KR102373077B1 - Coloring composition, colored cured film and display divice - Google Patents

Abstract

(화학식 (1), (2)에 있어서,
환 Z¹, 환 Z², 환 Z³ 및 환 Z⁴는 서로 독립적으로 치환 또는 비치환된 복소환을 나타내고, R¹ 내지 R⁶은 서로 독립적으로 수소 원자, 할로겐 원자, 또는 치환 또는 비치환된 탄화수소기를 나타내되, 단, R¹, R², R⁴ 및 R⁵가 복수개 존재하는 경우, 동일할 수도 상이할 수도 있고, p는 1 또는 2를 나타내고, q는, p가 1일 때에는 2 이상의 정수를 나타내고, p가 2일 때에는 3 이상의 정수를 나타냄)The subject of this invention is providing the coloring composition with favorable storage stability containing a cyanine dye as a coloring agent.
A solution of the present invention is a coloring composition comprising (A) a colorant, (B) a binder resin, and (C) a polymerizable compound, wherein (A) the colorant is a compound having a structure represented by the following formula (1) and the following formula The content of a compound having a structure represented by the following formula (2), including a compound having a structure represented by (2), is represented by a compound having a structure represented by the following formula (1) and a compound having a structure represented by the following formula (2) It is a coloring composition of 0.001 mass % or more with respect to the total content of the compound which has a structure used.

(In the formula (1), (2),
Ring Z ¹ , Ring Z ² , Ring Z ³ , and Ring Z ⁴ each independently represent a substituted or unsubstituted heterocycle, and R ¹ to R ⁶ are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted A hydrocarbon group is represented, with the proviso that when a plurality of R ¹ , R ² , R ⁴ and R ⁵ exist, they may be the same or different, p represents 1 or 2, and q is 2 or more when p is 1 represents an integer, and when p is 2, represents an integer greater than or equal to 3)

Description

A coloring composition, a colored cured film, and a display element TECHNICAL FIELD

The present invention relates to a colored composition, a colored cured film, and a display element, and more particularly, it is used for the formation of a colored cured film used for a transmissive or reflective color liquid crystal display element, a solid-state image sensor, an organic EL display element, an electronic paper, etc. It is related with the display element provided with the coloring composition used as used, the colored cured film formed using the said coloring composition, and the said colored cured film.

In manufacturing a color filter using a colored radiation-sensitive composition, a pigment dispersion-type colored radiation-sensitive composition is applied on a substrate, dried, and then the dried coating film is irradiated with radiation in a desired pattern shape (hereinafter "exposure"). ), and a method (for example, refer to patent documents 1 and 2) which obtains the pixel of each color by developing is known. Moreover, the method of forming a black matrix using the photopolymerizable composition which disperse|distributed carbon black (for example, refer patent document 3) is also known. Moreover, the method (for example, refer patent document 4) which obtains the pixel of each color by the inkjet system using the pigment dispersion type colored resin composition is also known.

The coloring composition for forming a colored cured film WHEREIN: Using dye for a coloring agent for the purpose of forming a higher-intensity colored cured film is examined. For example, in patent document 5, it is reported that the coating film which has the outstanding brightness is obtained by using cyanine dye as a coloring agent.

Japanese Patent Laid-Open (Hei)2-144502 Japanese Patent Laid-Open No. 3-53201 (Hei) Japanese Patent Laid-Open (Hei)6-35188 Japanese Patent Laid-Open No. 2000-310706 Japanese Patent Laid-Open No. 2009-235392

However, according to examination of the present inventors, in the coloring composition containing a cyanine dye as a coloring agent, it became clear that the storage stability of a coloring composition may be inadequate.

Therefore, the subject of this invention is providing the coloring composition containing a cyanine dye as a coloring agent, and can form a high-intensity colored cured film with favorable storage stability. Moreover, the subject of this invention is providing the colored cured film formed using the said coloring composition, and a display element provided with the same.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject could be solved by using at least 2 types of cyanine compounds as a coloring agent, and controlling their content rate, as a result of earnestly examining.

That is, the present invention relates to a coloring composition comprising (A) a colorant, (B) a binder resin, and (C) a polymerizable compound, wherein (A) the colorant has a structure represented by the following formula (1), and the following formula ( 2) including 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) is a compound having a structure represented by the following formula (1) and a compound represented by the following formula (2) It is providing a coloring composition which is 0.001 mass % or more with respect to the total content of the compound which has a structure.

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), wherein the content of the compound having a structure represented by the following formula (2) is It is to provide a coloring agent which is 0.001 mass % or more with respect to the total content of the compound which has a structure represented by general formula (1), and a compound which has a structure shown by following general formula (2).

[In the formula (1),

Ring Z ¹ And Ring Z ² Represent independently of each other a substituted or unsubstituted heterocycle,

p represents 1 or 2, with the proviso that 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 the formula (2),

Ring Z ³ and ring Z ⁴ 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 independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group, provided that a plurality of R ⁴ and R ⁵ may be the same or different)

Moreover, this invention provides the colored cured film formed using the said coloring composition, and the display element provided with this colored cured film. Here, a "colored cured film" means each color pixel, a black matrix, a black spacer, etc. used for a display element and a solid-state image sensor.

The coloring composition of this invention has favorable storage stability. Moreover, when the coloring composition of this invention is used, a high-intensity colored cured film can be formed.

Therefore, the coloring composition of this invention can be used suitably for manufacture of solid-state image sensors, such as display elements, such as a color liquid crystal display element, an organic electroluminescent display element, electronic paper, and a CMOS image sensor.

Hereinafter, the present invention will be described in detail.

coloring composition

Hereinafter, the structural component of the coloring composition of this invention is demonstrated in detail.

-(A) Colorant-

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

[In the formula (1),

Ring Z ¹ And Ring Z ² Represent independently of each other a substituted or unsubstituted heterocycle,

p represents 1 or 2, with the proviso that 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 the formula (2),

Ring Z ³ and ring Z ⁴ 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 independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group, and a plurality of R ⁴ and R ⁵ may be the same or different]

The heterocycle in the ring Z ¹ to the ring Z ⁴ may be a monocyclic heterocycle or a polycyclic heterocycle. The heterocyclic ring may be an unsaturated ring or a saturated ring, and may have two or more heteroatoms (eg, nitrogen atom, oxygen atom, sulfur atom) of the same 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 and 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 Other aromatic heterocycles, such as nitrogen-containing aromatic heterocycles, such as a ring, an indazole ring, a benzimidazole ring, benzoxazole, and a phthalimide ring, a thienyl ring, a furan ring, and a purine ring, are mentioned. Among these, a nitrogen-containing aromatic heterocycle is preferable, an indole ring, a benzoxazole ring, and a benzothiazole ring are more preferable, and an indole ring is still more preferable.

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

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

As a combination of p and q, it is preferable that p is 1 and q is 2 or more, It is more preferable that 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 for 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. In addition, these aliphatic hydrocarbon groups may be linear or branched. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a 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 Sil group, octadecyl group, henicosan-1-yl group, docosan-1-yl group, tricosan-1-yl group, tetracosan-1-yl group, and the like can be mentioned. 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-hexyl group. Cenyl group, 2-ethyl-2-butenyl group, 2-octenyl group, (4-ethenyl)-5-hexenyl group, 2-decenyl group, etc. are mentioned. 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, 2-octynyl group, (4-ethynyl)-5-hexynyl group, 2-decynyl group, etc. are mentioned.

As the alicyclic hydrocarbon group, an alicyclic hydrocarbon group having 3 to 30 carbon atoms is preferable. 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 cross-linked hydrocarbon group, a spiro hydrocarbon group, and a cyclic terpene hydrocarbon 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, and a cyclooctyl group; cycloalkenyl groups such as 1-cyclohexenyl group; Condensed polycyclic hydrocarbon groups, such as a tricyclodecanyl group, a decahydro-2-naphthyl group, and an adamantyl group; cross-linked hydrocarbon groups such as tricyclo[5.2.1.0 ^2,6 ]decan-8-yl group, pentacyclopentadecanyl group, isobornyl group, dicyclopentenyl group and tricyclopentenyl group; spiro hydrocarbon groups such as spiro[3,4]heptane and monovalent groups in which one hydrogen atom has been removed from spiro[3,4]octane; and cyclic terpene hydrocarbon groups such as monovalent groups in which one hydrogen atom has been removed from p-mentane, tuzan, karan and the like. In the said cycloalkyl group and a cycloalkenyl group, it is more preferable that C3-C12.

As an aromatic hydrocarbon group, a C6-C20 thing is preferable, and a C6-C10 thing is more preferable. As an aromatic hydrocarbon group, an aryl group is mentioned, for example. Here, in the present specification, "aryl group" refers to a monocyclic to tricyclic aromatic hydrocarbon group, specifically, a phenyl group, a benzyl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, a xylyl group, a naphthyl group, An anthryl group, a phenanthryl group, an azulenyl group, 9-fluorenyl group, etc. are mentioned.

Examples of the substituent of the heterocycle 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 dialkyl group. Amino 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, heterocyclic group , an aromatic hydrocarbon group, and the like.

The compound having the 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)”). 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 the formula (1A),

R ¹ to R ³ are the same as above,

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

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

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

[In the formula (2A),

q, R ⁴ to R ⁶ are the same as above,

Ring Z ^3A and ring Z ^4A each independently 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 represent a substituted or unsubstituted hydrocarbon group]

As an aromatic hydrocarbon ring in ring Z1A - ring ^Z4A , a C6-C20 thing is preferable, ^A C6-C10 thing is more preferable, A benzene ring is especially preferable.

A hydrogen atom is preferable as R ¹ to R ⁶ .

As for q, 2 is preferable.

Q ¹ and Q ² are preferably -O- and -CR ¹³ R ¹⁴ -. As the hydrocarbon group for R ¹³ and R ¹⁴ , an aliphatic hydrocarbon group is preferable, and an alkyl group is more preferable. As the alkyl group, an alkyl group having 1 to 8 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group and an ethyl group are particularly preferable.

Q ³ and Q ⁴ are preferably -O- and -CR ²³ R ²⁴ -. As the hydrocarbon group for R ²³ and R ²⁴ , an aliphatic hydrocarbon group is preferable, and an alkyl group is more preferable. As the alkyl group, an alkyl group having 1 to 8 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group and an ethyl group are particularly preferable.

Examples of the hydrocarbon group for 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. As a specific example, the thing similar to what was illustrated by the hydrocarbon group in R< ¹ >-R< ⁶ > is mentioned. Among them, as the hydrocarbon group for R ¹¹ to R ¹² and R ²¹ to 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, the compound having the structure may have an anion so as to be electrically neutral. Examples of the anion include a halogen ion, a boron anion, a phosphate anion, a carboxylate anion, a sulfate anion, an organic sulfonic acid anion, a nitrogen anion, a methide anion, and an anion of a transition metal complex having an azo compound as a ligand.

As a halogen ion, a fluoride ion, a chloride ion, a bromide ion, and an iodide ion are mentioned. For example, as a boron anion, a phosphate anion, and a nitrogen anion, the thing of paragraphs [0037] - [0039] of Unexamined-Japanese-Patent No. 2012-173399 is mentioned. As a carboxylate anion, the carboxylate anion of Unexamined-Japanese-Patent No. 2009-265641 and Unexamined-Japanese-Patent No. 2008-096680 is mentioned, for example. As a sulfate anion, a sulfate anion, a sulfite anion, etc. are mentioned, for example. As an organic sulfonic acid anion, For example, Unexamined-Japanese-Patent No. 2012-173399, International Publication No. 2011/037195, International Publication No. 2011/162217, the specification of Japanese Patent No. 3736221, and Unexamined-Japanese-Patent No. 2011-070172 and those described in the Japanese publication. As a methide anion, For example, Unexamined-Japanese-Patent No. 2011-145540, U.S. Patent 5,554,664 Specification, Unexamined-Japanese-Patent No. 2005-309408, Unexamined-Japanese-Patent No. 2004-085657, Unexamined-Japanese-Patent No. 2010 -505787 publication etc. are mentioned.

As an anion of the transition metal complex which has an azo compound as a ligand, the anion of Unexamined-Japanese-Patent No. 2009-163226 and Unexamined-Japanese-Patent No. 2012-212089 is mentioned, for example.

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 C3F 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.

In addition, as a specific example of a nitrogen anion, [(CN) ₂ N] ^- , [(FSO ₂ ) ₂ N] ^- , [(FSO ₂ )N(CF ₃ SO ₂ )] ^- , [(FSO ₂ )N (CF ₃ CF ₂ SO ₂ )] ^- , [(FSO ₂ )N{(CF ₃ ) ₂ CFSO ₂ }] ^- , [(FSO ₂ )N(CF ₃ CF ₂ CF ₂ SO ₂ )] ^- , [( FSO ₂ )N(CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ )] ^- , [(FSO ₂ )N{(CF ₃ ) ₂ CFCF ₂ SO ₂ }] ^- , [(FSO ₂ )N{CF ₃ CF ₂ (CF ₃ )CFSO ₂ }] ^- , [(FSO ₂ )N{(CF ₃ ) ₃ CSO ₂ }] ^- , [(CF ₃ SO ₂ ) ₂ N] ^- , and the like.

In the coloring composition of this invention, content of compound (2) requires that it be 0.001 mass % or more with respect to total content of compound (1) and compound (2). Since the present inventors have low solubility with respect to a solvent, and crystallize and become a foreign material easily, the present inventors estimate that the storage stability of a coloring composition may have deteriorated. And by including the compound (2) in a predetermined amount or more with the compound (1), crystallization of the compound (1) is prevented, and it is estimated whether the storage stability of a coloring composition may be improved. The content of the compound (2) is preferably 0.003 mass % or more, more preferably 0.005 mass % or more, and 0.008 mass % or more with respect to the total content of the compound (1) and the compound (2) from the viewpoint of further improvement of storage stability. % or more is more preferable, and 0.01 mass % or more is especially preferable. Moreover, from a viewpoint of colored cured film formation with a higher brightness|luminance, 1 mass % or less is preferable, 0.4 mass % or less is more preferable, 0.1 mass % or less is still more preferable, 0.09 mass % or less is still more preferable, 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 mass%, more preferably 0.003 to 0.4 mass%, still more preferably 0.005 to 0.1 mass%, based on the total content of the compound (1) and compound (2), Even more preferably, it is 0.01-0.1 mass %, Especially preferably, it is 0.01-0.08 mass %.

The coloring composition of this invention can also contain coloring agents (henceforth "another coloring agent") other than a compound (1) and a compound (2). It does not specifically limit as another colorant, According to a use, a color and a material can be selected suitably, Any of pigments and dyes other than compound (1) and compound (2) can be used. Especially, in the meaning of obtaining the colored cured film with a high brightness|luminance and color purity, an organic pigment and organic dye are preferable.

As said organic pigment, the compound classified as a pigment in the color index (C.I.; issued by The Society of Dyers and Colorists) is mentioned, for example. Among them, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 179, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 264, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Blue 15:6, C.I. Pigment Blue 80, C.I. Pigment Yellow 83, C.I. Pigment Yellow 129, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185, C.I. Pigment Yellow 211, C.I. Pigment Yellow 215, C.I. Pigment Orange 38, C.I. Pigment violet 23 and the like are preferable. In addition, Japanese Patent Application Laid-Open No. 2001-081348, Japanese Patent Application Laid-Open No. 2010-026334, Japanese Patent Application Laid-Open No. 2010-191304, Japanese Patent Application Laid-Open No. 2010-237384, and Japanese Patent Application Laid-Open No. 2010-237569 The brominated diketopyrrolopyrrole represented by the formula (Ic) of the lake pigment described in Unexamined-Japanese-Patent No. 2011-006602, Unexamined-Japanese-Patent No. 2011-145346, etc., and Unexamined-Japanese-Patent No. 2011-523433. Pigments are also preferred. Among the lake pigments, triarylmethane-based lake pigments, xanthene-based lake pigments, and azo-based lake pigments are preferable, and triarylmethane-based lake pigments and xanthene-based lake pigments are more preferable.

When a pigment is used as another colorant in the present invention, the pigment may be purified and used by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or a combination thereof. In addition, the pigment may be used by modifying the particle surface thereof with a resin, if necessary. As resin which modifies the particle|grain surface of a pigment, the vehicle resin of Unexamined-Japanese-Patent No. 2001-108817, or commercially available resin for various pigment dispersions is mentioned, for example. As a resin coating method of the carbon black surface, for example, the method described in Unexamined-Japanese-Patent No. 9-71733, Unexamined-Japanese-Patent No. 9-95625, Unexamined-Japanese-Patent No. 9-124969, etc., for example. can be adopted. In addition, the organic pigment may be used by refining the primary particles by so-called salt milling. As a method of salt milling, the method disclosed by Unexamined-Japanese-Patent No. Hei 8-179111 is employable, for example.

When using a pigment as another coloring agent in this invention, you may contain a well-known dispersing agent and a dispersing auxiliary agent further. Known dispersants include, for example, urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkylphenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants, and polyester dispersants. , an acrylic dispersing agent, etc., and a pigment derivative etc. are mentioned as a dispersing auxiliary agent.

Such dispersants are commercially available, for example, as acrylic dispersants, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, Big-LPN21116, Big-LPN22102 (above, BYK ), Dispervic-161, Dispervic-162, Dispervic-165, Dispervic-167, Dispervic-170, Dispervic-182, and Dispervic-2164 (above, BYK) as urethane-based dispersants Corporation), Solsperse 76500 (manufactured by Lubrizol Corporation), Solsperse 24000 (manufactured by Lubrizol Corporation) as a polyethyleneimine-based dispersant, Azisper PB821, Azisper PB822 as a polyester-based dispersant; In addition to Ajisper PB880 and Ajisper PB881 (above, manufactured by Ajinomoto Fine Techno Co., Ltd.), Big-LPN21324 (40% by mass of non-volatile components) (by BYK) etc. are mentioned.

Moreover, as a pigment derivative, copper phthalocyanine, diketopyrrolopyrrole, the sulfonic acid derivative of quinophthalone, etc. are mentioned specifically,.

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

It is preferable to use the coloring composition of this invention for formation of a red pixel or a green pixel.

When used for the formation of red pixels, (A) together with compound (1) as a colorant, as other colorants, red pigments, red dyes, purple pigments, purple dyes, yellow pigments, yellow dyes and orange pigments other than compound (1) It is preferable to include at least 1 sort(s) selected from the group which consists of. When used for the formation of green pixels, (A) at least one selected from the group consisting of a green pigment other than compound (1), a green dye, a yellow pigment, and a yellow dye, as another colorant, together with the compound (1) as a colorant It is preferable to include

As said red pigment, C.I. Pigment Red 177, and C.I. Pigment Red 254, C.I. A diketopyrrolopyrrole pigment, such as a pigment represented by the formula (Ic) of Pigment Red 264 and Unexamined-Japanese-Patent No. 2011-523433, is preferable. As the purple pigment, C.I. Pigment Violet 23 is preferred. As said 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 is preferred. As said orange pigment, C.I. Pigment Orange 38 is preferred. As the green pigment, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Phthalocyanine pigments, such as Pigment Green 58, are preferable.

As said red dye and purple dye, a xanthene type dye is preferable.

(A) The content of the coloring agent is usually 5 to 70% by mass, preferably in the solid content of the coloring composition, from the viewpoint of forming a pixel that is not easily defective while having excellent chromaticity characteristics even at a low exposure amount, or a black matrix or black spacer excellent in light-shielding property, preferably 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 coloring agent, 99 mass % or less is preferable with respect to the total content of a coloring agent, and, as for the content rate of another coloring agent, 95 mass parts or less are more preferable. A lower limit is not specifically limited, What is necessary is just 0.01 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 phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as a “carboxyl group-containing polymer”) is preferable, for example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter also referred to as “unsaturated monomer (b1)”) and other copolymerization copolymers of possible ethylenically unsaturated monomers (hereinafter also referred to as "unsaturated monomers (b2)") are mentioned.

As said unsaturated monomer (b1), (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono[2-(meth)acryloyloxyethyl], omega -carboxy polycaprolactone mono(meth)acrylate, for example , p-vinylbenzoic acid, and the like.

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

In addition, as said unsaturated monomer (b2), for example,

N-position 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, and acenaphthylene;

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 to 10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, poly Propylene glycol (degree of polymerization 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 paracumyl phenol, glycidyl ( Meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, 3,4-epoxy Tricyclo[5.2.1.0 ^2,6 ]decan-9-yl (meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]-3 - (meth)acrylic acid esters such as ethyloxetane;

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 vinyl ethers such as;

and macromonomers having a mono(meth)acryloyl group at the terminal 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 individually or in mixture of 2 or more types.

Among these unsaturated monomers (b2), an ethylenic unsaturated monomer having an oxiranyl group, an ethylenically unsaturated monomer having an oxetanyl group, and an ethylenically unsaturated monomer having a tetrahydrofuranyl group having a cyclic ether structure having 2 to 4 carbon atoms. It is preferable that an unsaturated monomer is included, and it is more preferable that the ethylenically unsaturated monomer which has an oxiranyl group is 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, 3 ,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-yl(meth)acrylate is 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 mass%, more preferably 10 to 40 mass%. By copolymerizing an unsaturated monomer (b1) in such a range, the coloring composition excellent in alkali developability and storage stability can be obtained.

As a specific example of the copolymer of an unsaturated monomer (b1) and an unsaturated monomer (b2), For example, Unexamined-Japanese-Patent No. 7-140654, Unexamined-Japanese-Patent No. 8-259876, Unexamined-Japanese-Patent No. Hei (Hei), for example. )10-31308, Japanese Patent Laid-Open (Hei)10-300922, Japanese Patent Laid-Open (Hei)11-174224, Japanese Patent Laid-Open (Hei)11-258415, Japanese Patent Laid-Open No. 2000-56118 and copolymers disclosed in Japanese Patent Application Laid-Open No. 2004-101728 and the like.

Further, in the present invention, for example, Japanese Patent Laid-Open No. (Hei) 5-19467, Japanese Patent Application Laid-Open (Hei) 6-230212, Japanese Patent Laid-Open (Hei) 7-207211, and Japanese Patent Laid-Open (Hei) (Hei) ) 9-325494, as disclosed in Japanese Unexamined Patent Publication (Kokai) No. Hei 11-140144, Japanese Unexamined Patent Publication No. 2008-181095, etc., a polymerizable unsaturated bond such as a (meth)acryloyl group in the side chain The carboxyl group-containing polymer which has can also be used as binder resin.

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

Moreover, ratio (Mw/Mn) of the weight average molecular weight (Mw) and number average molecular weight (Mn) of binder resin in this invention becomes like this. Preferably it is 1.0-5.0, More preferably, it is 1.0-3.0. In addition, Mn here means the number average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran).

Although binder resin in this invention can be manufactured by a well-known method, For example, Unexamined-Japanese-Patent No. 2003-222717, Unexamined-Japanese-Patent No. 2006-259680, International Unexamined-Japanese-Patent No. 07/029871, etc. The structure, Mw, and Mw/Mn can also be controlled by the disclosed method.

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

In the present invention, the content of the binder resin (B) is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, more preferably 50 to 200 parts by mass, still more preferably based on 100 parts by mass of the (A) colorant. is 80 to 150 parts by mass. By setting it as such a form, alkali developability, the storage stability of a coloring composition, a 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 polyfunctional (meth)acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylate, Polyfunctional urethane (meth)acrylate obtained by reacting alkylene oxide-modified polyfunctional (meth)acrylate, (meth)acrylate having a hydroxyl group and polyfunctional isocyanate, (meth)acrylate having a hydroxyl group and an acid anhydride The polyfunctional (meth)acrylate etc. which have a carboxyl group obtained by making it react are mentioned.

Here, as an aliphatic polyhydroxy compound, For example, a bivalent aliphatic polyhydroxy compound like ethylene glycol, propylene glycol, polyethyleneglycol, and polypropylene glycol; and trivalent or higher aliphatic polyhydroxy compounds such as glycerin, trimethylolpropane, pentaerythritol and dipentaerythritol. As (meth)acrylate which has the said hydroxyl group, 2-hydroxyethyl (meth)acrylate, trimethylol propane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta (meth)acrylate, glycerol dimethacrylate, etc. are mentioned. As said polyfunctional isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate etc. are mentioned, for example. Examples of the acid anhydride include an anhydride of a dibasic acid such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride and hexahydrophthalic anhydride, pyromellitic anhydride, and biphenyltetracarboxylic dianhydride. and tetrabasic acid dianhydrides such as water and benzophenone tetracarboxylic dianhydride.

Further, examples of the caprolactone-modified polyfunctional (meth)acrylate include compounds described in paragraphs [0015] to [0018] of Japanese Patent Application Laid-Open No. 11-44955. The alkylene oxide-modified polyfunctional (meth)acrylate is selected from bisphenol A di(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide, ethylene oxide and propylene oxide. Trimethylolpropane tri(meth)acrylate modified with at least one selected from isocyanuric acid tri(meth)acrylate, ethylene oxide and propylene oxide modified by at least one, ethylene oxide and propylene Pentaerythritol tetra(meth)acrylate modified with at least one selected from pentaerythritol tri(meth)acrylate, ethylene oxide and propylene oxide modified with at least one selected from oxide, ethylene Dipentaerythritol penta (meth) acrylate modified with at least one selected from oxide and propylene oxide, dipentaerythritol hexa modified with at least one selected from ethylene oxide and propylene oxide ( Meth) acrylate etc. are mentioned.

Moreover, as a compound which has two or more N-alkoxy methylamino groups, the compound etc. which have a melamine structure, a benzoguanamine structure, and a urea structure are mentioned, for example. In addition, the melamine structure and the benzoguanamine structure refer to a chemical structure having at least one triazine ring or a phenyl-substituted triazine ring as a basic skeleton, and is a concept including melamine, benzoguanamine, or condensates 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(alkoxy methyl) benzoguanamine, N,N,N',N'-tetra(alkoxymethyl)glycoluril, etc. are mentioned.

Among these polymerizable compounds, polyfunctional (meth)acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylate, and polyfunctional urethane (meth)acrylic rate, 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 a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipenta Among the polyfunctional (meth)acrylates in which erythritol hexaacrylate has a carboxyl group, a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, and a compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride It is particularly preferable from the viewpoints of high strength of the colored layer, excellent surface smoothness of the colored layer, and difficulty in causing background contamination, film residue, and the like on the substrate and light-shielding layer of the unexposed portion.

In this invention, (C) polymeric compound can be used individually or in mixture of 2 or more types.

10-1,000 mass parts is preferable with respect to 100 mass parts of (A) coloring agents, as for content of (C) polymeric compound in this invention, 20-700 mass parts is more preferable, 50-500 mass parts is still more preferable, 80 - 250 mass parts is more preferable. Moreover, 50-300 mass parts is preferable with respect to 100 mass parts of (B) binder resin, as for content of (C) polymeric compound, 70-200 mass parts is more preferable, 100-150 mass parts is still more preferable. By setting it in this form, curability and alkali developability are further improved, and generation|occurrence|production of a background contamination, a film|membrane residue, etc. on the board|substrate of an unexposed part or a light-shielding layer can be suppressed to a high level.

-(D) Photoinitiator-

The coloring composition of this invention can be made to contain a photoinitiator. Thereby, radiation sensitivity can be provided to a coloring composition. The photopolymerization initiator used in the present invention is a compound that generates active species capable of initiating polymerization of the polymerizable compound upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray.

Examples of the photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, an O-acyloxime compound, an onium salt compound, a benzoin compound, a benzophenone compound, an α-diketone compound, and a polynuclear compound. A quinone compound, a diazo compound, an imide sulfonate compound, etc. are mentioned.

In the present invention, the photopolymerization initiator may be used alone or in mixture of two or more. As a photoinitiator, at least 1 sort(s) chosen from the group of a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, and an O- acyl oxime compound is preferable.

Specific examples of the thioxanthone compound among the preferred photoinitiators in the present invention include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone. , 2,4-dichlorothioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, and the like.

Further, specific examples of the acetophenone compound include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4 -morpholinophenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc. are mentioned.

Moreover, as a specific example of the said biimidazole compound, 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, etc. are mentioned.

Moreover, when using a biimidazole compound as a photoinitiator, it is preferable at the point which can improve a sensitivity to use a hydrogen donor together. The term "hydrogen donor" as used herein means a compound capable of providing a hydrogen atom to a radical generated from a biimidazole compound upon exposure. Examples of the hydrogen donor include mercaptan hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzooxazole, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-bis(di and amine hydrogen donors such as ethylamino)benzophenone. In the present invention, the hydrogen donor may be used alone or in combination of two or more, but it is more preferable to use one or more mercaptan hydrogen donors and one or more amine hydrogen donors in combination to improve the sensitivity. Do.

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-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)- and triazine compounds having a halomethyl group such as 4,6-bis(trichloromethyl)-s-triazine.

Moreover, as a specific example of an O-acyl oxime compound, 1,2-octanedione, 1- [4- (phenylthio) phenyl] -, 2- (O-benzoyl oxime), ethanone, 1- [9-ethyl- 6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), ethanone,1-[9-ethyl-6-(2-methyl-4-detra) Hydrofuranylmethoxybenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), ethanone,1-[9-ethyl-6-{2-methyl-4-(2,2) -Dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-,1-(O-acetyloxime) etc. are mentioned. Commercially available products of the O-acyloxime compound include NCI-831, NCI-930 (above, manufactured by ADEKA, Ltd.), DFI-020, DFI-091 (above, manufactured by Daitokemix Co., Ltd.), etc. 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, and 4-dimethylaminopropiophenone. , 4-dimethylaminobenzoate ethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl ) coumarin, 4-(diethylamino)chalcone, etc. are mentioned.

In this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (C) polymeric compound, as for content of (D) photoinitiator, 1-100 mass parts is more preferable, 5-50 mass parts is still more preferable, 10 -30 mass parts is especially preferable. By setting it as such a form, sclerosis|hardenability and film characteristic can be improved further.

-(E) solvent-

Although the coloring composition of this invention contains the said (A)-(C) component, and the other component optionally added, it mixes a solvent normally, and is manufactured as a liquid composition.

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

Among these 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 monomethyl ether -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, tri (poly)alkylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and tripropylene glycol monoethyl 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 and 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 (poly)alkylene glycol monoalkyl ether acetates such as acetate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate;

other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran;

ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;

diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate;

Alkoxycarboxyl such as 3-methylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, and 3-methyl-3-methoxybutylpropionate acid esters; 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, i-propyl butyrate , other esters such as n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate;

aromatic hydrocarbons such as toluene and xylene;

Amides or lactams such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone

and the like.

From the viewpoints of solubility in these solvents, pigment dispersibility, applicability, etc., (poly) alkylene glycol monoalkyl ethers, lactic acid alkyl esters, (poly) alkylene glycol monoalkyl ether acetates, other ethers, ketones, di Acetates, alkoxycarboxylic acid esters and other esters are preferable, and propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate are particularly preferred. , 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexane Dioldiacetate, ethyl lactate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxypropionate ethyl, 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, etc. 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 used as the total density|concentration of each component of the coloring composition except the solvent of 5-50 mass % is preferable, and the quantity used as 10-40 mass % is more preferable. By setting it as such a form, a coloring agent dispersion liquid with favorable dispersibility and stability, and a coloring composition with favorable applicability|paintability and stability can be obtained.

-additive-

The coloring composition of this invention may contain various additives as needed.

As an additive, For example, fillers, such as glass and alumina; high molecular compounds such as polyvinyl alcohol and poly(fluoroalkyl acrylate); surfactants such as fluorosurfactants 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-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. adhesion promoter; 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, pentaerythritoltetrakis[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] Oxidation of -2,4,8,10-tetraoxa-spiro[5.5]undecane, thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], etc. inhibitor; UV absorbers such as 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and alkoxybenzophenones; Aggregation inhibitors, 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-propane residue improving agents such as diol, 2-amino-1,3-propanediol, and 4-amino-1,2-butanediol; Developability improvers such as succinic acid mono[2-(meth)acryloyloxyethyl], phthalic acid mono[2-(meth)acryloyloxyethyl], ω-carboxypolycaprolactone mono(meth)acrylate, etc. can be heard

In addition, in the case of using both a dye and a pigment as a colorant in the coloring composition of the present invention, as disclosed in Japanese Patent Application Laid-Open No. 2010-132874, after passing the dye solution through the first filter, the first filter A method of mixing the passed dye solution with a separately prepared pigment dispersion or the like and passing the obtained coloring composition through a second filter may be adopted. In addition, the dye, the components (B) to (C), and other components used as needed are dissolved in a solvent, and the obtained solution is passed through the first filter, and then the solution passed through the first filter is prepared separately. The method of manufacturing by mixing with a pigment dispersion liquid and passing the obtained coloring composition through a 2nd filter can also be employ|adopted. Further, after passing the dye solution through the first filter, the dye solution passed through the first filter, the components (B) to (C), and other components used as needed are mixed and dissolved, and the resulting solution is A method of manufacturing by passing through the second filter, mixing the solution which has passed through the second filter with a separately prepared pigment dispersion, and passing the obtained coloring composition through a third filter can also be adopted.

Colored cured film and method for forming the same

The colored cured film of this invention is formed using the coloring composition of this invention, Specifically, each color pixel which comprises a color filter, a black matrix, a black spacer, etc. are meant.

Hereinafter, the colored cured film used for the color filter which comprises a display element or a solid-state image sensor, and its formation method are demonstrated.

As a method of manufacturing a color filter, the following method is mentioned first. First, a light-shielding layer (black matrix) is formed on the surface of a substrate to partition a portion where pixels are to be formed as needed. Then, on this board|substrate, after apply|coating the liquid composition of the radiation-sensitive coloring composition of this invention of red, for example, prebaking is performed, a solvent is evaporated and a coating film is formed. Then, after exposing this coating film through a photomask, it develops using an alkali developing solution, and dissolves and removes the unexposed part of the coating film. Then, by post-baking, the pixel array in which the red pixel pattern (colored cured film) was arrange|positioned in predetermined arrangement|sequence is formed.

Then, using each green or blue radiation-sensitive coloring composition, it carries out similarly to the above, and each radiation-sensitive coloring composition is applied, pre-baked, exposed, developed and post-baked, and a green pixel array and a blue pixel array are applied. are sequentially formed on the same substrate. Thereby, the color filter in which the pixel array of the three primary colors of red, green, and blue is arrange|positioned on the board|substrate is obtained. However, in the present invention, the order of forming the 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 into a film by sputtering or vapor deposition into a desired pattern using a photolithography method, but using a radiation-sensitive coloring composition in which a black colorant is dispersed It can also be formed in the same manner as in the case of formation.

As a board|substrate used when forming a color filter, glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. are mentioned, for example.

In addition, the substrate may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction method, vacuum deposition, or the like, if necessary.

When applying the radiation-sensitive coloring composition to a substrate, an appropriate coating method such as a spray method, roll coating method, spin coating method (spin coating method), slit die coating method (slit coating method), bar coating method, etc. can be adopted, but , in particular, it is preferable to adopt a spin coating method or a slit die coating method.

The prebaking is usually performed by combining drying under reduced pressure and drying by heating. Drying under reduced pressure is usually performed until it reaches 50 to 200 Pa. In addition, the conditions of heat drying are about 1 to 10 minutes at 70-110 degreeC normally.

Application thickness is 0.6-8 micrometers normally as a film thickness after drying, Preferably it is 1.2-5 micrometers.

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

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

Moreover, as said alkaline developing solution, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1 Aqueous solutions, such as ,5-diazabicyclo-[4.3.0]-5-nonene, are preferable.

An appropriate amount of water-soluble organic solvents, surfactants, etc., such as methanol and ethanol, can also be added to alkaline developing solution, for example. In addition, after alkali development, it washes with water normally.

As a developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (liquid pooling) developing method, etc. are applicable. The developing conditions are preferably 5 to 300 seconds at room temperature.

The conditions of post-baking are about 10 to 60 minutes at 180-280 degreeC normally.

The film thickness of the pixel formed in this way is 0.5-5 micrometers normally, Preferably it is 1-3 micrometers.

In addition, as a second method of manufacturing a color filter, a method of obtaining pixels of each color by an inkjet method disclosed in Japanese Patent Application Laid-Open No. 7-318723, Japanese Patent Application Laid-Open No. 2000-310706, etc. may be adopted. can In this method, first, a barrier rib also serving as a light-shielding function is formed on the surface of the substrate. Then, in the partition formed, after discharging the liquid composition of a red thermosetting coloring composition with an inkjet apparatus, for example, prebaking is performed and a solvent is evaporated. Then, after exposing this coating film as needed, it hardens|cures by post-baking, and a blue pixel pattern is formed.

Then, using each green or blue thermosetting coloring composition, it carries out similarly to the above, and forms a green pixel pattern and a blue pixel pattern one by one on the same board|substrate. Thereby, the color filter in which the pixel pattern of the three primary colors of red, green, and blue is arrange|positioned on the board|substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

In addition, since the barrier rib functions not only as a light-shielding function but also as a function for preventing color mixing of the thermosetting coloring composition of each color discharged into the compartment, the barrier rib has a greater film thickness than the black matrix used in the first method. Accordingly, the barrier ribs are usually formed using a black radiation-sensitive composition.

The board|substrate used when forming a color filter, the light source of a radiation, and the method and conditions of pre-baking and post-baking are the same as that of the above-mentioned 1st method. In this way, the film thickness of the pixel formed by the inkjet method is about the same as the height of the barrier rib.

After forming a protective film as needed on the pixel pattern obtained in this way, a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer may be further formed to obtain a color filter. The spacer is usually formed using a radiation-sensitive composition, but a spacer having light-shielding properties (black spacer) can also be used. In this case, although the radiation-sensitive coloring composition in which the black coloring agent is disperse|distributed is used, the coloring composition of this invention can be used suitably also for formation of such a black spacer.

The radiation-sensitive coloring composition of this invention can be used suitably also in formation of any colored cured film, such as each color pixel used for the said color filter, a black matrix, and a black spacer.

Since the color filter comprising the colored cured film of the present invention formed in this way has very high luminance and color purity, it is very useful for a color liquid crystal display element, a color image tube element, a color sensor, an organic EL display element, an electronic paper, and the like. In addition, the display element mentioned later should just be equipped with at least 1 layer or more of the colored cured films formed using the radiation-sensitive coloring composition of this invention.

display element

The display element of this invention is equipped with the colored cured film of this invention. As a display element, a color liquid crystal display element, an organic electroluminescent display element, electronic paper, etc. are mentioned.

The color liquid crystal display element provided with the colored cured film of this invention may be a transmission type or a reflection type may be sufficient, and an appropriate structure can be employ|adopted. For example, by forming the color filter on a substrate separate from the driving substrate on which the thin film transistor (TFT) is disposed, a structure in which the driving substrate and the substrate on which the color filter is formed face each other through the liquid crystal layer may be adopted. In addition, a structure in which a substrate on 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 on which an ITO (tin-doped indium oxide) electrode is formed face each other through a liquid crystal layer may be adopted. there is. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright, high-definition liquid crystal display element is obtained. In addition, when adopting the latter structure, a black matrix and a black spacer may be formed in either the side of the board|substrate in which the color filter was formed, and the board|substrate side in which the ITO electrode was formed.

The color liquid crystal display element provided with the colored cured film of this invention may be equipped with the backlight unit which uses 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 mixing a red LED, a green LED, and a blue LED, a white LED that obtains white light by mixing a blue LED, a red LED, and a green phosphor, and a blue LED and a red A white LED that obtains white light by mixing a light-emitting phosphor and a green light-emitting phosphor, a white LED that obtains white light by mixing a blue LED and a YAG-based phosphor, a white LED which obtains white light, a white LED which obtains white light by mixing an ultraviolet LED, a red light-emitting fluorescent substance, a green light-emitting fluorescent substance, and a blue light-emitting fluorescent substance, etc. are mentioned.

In the color liquid crystal display element provided with the colored cured film of the present invention, TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, IPS (In-Planes Switching) type, VA (Vertical Alignment) type, OCB (Optically Compensated Birefringence) type An appropriate liquid crystal mode, such as a type, can be applied.

Moreover, the organic electroluminescent display element provided with the colored cured film of this invention can take a suitable structure, for example, the structure currently disclosed by Unexamined-Japanese-Patent No. 11-307242 is mentioned.

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

<Example>

EXAMPLES Hereinafter, embodiment of this invention is described more concretely with reference to an Example. However, the present invention is not limited to the following examples.

<Synthesis of Colorant>

Synthesis Example 1

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

Synthesis Example 2

8.1 g of compound (A1) obtained in Synthesis Example 1, 12.0 g of ethyl orthoformate, and 24 mL of pyridine were added to a 100 mL eggplant-type 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 in a rotary evaporator. Then, 20 mL of acetone was added, and it stirred at 40 degreeC for 30 minutes. Then, it added to 200 mL of diisopropyl ether, ice-cooled and left still for 30 minutes. Thereafter, the precipitate was filtered out by suction filtration, and the obtained solid was dried under reduced pressure to obtain 6.3 g of a reddish-purple solid. Analysis by ¹ H-NMR and LC-MS confirmed that the obtained solid was a mixture of the compound represented by the formula (A2-1) and the compound represented by the formula (A2-2). This compound is used as a colorant (A-2).

Synthesis Example 3

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

Synthesis Example 4

The coloring agent (A-3) was recrystallized by the following method. That is, 5.0 g of the coloring agent (A-3) obtained in Synthesis Example 3 and 100 g of ion-exchanged water containing 10 mass % ethanol were put into a 300 mL eggplant-type flask containing a stirrer, and the mixture was stirred at 80° C. for 2 hours. After that, the solution was cooled and left at 5 DEG C overnight. The precipitate was filtered off by suction filtration, and the obtained solid was dried under reduced pressure to obtain 4.3 g of a reddish-purple solid. This compound is used 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 ion-exchanged water 30 mL was added, and it 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 in a rotary evaporator, and vacuum dried at 50°C overnight 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 formula (A5-1) and the compound represented by the formula (A5-2). This compound is used as a colorant (A-5).

Synthesis Example 6

The same reaction operation as in Synthesis Example 5 was performed except that the colorant (A-3) was used instead of the colorant (A-2) in Synthesis Example 5, and the compound represented by the formula (A5-1) and the formula (A5- A mixture of the compounds represented by 2) was obtained. Let the obtained compound be a coloring agent (A-6).

Synthesis Example 7

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

Synthesis Example 8

Synthesis Example 5 except that in Synthesis Example 5, 2.4 g of p-(vinyl phenyl) trifluoromethanesulfonyl imide acid triethylamine salt was used instead of 2.7 g of lithium-bis(trifluoromethanesulfonyl)imide A reaction operation similar to that was performed. Analysis by ¹ H-NMR and LC-MS confirmed that the obtained solid was a mixture of the compound represented by the formula (A8-1) and the compound represented by the formula (A8-2). Let the obtained compound be a coloring agent (A-8).

Synthesis Example 9

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

Synthesis Example 10

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

Synthesis Example 11

Compound (A11) represented by the above formula was obtained by performing the same reaction operation as in Synthesis Example 1 except that 30.9 g of 1-iodopropane was used in place of 25.9 g of 1-iodomethane in Synthesis Example 1.

Synthesis Example 12

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

Synthesis Example 13

In Synthesis Example 3, recrystallization operation similar to 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, recrystallization operation similar to 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

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

Synthesis Example 16

The same reaction operation as in Synthesis Example 5 was performed except that 3.3 g of the colorant (A-13) was used in place of 3.0 g of the colorant (A-2) in Synthesis Example 5, and the compound represented by the above formula (A15-1) and A mixture of the compound represented by the above formula (A15-2) was obtained. Let the obtained compound be a coloring agent (A-16).

Synthesis Example 17

The same reaction operation as in Synthesis Example 5 was performed except that 3.3 g of the colorant (A-14) was used in place of 3.0 g of the colorant (A-2) in Synthesis Example 5, and the compound represented by the above formula (A15-1) and A mixture of the compound represented by the above formula (A15-2) was obtained. Let the obtained compound be a coloring agent (A-17).

Purity check

Acetonitrile solutions (colorant concentration: 1000 ppm) of colorants (A-5) to (A-10) and (A-15) to (A-17) were respectively prepared, and purity was determined by high performance liquid chromatography under the following analysis conditions was quantified. The concentration of the compound (2) in each colorant, that is, the compound having the structure represented by the formula (2) was measured, and the content of the compound (2) with respect to the total content of the compound (1) and the compound (2) was calculated. A result is shown in Table 1.

[Analysis Conditions]

- Apparatus: 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℃

・Sample injection volume: 10 μL

Flow rate: 0.5mL/min

In Table 1, it is shown that the concentration of compound (2) in the colorants (A-7), (A-10) and (A-17) was below the detection limit in the high performance liquid chromatograph.

<Preparation of pigment dispersion>

Preparation Example 1

As a colorant, C.I. 15 parts by mass of Pigment Red 254, 12.5 parts by mass of Pigment Red 254 (manufactured by BYK) as a dispersant and 72.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent to a bead mill was treated to prepare a pigment dispersion (a-1).

<Preparation of colorant solution>

Preparation 2

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

Preparation Examples 3 to 10

Colorant solutions (A-6) to (A-10) and (A-15) to (A-17) were carried out in the same manner as in Production Example 2, except that in Production Example 2, the colorant was changed as shown in Table 2. was prepared.

<(B) Synthesis of binder resin>

Synthesis Example 18

100 parts by mass of propylene glycol monomethyl ether acetate was put into a flask equipped with a cooling tube and a stirrer, and nitrogen was substituted. At the same temperature by heating to 80° C., 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of monosuccinate (2-acryloyloxyethyl) and 2,2'-azobis(2,4-dimethylvalero) The mixed solution of 6 mass parts of nitriles was dripped over 1 hour, this temperature was maintained and it superposed|polymerized for 2 hours. Then, the temperature of the reaction solution was raised to 100 degreeC, and the binder resin solution (B1) (33 mass % of solid content concentration) was obtained by superposing|polymerizing for 1 hour more. The obtained binder resin had Mw of 12,200 and Mn of 6,500.

Synthesis Example 19

According to the method described in Synthesis Example 6 of Japanese Patent Laid-Open No. 2013-203955, a solution containing a resin having the following structural unit was obtained. Then, propylene glycol monomethyl ether acetate was added, it adjusted so that solid content concentration might be set to 33 mass %, and binder resin solution (B2) (solid content concentration 33 mass %) was obtained.

Preparation of coloring composition

Example 1

(A) 30.5 parts by mass of the pigment dispersion (a-1) as a colorant, 23.0 parts by mass of a colorant solution (A-5), (B) 26.3 parts by mass of a binder resin solution (B1) as a binder resin, (C) as a polymerizable compound 9.9 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Chemical Co., Ltd., trade name KAYARAD DPHA), 2-benzyl-2-dimethyl as a photoinitiator 1.8 parts by mass of amino-1-(4-morpholinophenyl)butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals) and NCI-930 (ADEKA, Ltd.) Production) 0.1 parts by mass of Megaface F-554 (manufactured by DIC Corporation) as a fluorine-based surfactant, 0.05 parts by mass, and propylene glycol monomethyl ether acetate as a solvent, mixed with a solid content concentration of 20% by mass (S-1) ) was prepared.

Evaluation of chromaticity characteristics

After apply|coating the obtained coloring composition using a spin coater on a glass substrate, it prebaked for 10 minutes on an 80 degreeC hotplate, and formed the coating film. The number of revolutions of the spin coater was changed, and three coating films having different film thicknesses were formed by the same operation.

Subsequently, after cooling this substrate to room temperature, using a high-pressure mercury lamp, without passing through a photomask, each coating film is exposed to radiation including wavelengths of 365 nm, 405 nm and 436 nm at an exposure dose of 2,000 J/m ² . did Then, shower development was performed for 90 second by discharging the developing solution containing the 0.04 mass % potassium hydroxide aqueous solution at 23 degreeC with respect to these board|substrates at the developing pressure of 1 kgf/cm< ² > (nozzle diameter 1mm). Then, after wash|cleaning this board|substrate with ultrapure water and air-drying, the colored cured film for evaluation was formed further by performing post-baking in 200 degreeC clean oven for 30 minutes.

Chromaticity coordinate values (x, y) and stimulus value (Y) in the CIE color space system in the C light source and 2 degree field of view using a color analyzer (MCPD2000 manufactured by Otsuka Denshi Co., Ltd.) about the obtained colored cured film of 3 sheets was measured. From the measurement results, the chromaticity coordinate value x and the stimulus value (Y) were obtained when the chromaticity coordinate value y=0.329. Table 3 shows the evaluation results. In addition, it can be said that the higher the stimulus value Y, the higher the luminance.

foreign body evaluation

The coloring composition (S-1), which was left standing at 5 ° C. for 3 days, was applied using a spin coater on a 10 cm × 10 cm soda glass substrate on which a SiO ₂ film to prevent elution of sodium ions was formed on the surface, followed by hot at 90 ° C. Prebaking was performed on the plate for 4 minutes to form a coating film having a film thickness of 2.5 µm after prebaking. Observe the obtained substrate with an optical microscope. If no foreign matter is observed on the coating film, “○”, if the number of foreign substances on the coating is 1 or more and 10 or less, “Δ”, and the number of foreign substances on the coating film is 11 or more. When it was, it was set as "x". Table 3 shows the evaluation results. Moreover, it means that it is excellent in the storage stability of a coloring composition, so that there are few foreign substances.

Examples 2 to 4 and Comparative Examples 1,2

In Example 1, except having changed the kind of a coloring agent solution as Table 3 showed, it carried out similarly to Example 1, and produced the coloring composition. And it carried out similarly to Example 1, and evaluated. A result is shown in Table 3.

Examples 5, 6 and Comparative Example 3

In Example 1, except having changed the kind of the coloring agent solution and binder resin as Table 3 showed, it carried out similarly to Example 1, and produced the coloring composition. And it carried out similarly to Example 1, and evaluated. A result is shown in Table 3.

Claims (9)

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), the content of the compound having a structure represented by the following formula (2), The coloring composition which is 0.001 mass % - 1 mass % with respect to the total content of the compound which has a structure represented by following formula (1), and a compound which has a structure represented by following formula (2).

(In the formula (1),
Ring Z ¹ And Ring Z ² Represent independently of each other a substituted or unsubstituted heterocycle,
p represents 1 or 2, with the proviso that 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,
The substituent of the substituted heterocyclic ring in the ring Z ¹ and the ring Z ² and the substituent of the substituted hydrocarbon group in the R ¹ to R ³ are, respectively, a halogen atom, a hydroxyl group, a cyano group, and a formyl group , carboxyl group, nitro group, amino group, dialkylamino group, diarylamino group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylthio group, arylthio group, trialkylsilyl group, mercapto group, allyl group, alkylsulfonyl group, alkyl a sulfamoyl group, an aliphatic hydrocarbon group, a heterocyclic group, or an aromatic hydrocarbon group)

(In the formula (2),
Ring Z ³ and ring Z ⁴ 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 are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group, provided that a plurality of R ⁴ and R ⁵ may be the same or different,
The substituent of the substituted heterocyclic ring in the ring Z ³ and the ring Z ⁴ and the substituent of the substituted hydrocarbon group in the R ⁴ to R ⁶ are, respectively, a halogen atom, a hydroxyl group, a cyano group, and a formyl group , carboxyl group, nitro group, amino group, dialkylamino group, diarylamino group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylthio group, arylthio group, trialkylsilyl group, mercapto group, allyl group, alkylsulfonyl group, alkyl a sulfamoyl group, an aliphatic hydrocarbon group, a heterocyclic group, or an aromatic hydrocarbon group) The coloring composition of Claim 1 used for formation of a red pixel or a green pixel. The coloring composition according to claim 1 or 2, wherein the compound having a structure represented by the formula (1) and the compound having a structure represented by the formula (2) are a compound having an anion. The coloring composition according to claim 1 or 2, comprising a colorant other than the compound having a structure represented by the formula (1) and the compound having a structure represented by the formula (2). The coloring composition according to claim 1 or 2, wherein the (B) binder resin comprises a copolymer of an ethylenically unsaturated monomer having at least one carboxyl group and another copolymerizable ethylenically unsaturated monomer. The compound according to claim 1 or 2, wherein 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 The coloring composition which is a compound which has a structure represented by following formula (2A).

(In the formula (1A),
R ¹ to R ³ are the same as above,
Ring Z ^1A and ring Z ^2A each independently represent a substituted or unsubstituted aromatic hydrocarbon ring,
Q ¹ and Q ² independently represent -O-, -S- or -CR ¹³ R ¹⁴ -,
R ¹¹ to R ¹⁴ independently represent a substituted or unsubstituted hydrocarbon group,
The substituent of the substituted aromatic hydrocarbon ring in Ring Z ^1A and Ring Z ^2A and the substituent of the substituted hydrocarbon group in R ¹¹ to R ¹⁴ are, respectively, a halogen atom, a hydroxyl group, a cyano group, and a formyl group. , carboxyl group, nitro group, amino group, dialkylamino group, diarylamino group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylthio group, arylthio group, trialkylsilyl group, mercapto group, allyl group, alkylsulfonyl group, alkyl a sulfamoyl group, an aliphatic hydrocarbon group, a heterocyclic group, or an aromatic hydrocarbon group)

(In the formula (2A),
q, R ⁴ to R ⁶ are the same as above,
Ring Z ^3A and ring Z ^4A each independently 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 represent a substituted or unsubstituted hydrocarbon group,
The substituents of the substituted aromatic hydrocarbon ring in Ring Z ^3A and Ring Z ^4A and the substituent of the substituted hydrocarbon group in R ²¹ to R ²⁴ are, respectively, a halogen atom, a hydroxyl group, a cyano group, and a formyl group. , carboxyl group, nitro group, amino group, dialkylamino group, diarylamino group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylthio group, arylthio group, trialkylsilyl group, mercapto group, allyl group, alkylsulfonyl group, alkyl a sulfamoyl group, an aliphatic hydrocarbon group, a heterocyclic group, or an aromatic hydrocarbon group) The content of the compound having a structure represented by the following formula (2), including a compound having a structure represented by the following formula (1) and a compound having a structure represented by the following formula (2), is the following formula (1) The colored cured film which is 0.001 mass % - 1 mass % with respect to the total content of the compound which has a structure represented by and the compound which has a structure represented by following formula (2).

(In the formula (1),
Ring Z ¹ And Ring Z ² Represent independently of each other a substituted or unsubstituted heterocycle,
p represents 1 or 2, with the proviso that 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.
The substituent of the substituted heterocyclic ring in the ring Z ¹ and the ring Z ² and the substituent of the substituted hydrocarbon group in the R ¹ to R ³ are, respectively, a halogen atom, a hydroxyl group, a cyano group, and a formyl group , carboxyl group, nitro group, amino group, dialkylamino group, diarylamino group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylthio group, arylthio group, trialkylsilyl group, mercapto group, allyl group, alkylsulfonyl group, alkyl a sulfamoyl group, an aliphatic hydrocarbon group, a heterocyclic group, or an aromatic hydrocarbon group)

(In the formula (2),
Ring Z ³ and ring Z ⁴ 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 are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group, provided that a plurality of R ⁴ and R ⁵ may be the same or different,
The substituent of the substituted heterocyclic ring in the ring Z ³ and the ring Z ⁴ and the substituent of the substituted hydrocarbon group in the R ⁴ to R ⁶ are, respectively, a halogen atom, a hydroxyl group, a cyano group, and a formyl group , carboxyl group, nitro group, amino group, dialkylamino group, diarylamino group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylthio group, arylthio group, trialkylsilyl group, mercapto group, allyl group, alkylsulfonyl group, alkyl a sulfamoyl group, an aliphatic hydrocarbon group, a heterocyclic group, or an aromatic hydrocarbon group) A display element provided with the colored cured film of Claim 7. The content of the compound having a structure represented by the following formula (2), including a compound having a structure represented by the following formula (1) and a compound having a structure represented by the following formula (2), is the following formula (1) The coloring agent, which is 0.001 mass % to 1 mass % with respect to the total content of the compound which has a structure represented by and the compound which has a structure represented by following formula (2).

(In the formula (1),
Ring Z ¹ And Ring Z ² Represent independently of each other a substituted or unsubstituted heterocycle,
p represents 1 or 2, with the proviso that 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,
The substituent of the substituted heterocyclic ring in the ring Z ¹ and the ring Z ² and the substituent of the substituted hydrocarbon group in the R ¹ to R ³ are, respectively, a halogen atom, a hydroxyl group, a cyano group, and a formyl group , carboxyl group, nitro group, amino group, dialkylamino group, diarylamino group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylthio group, arylthio group, trialkylsilyl group, mercapto group, allyl group, alkylsulfonyl group, alkyl a sulfamoyl group, an aliphatic hydrocarbon group, a heterocyclic group, or an aromatic hydrocarbon group)

(In the formula (2),
Ring Z ³ and ring Z ⁴ 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 are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group, provided that a plurality of R ⁴ and R ⁵ may be the same or different,
The substituent of the substituted heterocyclic ring in the ring Z ³ and the ring Z ⁴ and the substituent of the substituted hydrocarbon group in the R ⁴ to R ⁶ are, respectively, a halogen atom, a hydroxyl group, a cyano group, and a formyl group , carboxyl group, nitro group, amino group, dialkylamino group, diarylamino group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylthio group, arylthio group, trialkylsilyl group, mercapto group, allyl group, alkylsulfonyl group, alkyl a sulfamoyl group, an aliphatic hydrocarbon group, a heterocyclic group, or an aromatic hydrocarbon group)