JP6398650B2 - Colored composition, colored cured film, and display element - Google Patents

Description

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

  In producing a color filter using a colored radiation-sensitive composition, a pigment-dispersed colored radiation-sensitive composition is applied on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape. A method of obtaining pixels of each color by irradiation (hereinafter referred to as “exposure”) and development is known (for example, see Patent Documents 1 and 2). In addition, a method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (see, for example, Patent Document 3) is also known. Furthermore, a method for obtaining pixels of each color by an ink jet method using a pigment-dispersed colored resin composition is also known (for example, see Patent Document 4).

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

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A JP 2009-235392 A

However, according to the study by the present inventors, it has been clarified that in a colored composition containing a cyanine dye as a colorant, the storage stability of the colored composition may be insufficient.
Accordingly, an object of the present invention is to provide a coloring composition containing a cyanine dye as a colorant and having good storage stability and capable of forming a colored cured film having high luminance. Moreover, the subject of this invention is providing the colored cured film formed using the said coloring composition, and the display element which comprises the same.

  As a result of intensive studies, the present inventors have 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, this invention is a coloring composition containing (A) a coloring agent, (B) binder resin, and (C) polymeric compound, Comprising: (A) A coloring agent is a structure represented by following formula (1). And the content of the compound having the structure represented by the following formula (2) includes the compound represented by the following formula (1). The present invention provides a colored composition that is 0.001% by mass or more based on the total content of the compound and the compound having a structure represented by the following formula (2).

  The present invention also includes a compound having a structure represented by the following formula (1) and a compound having a structure represented by the following formula (2), including a compound having a structure represented by the following formula (2). Provided a colorant whose amount is 0.001% by mass or more 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) To do.

[In Formula (1),
Ring Z ¹ and ring Z ² each independently represent a substituted or unsubstituted heterocycle.
p represents 1 or 2. However, 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 each independently represent a substituted or unsubstituted heterocycle.
q represents an integer of 2 or more when p is 1, and represents an integer of 3 or more when p is 2.
R ^{4 to} R ⁶ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group. However, a plurality of R ⁴ and R ⁵ may be the same or different. ]

  Moreover, this invention provides the display element which comprises the colored cured film formed using the said coloring composition, and this colored cured film. Here, the “colored cured film” means each color pixel, black matrix, black spacer, and the like used for a display element and a solid-state imaging element.

The coloring composition of the present invention has good storage stability. Moreover, if the colored composition of this invention is used, a highly bright colored cured film can be formed.
Therefore, the colored composition of the present invention can be used very suitably for the production of solid-state imaging devices such as color liquid crystal display devices, organic EL display devices, display devices such as electronic paper, and CMOS image sensors.

Hereinafter, the present invention will be described in detail.
Coloring composition will be described in detail components of the colored composition of the present invention.

-(A) Colorant-
The colored composition of the present invention is represented by (A) a colorant having a structure represented by the following formula (1) (hereinafter also referred to as “compound (1)”) and the following formula (2). And a compound having the structure (hereinafter also referred to as “compound (2)”).

[In Formula (1),
Ring Z ¹ and the ring Z ² are independently of each other, a substituted or unsubstituted heterocyclic.
p represents 1 or 2. However, 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 each independently represent a substituted or unsubstituted heterocycle.
q represents an integer of 2 or more when p is 1, and represents an integer of 3 or more when p is 2.
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. ]

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 may have two or more hetero atoms (for example, a nitrogen atom, an oxygen atom, and a sulfur atom) of the same type or different types in the ring. For example, nitrogen-containing alicyclic heterocycles such as pyrrolidine ring, pyrazoline ring, morpholine ring, thiomorpholine ring, piperidine ring, piperazine ring, homopiperazine ring, tetrahydropyrimidine ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, Quinoline ring, isoquinoline ring, phthalazine ring, quinoxaline ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, benzothiazole ring, oxazole ring, indole ring, indazole ring, benzimidazole ring, benzoxazole, phthalimide ring, etc. And other aromatic heterocycles such as a nitrogen-containing aromatic heterocycle, thienyl ring, furan ring, and purine ring. Among these, a nitrogen-containing aromatic heterocyclic ring is preferable, an indole ring, a benzoxazole ring, and a benzothiazole ring are more preferable, and an indole ring is still more preferable.

p represents 1 or 2, and p is preferably 1.
When p is 1, q represents an integer of 2 or more, preferably 2 or 3, and more preferably 2. When p is 2, q represents an integer of 3 or more, but 3 is preferable.
As a combination of p and q, p is 1 and q is preferably 2 or more, p is 1 and q is more preferably 2.
As a halogen atom in R < ¹ > -R < ⁶ >, a fluorine atom, a chlorine atom, a bromine atom can be mentioned, for example.
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. 1-30 are preferable, as for carbon number of these aliphatic hydrocarbon groups, 1-24 are more preferable, and 1-20 are especially preferable. These aliphatic hydrocarbon groups may be linear or branched. Specifically, as the alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, hexyl group, heptyl group, octyl group, nonyl Group, decyl group, undecyl group, 1-methyldecyl group, dodecyl group, 1-methylundecyl group, 1-ethyldecyl group, tridecyl group, tetradecyl group, tert-dodecyl group, pentadecyl group, 1-heptyloctyl group, hexadecyl group , Octadecyl group, heneicosan-1-yl group, docosan-1-yl group, tricosan-1-yl group, tetracosan-1-yl group and the like. Examples of the alkenyl group include ethenyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 1,3-butadienyl group, 1-pentenyl group, 2-pentenyl group, 1-hexenyl. Group, 2-ethyl-2-butenyl group, 2-octenyl group, (4-ethenyl) -5-hexenyl group, 2-decenyl group and the like. Examples of the alkynyl group include ethynyl group, 1-propynyl group, 1-butynyl group, 1-pentynyl group, 3-pentynyl group, 1-hexynyl group, 2-ethyl-2-butynyl group, and 2-octynyl group. , (4-ethynyl) -5-hexynyl group, 2-decynyl group and the like.

As an alicyclic hydrocarbon group, a C3-C30 alicyclic hydrocarbon group is preferable. The alicyclic hydrocarbon group may be saturated or unsaturated, for example, a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a bridged ring hydrocarbon group, a spiro hydrocarbon group, a cyclic terpene hydrocarbon group, etc. Can be mentioned. 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, and a cyclooctyl group; a cycloalkenyl group such as a 1-cyclohexenyl group; Condensed polycyclic hydrocarbon groups such as cyclodecanyl group, decahydro-2-naphthyl group, adamantyl group; tricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, pentacyclopentadecanyl group, Bridged ring hydrocarbon groups such as isobonyl group, dicyclopentenyl group, tricyclopentenyl group; monovalent group obtained by removing one hydrogen atom from spiro [3,4] heptane, spiro [3,4] octane, etc. Spiro hydrocarbon groups; cyclic terpene hydrocarbon groups such as monovalent groups obtained by removing one hydrogen atom from p-menthane, tujang, caran, etc. Can. The cycloalkyl group and cycloalkenyl group preferably have 3 to 12 carbon atoms.

  As an aromatic hydrocarbon group, a C6-C20 thing is preferable and a C6-C10 thing is more preferable. Examples of the aromatic hydrocarbon group include an aryl group. Here, the “aryl group” in this specification refers to a monocyclic to tricyclic aromatic hydrocarbon group, and specifically includes a phenyl group, a benzyl group, an o-tolyl group, an m-tolyl group, p. -Tolyl group, xylyl group, naphthyl group, anthryl group, phenanthryl group, azulenyl group, 9-fluorenyl group and the like can be mentioned.

Examples of the substituent of the heterocyclic ring in ring Z ¹ to ring Z ⁴ and the hydrocarbon group in R ^{1 to} R ⁶ include a halogen atom, a hydroxyl group, a cyano group, a formyl group, a carboxy group, a nitro group, an amino group, and a dialkylamino group. Group, diarylamino group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylthio group, arylthio group, trialkylsilyl group, mercapto group, allyl group, alkylsulfonyl group, alkylsulfamoyl group, aliphatic hydrocarbon group, A heterocyclic group, an aromatic hydrocarbon group, etc. can be mentioned.

  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, the compound having the structure represented by the formula (2) is preferably a compound having a structure represented by the following formula (2A) (hereinafter also referred to as “compound (2A)”).

[In Formula (1A),
R ^{1 to} R ³ have the same meanings as described above.
Ring Z ^1A and ring Z ^2A each independently represent a substituted or unsubstituted aromatic hydrocarbon ring.
Q ¹ and Q ² each independently represent —O—, —S—, or —CR ¹³ R ¹⁴ —.
R ^{11 to} R ¹⁴ each independently represent a substituted or unsubstituted hydrocarbon group. ]

[In Formula (2A),
q and R ^{4 to} R ⁶ are as defined above.
Ring Z ^3A and ring Z ^4A each independently represent a substituted or unsubstituted aromatic hydrocarbon ring.
Q ³ and Q ⁴ each independently represent —O—, —S—, or —CR ²³ R ²⁴ —.
R ^{21 to} R ²⁴ each independently represent a substituted or unsubstituted hydrocarbon group. ]

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

As R < ¹ > -R < ⁶ >, a hydrogen atom is preferable.
q is preferably 2.
Q ¹ and Q ^{2, -O -, - CR 13 R} 14 - are preferred. The hydrocarbon group for R ¹³ and R ¹⁴ is preferably an aliphatic hydrocarbon group, more preferably an alkyl group. As an alkyl group, a C1-C8 alkyl group is preferable, a C1-C4 alkyl group is more preferable, and a methyl group and an ethyl group are especially preferable.
Q ³ and Q ⁴ are preferably —O— or —CR ²³ R ²⁴ —. The hydrocarbon group for R ²³ and R ²⁴ is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. As an alkyl group, a C1-C8 alkyl group is preferable, a C1-C4 alkyl group is more preferable, and a methyl group and an ethyl group are especially preferable.

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 include the same ones as exemplified for the hydrocarbon group for R ¹ to R ^6. Especially, as a hydrocarbon group in R < ¹¹ > -R < ¹² > and R < ²¹ > -R < ²² >, an aliphatic hydrocarbon group is preferable and an alkyl group is more preferable. 1-12 are preferable, as for carbon number of an alkyl group, 1-8 are more preferable, and 1-6 are especially preferable.

  When the structure represented by the formula (1) and the structure represented by the formula (2) are cationic, an anion can be included so that the compound having the structure is electrically neutral. Examples of the anion include a halogen ion, a boron anion, a phosphate anion, a carboxylate anion, a sulfate anion, an organic sulfonate anion, a nitrogen anion, a metide anion, and an anion of a transition metal complex having an azo compound as a ligand. Can do.

Examples of the halogen ion include fluoride ion, chloride ion, bromide ion, and iodide ion. Examples of boron anions such as phosphate anions and nitrogen anions include those described in paragraphs [0037] to [0039] of JP2012-173399A. Examples of the carboxylate anion include the carboxylate anions described in JP-A-2009-265641 and JP-A-2008-096680. Examples of the sulfate anion include a sulfate anion and a sulfite anion. Examples of the organic sulfonate anion include, for example, JP 2012-173399 A, WO 2011/037195 pamphlet, WO 2011/162217 pamphlet, JP 3736221 pamphlet and JP 2011-070172 A. What has been described can be mentioned. Examples of the methide anion include, for example, JP 2011-145540 A, US Pat. No. 5,554,664, JP 2005-309408 A, JP 2004-085657 A, and JP 2010-505787 A. Can be mentioned.
Examples of the anion of the transition metal complex having an azo compound as a ligand include anions described in JP2009-163226A and JP2012-212089A.

Among these anions, a boron anion, a nitrogen anion, and an anion of a transition metal complex having an azo compound as a ligand are preferable, and a boron anion and a nitrogen anion are more preferable.
Specific examples of the boron anion include, for example, 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 -, (n-C 3 F 7 CH 2) 2 B (CN) 2 -, (C 6 H 5) 3 B (CN) -, tetrakis ( And pentafluorophenyl) borate anion.
Specific examples of the nitrogen anion include, for example, [(CN) ₂ N] ⁻ , [(FSO ₂ ) ₂ N] ⁻ , [(FSO ₂ ) N (CF ₃ SO ₂ )] ⁻ , and [(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 this invention, content of a compound (2) needs to be 0.001 mass% or more with respect to the total content of a compound (1) and a compound (2). The present inventors presume that the compound (1) has low solubility in a solvent and is likely to be crystallized into a foreign substance, so that the storage stability of the colored composition may be deteriorated. And it is speculated that the compound (1) is prevented from crystallizing by containing a predetermined amount or more of the compound (2) together with the compound (1), and the storage stability of the colored composition is improved. The content of the compound (2) is preferably 0.003% by mass or more based on the total content of the compound (1) and the compound (2) from the viewpoint of further improving the storage stability. More preferably, it is more preferably 0.008% by mass or more, and particularly preferably 0.01% by mass or more. Further, from the viewpoint of forming a colored cured film having higher luminance, 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 further preferably 0.09% by mass or less. 0.08 mass% or less is still more preferable, and 0.07 mass% or less is still more preferable. The content of the compound (2) is preferably 0.001 to 1% by mass, more preferably 0.003 to 0.4% by mass, more preferably the total content of the compound (1) and the compound (2). Preferably it is 0.005-0.1 mass%, More preferably, it is 0.01-0.1 mass%, Most preferably, it is 0.01-0.08 mass%.

  The colored composition of the present invention can also contain a colorant other than the compound (1) and the compound (2) (hereinafter also referred to as “other colorant”). The other colorant is not particularly limited, and the color and material can be appropriately selected depending on the application, and any of pigments and dyes other than compound (1) and compound (2) is used. be able to. Among these, organic pigments and organic dyes are preferable in terms of obtaining a colored cured film having high luminance and color purity.

  Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists). Among them, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 179, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment red 264, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 80, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 211, C.I. I. Pigment yellow 215, C.I. I. Pigment orange 38, C.I. I. Pigment Violet 23 and the like are preferable. JP-A-2001-081348, JP-A-2010-026334, JP-A-2010-191304, JP-A-2010-237384, JP-A-2010-237569, JP-A-2011-006602, Lake pigments described in JP 2011-145346 A and the like, and brominated diketopyrrolopyrrole pigments represented by formula (Ic) in JP 2011-523433 A are also preferable. Among the lake pigments, triarylmethane lake pigments, xanthene lake pigments, and azo lake pigments are preferable, and triarylmethane lake pigments and xanthene lake pigments are more preferable.

  In the present invention, when a pigment is used as another colorant, the pigment may be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Moreover, the pigment surface may be used by modifying the particle surface with a resin if desired. Examples of the resin that modifies the particle surface of the pigment include vehicle resins described in JP-A No. 2001-108817, and various commercially available resins for dispersing pigments. As a resin coating method on the carbon black surface, for example, methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969 and the like can be employed. The organic pigment may be used after the primary particles are refined by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Laid-Open No. 8-179111 can be employed.

  In the present invention, when a pigment is used as another colorant, a known dispersant and dispersion aid can be further contained. Known dispersants include, for example, urethane dispersants, polyethylene imine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants. A dispersant, a polyester-based dispersant, an acrylic-based dispersant and the like, and examples of the dispersion aid include a pigment derivative and the like.

  Such dispersants are commercially available. For example, acrylic dispersants such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (above, BYK Corporation (BYK) ), And as a urethane-based dispersant, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182, Disperbyk-2164 (manufactured by BYK Corporation (BYK) 76) Lubrizol Co., Ltd.), polyethyleneimine dispersant, Solsperse 24000 (Lubrisol Co., Ltd.), polyester dispersant In addition to Ajisper PB821, Azisper PB822, Azisper PB880, Azisper PB881 (above, Ajinomoto Fine Techno Co., Ltd.), BYK-LPN21324 (non-volatile component 40% by mass) (Bikchemy (BYK) Co., Ltd.), etc. be able to.

  Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivative of quinophthalone.

  In the present invention, other colorants can be used alone or in admixture of two or more.

The colored composition of the present invention is preferably used for forming a red pixel or a green pixel.
When used for forming a red pixel, (A) as a colorant, together with compound (1), as other colorants, red pigments other than compound (1), red dye, purple pigment, purple dye, yellow pigment, yellow It is preferable to include at least one selected from the group consisting of a dye and an orange pigment. When used for forming a green pixel, (A) the colorant is selected from the group consisting of the compound (1) and the other colorants, other than the compound (1), a green pigment, a green dye, a yellow pigment, and a yellow dye. It is preferable to contain at least one kind.
Examples of the red pigment include C.I. I. Pigment red 177, and C.I. I. Pigment red 254, C.I. I. Pigment red 264 and diketopyrrolopyrrole pigments such as pigments represented by formula (Ic) of JP-T-2011-523433 are preferred. Examples of the purple pigment include C.I. I. Pigment Violet 23 is preferable. Examples of the yellow pigment include C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment Yellow 185 is preferable. Examples of the orange pigment include C.I. I. Pigment Orange 38 is preferable. Examples of the green pigment include C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. A phthalocyanine pigment such as CI Pigment Green 58 is preferred.
As the red dye and purple dye, xanthene dyes are preferable.

(A) The content of the colorant is excellent in chromaticity characteristics even at a low exposure amount and is difficult to cause chipping, or from the point of forming a black matrix and a black spacer excellent in light-shielding properties. Usually, it is 5-70 mass%, Preferably it is 10-60 mass%, More preferably, it is 15-40 mass%. Here, solid content is components other than the solvent mentioned later.
Moreover, when using another colorant, 99 mass% or less is preferable with respect to the total content of a colorant, and, as for the content rate of another colorant, 95 mass parts or less are more preferable. The lower limit is not particularly limited and may be 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 resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). And a copolymer of 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- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meta ) Acrylate, p-vinylbenzoic acid and the like.
These unsaturated monomers (b1) can be used alone or in admixture of two or more.

Moreover, as said unsaturated monomer (b2), for example,
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;

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 10) methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate Glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4- Epoxy tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl ( (Meth) acrylic acid esters such as (meth) acrylate, 3-[(meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These unsaturated monomers (b2) can be used alone or in admixture of two or more.

Of these unsaturated monomers (b2), an ethylenically unsaturated monomer having an oxiranyl group, an ethylenically unsaturated monomer having an oxetanyl group, and an ethylenically unsaturated monomer having a tetrahydrofuranyl group Such an ethylenically unsaturated monomer having a cyclic ether structure having 2 to 4 carbon atoms is preferably included, and an ethylenically unsaturated monomer having an oxiranyl group is more preferably included. Examples of the ethylenically unsaturated monomer having an oxiranyl group include 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl. (Meth) acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl (meth) acrylate are preferred.

  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. More preferably, it is 10 to 40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, a colored 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, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. No. 10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Coalescence can be mentioned.

  In the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, As disclosed in Kaikai 2008-181095 and the like, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as a binder resin.

  The binder resin in the present invention has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran), usually 1,000 to 100,000, preferably Is 3,000 to 50,000. By setting it as such an aspect, the remaining-film rate of a film, a pattern shape, heat resistance, an electrical property, and the resolution can be improved further, and generation | occurrence | production of the dry foreign material at the time of application | coating can be suppressed at a high level.

  Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3. .0. In addition, Mn here says the number average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran).

  The binder resin in the present invention can be produced by a known method. For example, it is disclosed in JP2003-222717A, JP2006-259680A, International Publication No. 2007/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.

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

  In this invention, content of (B) binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts, More preferably, it is 50-200 mass. Part, more preferably 80 to 150 parts by weight. By setting it as such an aspect, alkali developability, the storage stability of a coloring composition, pattern shape, and chromaticity characteristic can be improved further.

-(C) Polymerizable compound-
In the present invention, the polymerizable compound refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl 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) acryloyl groups or a compound having two or more N-alkoxymethylamino groups.

  Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, a polyfunctional (meta) modified with caprolactone. ) Acrylate, alkylene oxide modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting hydroxyl-functional (meth) acrylate and polyfunctional isocyanate, hydroxyl-functional (meth) acrylate and acid anhydride The polyfunctional (meth) acrylate which has a carboxyl group obtained by making a product react can be mentioned.

  Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and 3 such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of aliphatic polyhydroxy compounds having a valence higher than that. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol diester. A methacrylate etc. can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. The alkylene oxide-modified polyfunctional (meth) acrylate is at least one selected from bisphenol A di (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide, ethylene oxide and propylene oxide. Modified with at least one selected from trimethylolpropane tri (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from modified isocyanuric acid tri (meth) acrylate, ethylene oxide and propylene oxide Pen modified with at least one selected from pentaerythritol tri (meth) acrylate, ethylene oxide and propylene oxide. Dipentaerythritol modified with at least one selected from dipentaerythritol penta (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from taerythritol tetra (meth) acrylate, ethylene oxide and propylene oxide Examples include hexa (meth) acrylate.

  Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and is a concept including melamine, benzoguanamine or a condensate thereof. 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′-tetra (alkoxymethyl) benzoguanamine, N, N, N ′, N′-tetra (alkoxymethyl) glycoluril and the like.

Among these polymerizable compounds, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, polyfunctional urethanes (Meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′, N ′ -Tetra (alkoxymethyl) benzoguanamine is preferred. Among the polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Erythritol hexaacrylate is a compound obtained by reacting pentaerythritol triacrylate and succinic anhydride, among polyfunctional (meth) acrylates having a carboxyl group, obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride. The compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and background stains and film residues are hardly generated on the unexposed substrate and the light shielding layer.
In this invention, (C) polymeric compound can be used individually or in mixture of 2 or more types.

  The content of the polymerizable compound (C) in the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 700 parts by mass, and 50 to 500 parts by mass with respect to 100 parts by mass of the (A) colorant. Is more preferable, and 80-250 mass parts is still more preferable. Moreover, 50-300 mass parts is preferable with respect to 100 mass parts of (B) binder resin, and, as for content of (C) polymeric compound, 70-200 mass parts is more preferable, and 100-150 mass parts is still more preferable. By setting it as such an aspect, sclerosis | hardenability and alkali developability can be improved further and generation | occurrence | production of a ground stain, a film | membrane residue, etc. on the board | substrate of a non-exposed part or a light shielding layer can be suppressed at a high level.

-(D) Photopolymerization initiator-
The coloring composition of the present invention can contain a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. The photopolymerization initiator used in the present invention is a compound that generates an active species capable of initiating polymerization of the polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray.

  Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, A diazo compound, an imide sulfonate compound, etc. can be mentioned.

  In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator is preferably at least one selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, and an O-acyloxime compound.

  Among the preferred photopolymerization initiators in the present invention, specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2, 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like can be mentioned.

  Specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- And morpholinophenyl) butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

  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 Examples include ', 5,5'-tetraphenyl-1,2'-biimidazole.

  In addition, when using a biimidazole compound as a photoinitiator, using a hydrogen donor together is preferable at the point which can improve a sensitivity. The term “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4′-bis (dimethylamino) benzophenone, and 4,4′-bis (diethylamino) benzophenone. Mention may be made of amine hydrogen donors. In the present invention, hydrogen donors can be used alone or in admixture of two or more, but one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. Is preferable in that the sensitivity can be further improved.

  Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) ) -S-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-eth Triazine compounds having a halomethyl group such as cistyryl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) ) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3- And dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime). As commercially available O-acyloxime compounds, NCI-831, NCI-930 (above, manufactured by ADEKA Corporation), DFI-020, DFI-091 (above, manufactured by Daito Chemix Corporation), and the like can also be used. .

  In this invention, when using photoinitiators other than biimidazole compounds, such as an acetophenone compound, a sensitizer can also be used together. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

  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, with respect to 100 parts by mass of the (C) polymerizable compound. 50 mass parts is still more preferable, and 10-30 mass parts is especially preferable. By setting it as such an aspect, sclerosis | hardenability and a film characteristic can be improved further.

-(E) Solvent-
The colored composition of the present invention contains the above components (A) to (C) and other components that are optionally added, but is usually prepared as a liquid composition by blending a solvent.
(E) As a solvent, as long as (A)-(C) component and other components which comprise a coloring composition are disperse | distributed or melt | dissolved, and it does not react with these components, but has moderate volatility. Can be appropriately selected and used.

Among such solvents, for example
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol 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, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol;
Keto alcohols such as diacetone alcohol;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Alkoxycarboxylic esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, butyric acid other esters such as i-propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

  Of these solvents, (poly) alkylene glycol monoalkyl ethers, lactic acid alkyl esters, (poly) alkylene glycol monoalkyl ether acetates, and other ethers from the viewpoints of solubility, pigment dispersibility, coatability, etc. , Ketones, diacetates, alkoxycarboxylic acid esters, and other esters are preferred, especially 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-hept Non, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3- Methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, Ethyl pyruvate and the like are preferable.

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

  (E) Although content of a solvent is not specifically limited, The quantity from which the total density | concentration of each component except the solvent of the coloring composition becomes 5-50 mass% is preferable, and it is 10-40 mass%. Is more preferred. By setting it as such an aspect, the coloring agent dispersion liquid with favorable dispersibility and stability and the coloring composition with favorable coating property and stability can be obtained.

-Additives-
The coloring composition of this invention can also contain a various additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorine surfactants and silicone surfactants; vinyltrimethoxysilane Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyl Adhesion promoters such as limethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- t-butylphenol, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis [2- [3- (3-t-butyl-4-hydroxy) -5-methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxa-spiro [5.5] undecane, thiodiethylenebis [3- (3,5-di- antioxidants such as t-butyl-4-hydroxyphenyl) propionate]; 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) Nyl) -5-chlorobenzotriazole, alkoxybenzophenones, etc .; anti-aggregation agents 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-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol Residue improving agents such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. An improving agent etc. can be mentioned.

  Moreover, when using both the dye and the pigment as the colorant, the coloring composition of the present invention, as disclosed in JP 2010-132874 A, after passing the dye solution through the first filter, A method can be employed in which the dye solution that has passed through the first filter is mixed with a separately prepared pigment dispersion or the like, and the resulting colored composition is passed through a second filter. In addition, the dye, the above components (B) to (C), and other components to be used as necessary are dissolved in a solvent, and the obtained solution is passed through the first filter, and then the first filter is used. You may employ | adopt the method prepared by mixing the solution which passed through with the pigment dispersion liquid prepared separately, and passing the obtained coloring composition through a 2nd filter. Also, after passing the dye solution through the first filter, the dye solution that has passed through the first filter, the above components (B) to (C), and other components used as necessary are mixed and dissolved. The obtained solution is passed through a second filter, and the solution that has passed through the second filter is further mixed with a separately prepared pigment dispersion, and the resulting colored composition is passed through a third filter. It is also possible to adopt a method to do this.

Colored cured film and formation method thereof The colored cured film of the present invention is formed using the colored composition of the present invention. Specifically, each color pixel, black matrix, black spacer, etc. constituting the color filter Means.

Hereinafter, the colored cured film used for the color filter which comprises a display element and a solid-state image sensor, and its formation method are demonstrated.
As a method for producing a color filter, first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, for example, after applying a red liquid composition of the radiation-sensitive colored composition of the present invention on the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which red pixel patterns (colored cured films) are arranged in a predetermined arrangement.

  Subsequently, using each radiation sensitive coloring composition of green or blue, application of each radiation sensitive coloring composition, pre-baking, exposure, development, and post-baking are performed in the same manner as described above to obtain a green pixel array and blue color. Are sequentially formed on the same substrate. Thereby, a color filter in which pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

  The black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithographic method. However, the radiation sensitive material in which a black colorant is dispersed is used. It can also be formed in the same manner as in the case of forming the above-mentioned pixel using a sexually colored composition.

Examples of the substrate used when forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

  When applying the radiation-sensitive coloring composition to the substrate, an appropriate coating method such as spraying, roll coating, spin coating (spin coating), slit die coating (slit coating), bar coating, etc. In particular, it is preferable to employ a spin coating method or a slit die coating method.

  Pre-baking is usually performed by combining vacuum drying and heat drying. The drying under reduced pressure is usually performed until the pressure reaches 50 to 200 Pa. Moreover, the conditions of heat drying are 70-110 degreeC normally for about 1 to 10 minutes.

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

  Examples of the radiation light source used when forming at least one selected from the pixel and the black matrix include, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, and a low pressure. Examples thereof include a lamp light source such as a mercury lamp, and a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. An ultraviolet LED can also be used as the exposure light source. The wavelength is preferably radiation in the range of 190 to 450 nm.

Exposure of the radiation is generally preferred 10~10,000J / m ^2.
Examples of the alkali developer include sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-. An aqueous solution of undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene or the like is preferable.

For example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

The post-baking conditions are usually 180 to 280 ° C. and about 10 to 60 minutes.
The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1 to 3 μm.

  Further, as a second method for producing a color filter, a method of obtaining pixels of each color by an ink jet method disclosed in JP-A-7-318723 and JP-A-2000-310706 can be employed. . In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, for example, a liquid composition of a red thermosetting coloring composition is discharged into the formed partition wall by an inkjet apparatus, and then prebaked to evaporate the solvent. Next, the coating film is exposed as necessary, and then cured by post-baking to form a blue pixel pattern.

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

In addition, since the partition plays not only a light shielding function but also a function for preventing the color mixing of the thermosetting coloring compositions discharged in the respective sections, it is compared with the black matrix used in the first method described above. The film thickness is thick. Therefore, a partition is normally formed using a black radiation sensitive composition.
The substrate used when forming the color filter, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as in the first method described above. In this way, the film thickness of the pixel formed by the ink jet method is approximately the same as the height of the partition wall.

  A protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but may be a light-shielding spacer (black spacer). In this case, a radiation-sensitive colored composition in which a black colorant is dispersed is used, but the colored composition of the present invention can also be suitably used for forming such a black spacer.

The radiation-sensitive colored composition of the present invention can be suitably used in forming any colored cured film such as each color pixel, black matrix, and black spacer used in the color filter.
Since the color filter including the colored cured film of the present invention formed in this way has extremely high luminance and color purity, it can be used in color liquid crystal display elements, color imaging tube elements, color sensors, organic EL display elements, electronic paper, and the like. Very useful. In addition, the display element mentioned later should just have at least 1 or more of colored cured films formed using the radiation sensitive coloring composition of this invention.

Display element 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 provided with the colored cured film of the present invention may be a transmissive type or a reflective type, and can take an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the 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. Can be taken. In addition, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (tin-doped indium oxide) electrode is formed face each other through a liquid crystal layer. A structure can also be adopted. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained. When the latter structure is adopted, the black matrix and the black spacer may be formed on either the substrate side on which the color filter is formed or the substrate side on which the ITO electrode is formed.

  The color liquid crystal display element including the colored cured film of the present invention can include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As the white LED, for example, a white LED that obtains white light by color mixing by combining a red LED, a green LED, and a blue LED, a white LED that obtains white light by color mixing by combining a blue LED, a red LED, and a green phosphor, and a blue LED White LED that obtains white light by mixing colors, red LED and green light emitting phosphor, white LED that obtains white light by mixing colors of blue LED and YAG phosphor, blue LED, orange light emitting phosphor and green light emitting fluorescence A white LED that obtains white light by color mixing by combining the body, a white LED that obtains white light by color mixing by combining an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor can be exemplified.

  The color liquid crystal display element having the colored cured film of the present invention includes TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, IPS (In-Plane Switching) type, VA (Vertical Alignment) type, OCB (Optical). An appropriate liquid crystal mode such as a Compensated Birefringence type is applicable.

Moreover, the organic EL display element provided with the colored cured film of the present invention can have an appropriate structure, and examples thereof include a structure disclosed in JP-A-11-307242.
Moreover, the electronic paper provided with the colored cured film of the present invention can have an appropriate structure, and examples thereof include a structure disclosed in JP-A-2007-41169.

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

<Synthesis of colorant>
Synthesis example 1

To a 300 mL eggplant-shaped flask containing a stir bar, 9.7 g of 2,3,3-trimethylindolenine, 25.9 g of 1-iodomethane, and 85 mL of acetonitrile were added and stirred for 10 hours while heating under reflux. After cooling to room temperature, the reaction solution was added to 425 mL of diisopropyl ether, cooled on ice, and allowed to stand for 30 minutes. Thereafter, the precipitate was collected by suction filtration, and the obtained solid was dried under reduced pressure to obtain 16.1 g of a light pink solid. Analysis by ¹ H-NMR and MS spectrum confirmed that the obtained solid was the compound (A1) represented by the above formula.

Synthesis example 2

To a 100 mL eggplant-shaped flask containing a stirring bar, 8.1 g of the compound (A1) obtained in Synthesis Example 1, 12.0 g of ethyl orthoformate, and 24 mL of pyridine were added 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 stirred at 40 ° C. for 30 minutes. Thereafter, the mixture was added to 200 mL of diisopropyl ether, cooled on ice, and allowed to stand for 30 minutes. Thereafter, the precipitate was collected by suction filtration, and the obtained solid was dried under reduced pressure to obtain 6.3 g of a red-purple solid. Analysis by ¹ H-NMR and LC-MS confirmed 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). It was done. Let this compound be a coloring agent (A-2).

Synthesis example 3
The colorant (A-2) was recrystallized by the following method. Specifically, 5.0 g of the colorant (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 containing a stirring bar, and the mixture was heated at 80 ° C. for 2 hours. Stir. The solution was then cooled and left at 5 ° C. overnight. The precipitate was collected by suction filtration, and the obtained solid was dried under reduced pressure to obtain 4.6 g of a red-purple solid. This compound is defined as a colorant (A-3).

Synthesis example 4
The colorant (A-3) was recrystallized by the following method. Specifically, 5.0 g of the colorant (A-3) obtained in Synthesis Example 3 and 100 g of ion-exchanged water containing 10% by mass of ethanol were placed in a 300 mL eggplant-shaped flask containing a stir bar, and the mixture was heated at 80 ° C. for 2 hours. Stir. The solution was then cooled and left at 5 ° C. overnight. The precipitate was collected by suction filtration, and the obtained solid was dried under reduced pressure to obtain 4.3 g of a red-purple solid. This compound is defined as a colorant (A-4).

Synthesis example 5

In a 300 mL eggplant type flask containing a stirrer, 3.0 g of the colorant (A-2) obtained in Synthesis Example 2, 2.7 g of lithium-bis (trifluoromethanesulfonyl) imide, 24 mL of acetonitrile, 36 mL of ethyl acetate and 30 mL of ion exchange water was added and stirred for 2 hours. Thereafter, the aqueous layer was separated and removed, and the organic layer was washed 3 times with 30 mL of ion-exchanged water. Subsequently, the organic layer was concentrated under reduced pressure using a rotary evaporator and vacuum-dried overnight at 50 ° C. to obtain 4.0 g of a dark red solid. Analysis by ¹ H-NMR and LC-MS confirmed that the obtained solid was a mixture of the compound represented by the above formula (A5-1) and the compound represented by the above formula (A5-2). It was done. This compound is defined as a colorant (A-5).

Synthesis Example 6
In Synthesis Example 5, a reaction operation similar to that of Synthesis Example 5 is performed except that the colorant (A-3) is used in place of the colorant (A-2), and is represented by the above formula (A5-1). A mixture of the compound and the compound represented by the above formula (A5-2) was obtained. Let the obtained compound be a coloring agent (A-6).

Synthesis example 7
In Synthesis Example 5, the same reaction operation as in Synthesis Example 5 is performed except that the colorant (A-4) is used in place of the colorant (A-2), and represented by the above formula (A5-1). A mixture of the compound and the compound represented by the above formula (A5-2) was obtained. Let the obtained compound be a coloring agent (A-7).

Synthesis example 8

In Synthesis Example 5, the reaction procedure was the same as in Synthesis Example 5 except that 2.4 g of p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt was used instead of 2.7 g of lithium-bis (trifluoromethanesulfonyl) imide. went. Analysis by ¹ H-NMR and LC-MS confirmed that the obtained solid was a mixture of the compound represented by the above formula (A8-1) and the compound represented by the above formula (A8-2). It was done. Let the obtained compound be a coloring agent (A-8).

Synthesis Example 9
In Synthesis Example 8, the same reaction operation as in Synthesis Example 8 is performed except that the colorant (A-3) is used in place of the colorant (A-2), and the compound is represented by the above formula (A8-1). A mixture of the compound and the compound represented by the above formula (A8-2) was obtained. Let the obtained compound be a coloring agent (A-9).

Synthesis Example 10
In Synthesis Example 8, the same reaction operation as in Synthesis Example 8 is performed except that the colorant (A-4) is used in place of the colorant (A-2), and represented by the above formula (A8-1). A mixture of the compound and the compound represented by the above formula (A8-2) was obtained. Let the obtained compound be a coloring agent (A-10).

Synthesis Example 11

  The same procedure as in Synthesis Example 1 was performed except that 30.9 g of 1-iodopropane was used instead of 25.9 g of 1-iodomethane in Synthesis Example 1, thereby obtaining the compound (A11) represented by the above formula. Obtained.

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 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). It was done. This compound is defined 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). Let the obtained compound be a coloring agent (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). Let the obtained compound be a coloring agent (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), and the above formula (A15- A mixture of the compound represented by 1) and the compound represented by the above formula (A15-2) was obtained. Let the obtained compound be a coloring agent (A-15).

Synthesis Example 16
In Synthesis Example 5, the same reaction operation as in Synthesis Example 5 was performed 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- A mixture of the compound represented by 1) and the compound represented by the above formula (A15-2) was obtained. Let the obtained compound be a coloring agent (A-16).

Synthesis Example 17
In Synthesis Example 5, the same reaction operation as in Synthesis Example 5 was performed 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- A mixture of the compound represented by 1) and the compound represented by the above formula (A15-2) was obtained. Let the obtained compound be a coloring agent (A-17).

Purity confirmation colorants (A-5) to (A-10) and (A-15) to (A-17) acetonitrile solutions (colorant concentration 1000 ppm) were prepared, respectively, and subjected to high performance liquid chromatography under the following analysis conditions. The purity was quantified using a graph. Concentration of compound (2) relative to the total content of compound (1) and compound (2) by measuring the concentration of compound (2) in each colorant, that is, the compound having the structure represented by formula (2) The amount was calculated. The results are shown in Table 1.

〔Analysis conditions〕
・ Device: High-performance liquid chromatograph [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, manufactured by Shiseido)
-Column oven set temperature: 40 ° C
Sample injection volume: 10 μL
・ Flow rate: 0.5mL / min

  In Table 1, it shows that the density | concentration of the compound (2) in a coloring agent (A-7), (A-10) and (A-17) was less than the detection limit in a high performance liquid chromatograph.

<Preparation of pigment dispersion>
Preparation Example 1
As a coloring agent, C.I. I. 15 parts by mass of Pigment Red 254, 12.5 parts by mass of BYK-LPN21116 (manufactured by BYK Corporation) as a dispersant (solid content concentration 40% by mass), and 72.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent Then, a pigment dispersion (a-1) was prepared by treatment with a bead mill.

<Preparation of colorant solution>
Preparation Example 2
10 parts by weight of the colorant (A-5) and 90 parts by weight of propylene glycol monomethyl ether were mixed to prepare a colorant solution (A-5).

Preparation Examples 3 to 10
In Preparation Example 2, the colorant solutions (A-6) to (A-10) and (A-15) to (A-15) to (A) are used in the same manner as Preparation Example 2, except that the type of the colorant is changed as shown in Table 2. A-17) was prepared.

<(B) Synthesis of binder resin>
Synthesis Example 18
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same 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, 15 parts by mass of 2-hydroxyethyl methacrylate, 2-ethylhexyl methacrylate 23 parts by mass, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid mono (2-acryloyloxyethyl) and 6 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) The solution was added dropwise over a period of time and polymerized for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and further polymerized for 1 hour to obtain 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 JP2013-203955A, a solution containing a resin having the following structural units 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 coloring composition Example 1
(A) 30.5 parts by mass of the pigment dispersion (a-1) as the colorant, 23.0 parts by mass of the colorant solution (A-5), (B) 26.3 parts by mass of the binder resin solution (B1) as the binder resin 9.9 parts by weight of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as a polymerizable compound, 2-benzyl as a photopolymerization initiator 1.8 parts by mass of 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals) and NCI-930 (ADEKA Corporation) 0.1 part by mass), 0.05 part by mass of MegaFac F-554 (manufactured by DIC Corporation) as a fluorosurfactant, and Propylene glycol monomethyl ether acetate was mixed as a solvent to prepare a colored composition (S-1) having a solid 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 on an 80 ° C. hot plate for 10 minutes to form a coating film. Three coating films having different film thicknesses were formed by the same operation while changing the rotation speed of the spin coater.
Next, after cooling these substrates to room temperature, a high-pressure mercury lamp is used, and a radiation containing each wavelength of 365 nm, 405 nm, and 436 nm is applied to each coating film without using a photomask at an exposure dose of 2,000 J / m ² . And exposed. Then, shower development was performed for 90 seconds on these substrates by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 200 ° C. for 30 minutes to form a colored cured film for evaluation.
Using the color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), the chromaticity coordinate values (x, y) and stimuli in the CIE color system with a C light source and a 2-degree field of view for the three colored cured films obtained The value (Y) was measured. From the measurement result, the chromaticity coordinate value x and the stimulus value (Y) when the chromaticity coordinate value y = 0.329 were obtained. The evaluation results are shown in Table 3. It can be said that the higher the stimulus value (Y), the higher the luminance.

Foreign matter evaluation The colored composition (S-1) which was allowed to stand at 5 ° C. for 3 days was used on a 10 cm × 10 cm soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed. Then, prebaking was performed for 4 minutes on a 90 ° C. hot plate to form a coating film having a film thickness of 2.5 μm after prebaking. The obtained substrate is observed with an optical microscope. If no foreign matter is observed on the coating film, “◯” is indicated. If the number of foreign matters generated on the coating film is 1 or more and 10 or less, “△” is indicated. If the number of occurrences of foreign matter on the film was observed 11 or more, it was judged as “x”. The evaluation results are shown in Table 3. In addition, it means that it is excellent in the storage stability of a coloring composition, so that there are few foreign materials.

Examples 2 to 4 and Comparative Examples 1 and 2
A colored 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 in Example 1. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 3.

Examples 5 and 6 and Comparative Example 3
In Example 1, a colored 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. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 3.

Claims (3)

A coloring composition comprising (A) a colorant, (B) a binder resin and (C) a polymerizable compound,
(A) The colorant contains a compound having a structure represented by the following formula (1) and a compound having a structure represented by the following formula (2), and having a structure represented by the following formula (2) The content of is 0.001 to 1% by mass 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).
Coloring composition.

[In Formula (1),
Ring Z ¹ and ring Z ² each independently represent a substituted or unsubstituted heterocycle.
p represents 1 or 2. However, 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 each independently represent a substituted or unsubstituted heterocycle.
q represents an integer of 2 or more when p is 1, and represents an integer of 3 or more when p is 2.
R ^{4 to} R ⁶ each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group. However, a plurality of R ⁴ and R ⁵ may be the same or different. ]   The coloring composition of Claim 1 used for formation of a red pixel or a green pixel. The compound having a structure represented by the formula (1) is a compound having a structure represented by the following formula (1A), and the compound having a structure represented by the formula (2) is represented by the following formula (2A) The coloring composition of Claim 1 or 2 which is a compound which has a structure represented.

[In Formula (1A),
R ^{1 to} R ³ are as defined above.
Ring Z ^1A and ring Z ^2A each independently represent a substituted or unsubstituted aromatic hydrocarbon ring.
Q ¹ and Q ² each independently represent —O—, —S—, or —CR ¹³ R ¹⁴ —.
R ^{11 to} R ¹⁴ each independently represent a substituted or unsubstituted hydrocarbon group. ]

[In Formula (2A),
q and R ^{4 to} R ⁶ are as defined above.
Ring Z ^3A and ring Z ^4A each independently represent a substituted or unsubstituted aromatic hydrocarbon ring.
Q ³ and Q ⁴ each independently represent —O—, —S—, or —CR ²³ R ²⁴ —.
R ^{21 to} R ²⁴ each independently represent a substituted or unsubstituted hydrocarbon group. ]