylporphyrin, 25.9 g of 1-iodomethane, and 85 mL of acetonitrile were placed, and the mixture was stirred for 10 hours while heating under reflux. After cooling to room temperature, the reaction solution was added to 425 mL of diisopropyl ether, ice-cooled, and allowed to stand for 30 minutes. Thereafter, the precipitate was filtered by suction filtration, and the obtained solid was dried under reduced pressure to yield 16.1 g of 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

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

Synthesis Example 3

The coloring agent (A-2) was recrystallized by the following method. Specifically, 5.0 g of the color former (A-2) obtained in Synthesis Example 2 and 100 g of ion-exchanged water containing 10% by mass of ethanol were placed in a 300 mL eggplant-shaped flask equipped with a stirrer, and the mixture was stirred at 80 ° C for 2 hours. Thereafter, the solution was cooled and allowed to stand at 5 ° C overnight. The precipitate was filtered by suction filtration, and the obtained solid was dried under reduced pressure to yield 4.6 g of a reddish solid. This compound was used as a coloring agent (A-3).

Synthesis Example 4

The coloring agent (A-3) was recrystallized by the following method. That is, in the To a 300 mL eggplant-shaped flask of the stirrer, 5.0 g of the color former (A-3) obtained in Synthesis Example 3 and 100 g of ion-exchanged water containing 10% by mass of ethanol were placed, and the mixture was stirred at 80 ° C for 2 hours. Thereafter, the solution was cooled and allowed to stand at 5 ° C overnight. The precipitate was filtered by suction filtration, and the obtained solid was dried under reduced pressure to yield 4.3 g. This compound was used as a coloring agent (A-4).

Synthesis Example 5

3.0 g of the color former (A-2) obtained in Synthesis Example 2, 2.7 g of lithium bistrifluoromethanesulfonimide, 24 mL of acetonitrile, 36 mL of ethyl acetate, and ions were placed in a 300 mL eggplant-shaped flask equipped with a stir bar. 30 mL of water was exchanged and stirred 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. Then, the organic layer was concentrated under reduced pressure using a rotary evaporator, and dried under vacuum at 50 ° C overnight to give 4.0 g of dark red solid. The solid obtained was confirmed to be a mixture of the compound represented by the above formula (A5-1) and the compound represented by the above formula (A5-2) by analysis of ¹ H-NMR and LC-MS. This compound was used as a coloring agent (A-5).

Synthesis Example 6

In the synthesis example 5, the same reaction operation as in the synthesis example 5 was carried out except that the colorant (A-3) was used instead of the colorant (A-2), and the compound represented by the above formula (A5-1) and the above were obtained. A mixture of compounds represented by the formula (A5-2). The obtained compound was used as a coloring agent (A-6).

Synthesis Example 7

In the synthesis example 5, the same reaction operation as in the synthesis example 5 was carried out except that the coloring agent (A-4) was used instead of the coloring agent (A-2), and the compound represented by the above formula (A5-1) and the above were obtained. A mixture of compounds represented by the formula (A5-2). The obtained compound was used as a coloring agent (A-7).

Synthesis Example 8

In Synthesis Example 5, except that 2.4 g of (vinylphenyl)trifluoromethanesulfonimide triethylamine salt was used instead of 2.7 g of lithium bistrifluoromethanesulfonimide, and Synthesis Example 5 was used. The same reaction operation. The solid obtained was confirmed to be a mixture of the compound represented by the above formula (A8-1) and the compound represented by the above formula (A8-2) by analysis of ¹ H-NMR and LC-MS. The obtained compound was used as a coloring agent (A-8).

Synthesis Example 9

In the synthesis example 8, the same reaction operation as in Synthesis Example 8 was carried out except that the colorant (A-3) was used instead of the colorant (A-2), and the compound represented by the above formula (A8-1) and the above were obtained. A mixture of compounds represented by the formula (A8-2). The obtained compound was used as a coloring agent (A-9).

Synthesis Example 10

In the synthesis example 8, the same reaction operation as in Synthesis Example 8 was carried out except that the colorant (A-4) was used instead of the colorant (A-2), and the compound represented by the above formula (A8-1) and the above were obtained. A mixture of compounds represented by the formula (A8-2). The obtained compound was used as a coloring agent (A-10).

Synthesis Example 11

In the same manner as in Synthesis Example 1, except that 30.9 g of 1-iodopropane was used instead of 25.9 g of 1-iodomethane, the compound (A11) represented by the above formula was obtained.

Synthesis Example 12

In the synthesis example 2, the same reaction operation as in Synthesis Example 2 was carried out, 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). The obtained compound was confirmed to be a mixture of the compound represented by the above formula (A12-1) and the compound represented by the above formula (A12-2) by analysis of ¹ H-NMR and LC-MS. This compound was used as a coloring agent (A-12).

Synthesis Example 13

In the synthesis example 3, the same recrystallization operation as in the synthesis example 3 was carried out 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 coloring agent (A-13).

Synthesis Example 14

In the synthesis example 4, the same recrystallization operation as in the synthesis example 4 was carried out, 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 coloring agent (A-14).

Synthesis Example 15

In the synthesis example 5, the same reaction operation as in the synthesis example 5 was carried out, 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 above formula (A15-1) and the compound represented by the above formula (A15-2) is obtained. The obtained compound was used as a coloring agent (A-15).

Synthesis Example 16

In the synthesis example 5, the same reaction operation as in the synthesis example 5 was carried out except that 3.3 g of the colorant (A-13) was used instead of 3.0 g of the colorant (A-2), and the above formula (A15-1) was obtained. A mixture of a compound and a compound represented by the above formula (A15-2). The obtained compound was used as a coloring agent (A-16).

Synthesis Example 17

In the synthesis example 5, the same reaction operation as in the synthesis example 5 was carried out except that 3.3 g of the colorant (A-14) was used instead of 3.0 g of the colorant (A-2), and the above formula (A15-1) was obtained. A mixture of a compound and a compound represented by the above formula (A15-2). The obtained compound was used as a coloring agent (A-17).

Purity confirmation

The acetonitrile solutions (colorant concentration: 1000 ppm) of the colorants (A-5) to (A-10) and (A-15) to (A-17) were separately prepared, and the purity was determined by high performance liquid chromatography according to the following analysis conditions. Quantitative. The concentration of the compound (2) in each coloring agent, that is, the compound having the structure represented by the formula (2), 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% aqueous solution of trifluoroacetic acid = 7 / 3 (v / v) mixed solvent

‧Tube: CAPCELLPAK C18 MG (5μ150x4.6mm, manufactured by Shiseido Co., Ltd.)

‧column oven set temperature: 40 ° C

‧ Sample injection amount: 10μL

‧Flow: 0.5mL/min

The concentrations of the compounds (2) in the colorants (A-7), (A-10) and (A-17) are shown in Table 1 to be lower than the detection limits in the high performance liquid chromatography.

<Preparation of Pigment Dispersion>

Preparation Example 1

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

<Preparation of colorant solution>

Preparation Example 2

A colorant solution (A-5) was prepared by mixing 10 parts by mass of the colorant (A-5) and 90 parts by mass of propylene glycol monomethyl ether.

Preparation Example 3~10

In the preparation example 2, the colorant solutions (A-6) to (A-10) and (A-15)~ were prepared in the same manner as in Production Example 2 except that the type of the colorant was changed as shown in Table 2. A-17).

<(B) Synthesis of binder resin>

Synthesis Example 18

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. Heating to 80 ° C, at this temperature, 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, methyl group were added 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 maintained at this temperature 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 binder resin solution (B1) (solid content concentration: 33% by mass). The obtained binder resin had a Mw of 12,200 and an Mn of 6,500.

Synthesis Example 19

A solution containing a resin having the following structural unit was obtained by the method described in Synthesis Example 6 of JP-A-2013-203955. Then, 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 coloring composition

Example 1

30.5 parts by mass of the pigment dispersion liquid (a-1) as the coloring agent (A), 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 (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as a (C) polymerizable compound, 2-benzyl group as a photopolymerization initiator -2-dimethylamino-1-(4- 1.8 parts by mass of phenyl phenyl)butane-1-one (trade name: IRGACURE 369, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 0.1 parts by mass of NCI-930 (manufactured by ADEKA CORPORATION), MEGAFAC F as a fluorine-based surfactant 0.05 parts by mass of 554 (manufactured by DIC Corporation) and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a colored composition (S-1) having a solid content concentration of 20% by mass.

Evaluation of chromaticity characteristics

The obtained coloring composition was applied onto a glass substrate using a spin coater, and then pre-baked by a hot plate at 80 ° C for 10 minutes to form a coating film. The three rotation speeds of the spin coater were changed to form three coating films having different film thicknesses by the same operation.

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

The color coordinate analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) was used for the obtained three colored cured films, and the chromaticity coordinate values (x, y) and the stimulation 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) at the chromaticity coordinate value y=0.329 are obtained. The evaluation results are shown in Table 3. It should be noted that it can be said that the higher the stimulation value (Y), the higher the brightness.

Foreign body evaluation

After applying a coloring composition (S-1) which was allowed to stand on a 10 cm × 10 cm soda lime glass substrate having a SiO ₂ film for preventing elution of sodium ions on the surface by a spin coater and allowed to stand at 5 ° C for 3 days, heat of 90 ° C was used. The plate was prebaked for 4 minutes to form a coating film having a film thickness of 2.5 μm after prebaking. When the substrate was observed by an optical microscope, if no foreign matter was observed on the coating film, it was marked as "○", and if the number of foreign matter on the coating film was 1 to 10, it was recorded as "△". When it is observed that the number of foreign matter on the coating film is 11 or more, it is indicated as "x". The evaluation results are shown in Table 3. Incidentally, the smaller the foreign matter, the more excellent the storage stability of the colored composition.

Examples 2 to 4 and Comparative Examples 1, 2

In the same manner as in Example 1, except that the type of the colorant solution was changed as shown in Table 3, a colored composition was prepared. Then, evaluation was performed in the same manner as in Example 1. The results are shown in Table 3.

Examples 5, 6 and Comparative Example 3

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, a coloring composition was prepared. Then, evaluation was performed in the same manner as in Example 1. The results are shown in Table 3.

Claims (7)

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