JP2007277357A - Colored curable composition, color filter, and production method thereof. - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored curable composition excellent in hue (color purity) and fastness (heat resistance and light resistance). <P>SOLUTION: The colored curable composition contains a colorant represented by formula (I), wherein X is selected from among an oxygen atom, =C(CN)<SB>2</SB>, and =N(R<SB>6</SB>); and Y is selected from among -N(R<SB>7</SB>)-, an oxygen atom, and a sulfur atom. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a colored curable composition suitable for producing a color filter used for a liquid crystal display device, a solid-state imaging device or the like, a color filter, and a method for producing the same.

  A pigment dispersion method is used as one of methods for producing a color filter used for a liquid crystal display device, a solid-state imaging device, or the like. The pigment dispersion method is a method for producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions. This method is stable against light and heat due to the use of pigments, and can be secured with sufficient positional accuracy because it is patterned by photolithography, making it suitable for the production of color filters for large screens and high-definition color displays. It has been widely used as a new method.

  In order to produce a color filter by the pigment dispersion method, a radiation-sensitive composition is applied on a substrate with a spin coater, a roll coater or the like, dried to form a coating film, and the coating film is subjected to pattern exposure and development. To obtain a colored pixel. By repeating this operation for the hue, a color filter can be produced.

  However, in recent years, color filters for solid-state imaging devices have been desired to have higher definition, and it is difficult to further improve resolution with conventional pigment dispersion systems, and color unevenness due to coarse pigment particles is difficult. Because of the problems such as the occurrence of the above, it is not suitable for applications requiring a fine pattern such as a solid-state imaging device.

In order to achieve the above high resolution, it has been conventionally studied to use a dye as a coloring material. (For example, refer to Patent Document 1). However, it has been found that dye-containing curable compositions have further new problems. That is,
(1) Dyes are generally inferior in light resistance and heat resistance compared to pigments.
(2) Since ordinary dyes have low solubility in an alkaline aqueous solution or in an organic solvent (hereinafter also simply referred to as a solvent), it is difficult to obtain a liquid curable composition having a desired spectrum.
(3) The dye often exhibits an interaction with other components in the curable composition, and it is difficult to adjust the solubility (developability) of the cured part and the non-cured part.
(4) When the molar extinction coefficient (ε) of the dye is low, a large amount of dye must be added. For that purpose, the polymerizable compound (monomer), binder, photopolymerization initiator, etc. in the curable composition Other components must be reduced, causing problems such as a decrease in the curability of the composition, the heat resistance after curing, and the developability of the (non) cured portion.

  Because of these problems, it has heretofore been difficult to form a fine and thin colored pattern for a high-definition color filter. In addition, unlike a liquid crystal display device or the like, a thin film having a thickness of 1 μm or less is required for the production of a color filter for a solid-state imaging device. Therefore, in order to obtain a desired absorption, it is necessary to add a large amount of a dye in the curable composition, resulting in the above-mentioned problems.

  Next, conventional techniques relating to high fastness dyes will be described. In general, colorants used in various applications are required to have the following properties in common. That is, it has favorable absorption characteristics in terms of color reproducibility, fastness under the environmental conditions used, for example, good heat resistance, light resistance, moisture resistance, etc., has a large molar extinction coefficient and can be thinned. That is needed.

Specifically, azo dyes are widely used (for example, see Patent Documents 2 to 9).
JP-A-6-75375 JP 59-30509 A Japanese Patent Application Laid-Open No. 11-209673 Japanese Patent No. 3020660 JP 49-74718 European Patent Application No. 23309 German Patent Application Publication No. 2513949 German Patent Application No. 28332020 German Patent Application Publication No. 2525505

  However, the pigments (azo dyes) used in the above-described conventional techniques are still insufficient for achieving both spectral characteristics and fastness, and further improvements are desired.

  The present invention has been made in view of the above, and provides a colored curable composition excellent in hue (color purity) and fastness (heat resistance, light resistance), and hue (color purity). The object of the present invention is to provide a color filter excellent in fastness (heat resistance, light resistance) and a method for producing the same, and to achieve the object.

As a result of examining various dyes in detail, the present invention shows that azine-based dyes, oxazine-based dyes, and thiazine-based dyes having a heterocyclic structure have good hues as dyes and are good for heat and light. The knowledge that it has fastness was obtained, and based on such knowledge, a colored curable composition, a color filter and a production method thereof having the following constitution were provided, and the above-mentioned object was achieved.
Specific means for solving the above-mentioned problems are as follows.

<1> A colored curable composition containing a dye represented by the following general formula (I).

In general formula (I), R ₁ represents a hydrogen atom or a substituent, and R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxy group A carbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group is represented. R ₂ and R ₃ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. R ₄ and R ₅ each independently represents a hydrogen atom or a substituent. R ₄ and R ₅ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. X represents an oxygen atom, ═C (CN) ₂ , or ═N (R ₆ ), and R ₆ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, It represents a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group. Y represents —N (R ₇ ) —, an oxygen atom, or a sulfur atom, and R ₇ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, An alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group is represented. Za and Zb each independently represent ═C (R ₈ ) — or ═N—, and R ₈ represents a hydrogen atom or a substituent.

<2> A colored curable composition comprising a dye represented by the following general formula (II) or general formula (III).

In general formula (II) and general formula (III), R ₁ represents a hydrogen atom or a substituent, and R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic ring. A group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group; R ₂ and R ₃ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. R ₄ and R ₅ each independently represents a hydrogen atom or a substituent. R ₄ and R ₅ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. X represents an oxygen atom, ═C (CN) ₂ , or ═N (R ₆ ), and R ₆ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, It represents a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group. Y represents —N (R ₇ ) —, an oxygen atom, or a sulfur atom, and R ₇ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, An alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group is represented. R ₉ represents a hydrogen atom or a substituent, and m represents 0, 1, or 2.

<3> A colored curable composition comprising a dye represented by the following general formula (IV) or general formula (V).

In general formula (IV) and general formula (V), R ₁ represents a hydrogen atom or a substituent, and R ₂ and R ₃ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic ring. A group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group; R ₂ and R ₃ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. R ₄ and R ₅ each independently represents a hydrogen atom or a substituent. R ₄ and R ₅ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. Y represents —N (R ₇ ) —, an oxygen atom, or a sulfur atom, and R ₇ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, An alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group is represented. R ₉ represents a hydrogen atom or a substituent, and m represents 0, 1, or 2.

<4> A colored curable composition comprising a dye represented by the following general formula (VI) or general formula (VII).

In general formula (VI) and general formula (VII), R ₁ represents a hydrogen atom or a substituent, and R ₂ and R ₃ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic ring. A group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group; R ₂ and R ₃ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. R ₉ represents a hydrogen atom or a substituent, and m represents 0, 1, or 2. R ₁₀ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group. R ₁₁ represents a substituent, and n represents an integer of 0 to 4.

<5> A color filter comprising a dye represented by the following general formula (I).

In general formula (I), R ₁ represents a hydrogen atom or a substituent, and R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxy group A carbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group is represented. R ₂ and R ₃ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. R ₄ and R ₅ each independently represents a hydrogen atom or a substituent. R ₄ and R ₅ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. X represents an oxygen atom, ═C (CN) ₂ , or ═N (R ₆ ), and R ₆ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, It represents a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group. Y represents —N (R ₇ ) —, an oxygen atom, or a sulfur atom, and R ₇ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, An alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group is represented. Za and Zb each independently represent ═C (R ₈ ) — or ═N—, and R ₈ represents a hydrogen atom or a substituent.

<6> A color filter comprising the colored curable composition according to any one of <1> to <4>.

<7> A step of coating the colored curable composition according to any one of <1> to <4> on a support, exposing through a mask, and developing to form a pattern image. This is a method for manufacturing a color filter.

  According to the present invention, a colored curable composition having excellent hue (color purity) and fastness (heat resistance, light resistance) can be provided, and hue (color purity) is good and fastness ( A color filter excellent in heat resistance and light resistance and a method for producing the same can be provided.

  Hereinafter, the pigment represented by the general formula (I) will be described first, and then the colored curable composition, the color filter, and the production method thereof will be described in detail.

<< Dye Represented by Formula (I) >>
The colored curable composition and color filter of the present invention are configured to contain at least one dye represented by the following general formula (I).
The dye represented by the general formula (I) is one of an azine dye, an oxazine dye or a thiazine dye having a heterocyclic structure, and hue (color purity) and fastness (heat resistance, light resistance). In addition, it is less likely to precipitate over time when it is in the form of a liquid preparation or a coated film, and is excellent in storage stability (time stability).

In general formula (I), R ₁ represents a hydrogen atom or a substituent, and R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxy group A carbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group is represented. R ₂ and R ₃ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. R ₄ and R ₅ each independently represents a hydrogen atom or a substituent. R ₄ and R ₅ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. X represents an oxygen atom, ═C (CN) ₂ , or ═N (R ₆ ), and R ₆ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, It represents a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group. Y represents —N (R ₇ ) —, an oxygen atom, or a sulfur atom, and R ₇ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, An alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group is represented. Za and Zb each independently represent ═C (R ₈ ) — or ═N—, and R ₈ represents a hydrogen atom or a substituent.

In general formula (I), R ₁ represents a hydrogen atom or a substituent.
Examples of the substituent represented by R ₁ include a halogen atom (for example, fluorine, chlorine, bromine), an alkyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, straight chain, branched chain, Or a cyclic alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl, i-butyl, s-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, Cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), an alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms. For example, vinyl, allyl, 3-butene -1-yl), an aryl group (preferably an aryl having 6 to 48 carbon atoms, more preferably an aryl having 6 to 24 carbon atoms) For example, phenyl, naphthyl), a heterocyclic group (preferably a C1-C32, more preferably a C1-C18 heterocyclic group. For example, 2-thienyl, 4-pyridyl, 2-furyl. , 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), silyl group (preferably having 3 to 38 carbon atoms, more preferably silyl having 3 to 18 carbon atoms) For example, trimethylsilyl, triethylsilyl, tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), hydroxyl group, cyano group, nitro group, alkoxy group (preferably having 1 to 48 carbon atoms, more preferably An alkoxy group having 1 to 24 carbon atoms, for example, methoxy, ethoxy, 1-butoxy, 2-butyl Toxyl, isopropoxy, t-butoxy, dodecyloxy, cycloalkyloxy groups, for example, cyclopentyloxy, cyclohexyloxy), aryloxy groups (preferably having 6 to 48 carbon atoms, more preferably having 6 to 24 carbon atoms) For example, a phenoxy, 1-naphthoxy), a heterocyclic oxy group (preferably a C1-C32, more preferably a C1-C18 heterocyclic oxy group. For example, 1-phenyltetrazole-5 -Oxy, 2-tetrahydropyranyloxy),

A silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms. For example, trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), an acyloxy group (preferably having a carbon number) 2 to 48, more preferably an acyloxy group having 2 to 24 carbon atoms, for example, acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), an alkoxycarbonyloxy group (preferably having 2 to 48 carbon atoms, more preferably a carbon number). 2 to 24 alkoxycarbonyloxy groups such as ethoxycarbonyloxy, t-butoxycarbonyloxy, cycloalkyloxycarbonyloxy groups (for example, cyclohexyloxycarbonyloxy)), aryloxycarbonyloxy A group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms. For example, phenoxycarbonyloxy), a carbamoyloxy group (preferably having 1 to 48 carbon atoms, more preferably A carbamoyloxy group having 1 to 24 carbon atoms, for example, N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenylcarbamoyloxy), sulfamoyloxy group (Preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms. For example, N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy), alkylsulfonyloxy Group (preferably having 1 to 38 carbon atoms, more preferably carbon An alkylsulfonyloxy group having 1 to 24. For example, methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy), arylsulfonyloxy groups (preferably having 6 to 32 carbon atoms, more preferably aryl having 6 to 24 carbon atoms) A sulfonyloxy group, such as phenylsulfonyloxy),

An acyl group (preferably an acyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms. For example, formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl), an alkoxycarbonyl group (preferably An alkoxycarbonyl group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-tert-butyl-4-methyl Cyclohexyloxycarbonyl),

An aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms. For example, phenoxycarbonyl), a carbamoyl group (preferably having 1 to 48 carbon atoms, more preferably carbon A carbamoyl group of 1 to 24. For example, carbamoyl, N, N-diethylcarbamoyl, N-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methyl -N-phenylcarbamoyl, N, N-dicyclohexylcarbamoyl), amino group (preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms. For example, amino, methylamino, N, N- Dibutylamino, tetradecylamino, 2-ethylhexyl Amino, cyclohexylamino), anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24. For example, anilino, N-methylanilino), a heterocyclic amino group (preferably having 1 to 32 carbon atoms). More preferably a heterocyclic amino group of 1 to 18. For example, 4-pyridylamino),

Carboxamide group (preferably a carbonamide group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms. For example, acetamido, benzamide, tetradecanamide, pivaloylamide, cyclohexaneamide), ureido group (preferably having 1 to 32 carbon atoms). More preferably, it is a ureido group having 1 to 24 carbon atoms, for example, ureido, N, N-dimethylureido, N-phenylureido), an imide group (preferably having 36 or less carbon atoms, more preferably having 24 or less carbon atoms). An imide group, for example, N-succinimide, N-phthalimide), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms. For example, methoxycarbonylamino , Ethoxycarbonylamino, t-butoxy Carbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonylamino), aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms. For example, phenoxycarbonylamino ), A sulfonamide group (preferably a sulfonamide group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms. For example, methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide, cyclohexanesulfonamide ), A sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms. For example, N, N-dipropylsulfamoylamino, N-ethyl N- dodecyl sulfamoylamino), an azo group (preferably having 1 to 32 carbon atoms, more preferably an azo group having 1 to 24 carbon atoms. For example, phenylazo, 3-pyrazolyl azo),

An alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably an alkylthio group having 1 to 24 carbon atoms. For example, methylthio, ethylthio, octylthio, cyclohexylthio), an arylthio group (preferably having 6 to 48 carbon atoms, more preferably Is an arylthio group having 6 to 24 carbon atoms, for example, phenylthio), a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic thio group having 1 to 18 carbon atoms. For example, 2-benzo Thiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio), alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms. For example, dodecanesulfinyl group), aryl Sulfinyl group (preferably having 6 to 32 carbon atoms, more preferably carbon number An arylsulfinyl group having from 24 to 24. For example, phenylsulfinyl), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms. For example, methylsulfonyl, ethylsulfonyl, Propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), arylsulfonyl groups (preferably having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms) For example, phenylsulfonyl, 1-naphthylsulfonyl), a heterocyclic sulfonyl group (preferably a heterocyclic sulfonyl group having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms. For example, 2-thiofence Honiru, 2-pyrrole sulfonyl, 3-pyrazole-sulfonyl, 3-pyridine sulfonyl),

Sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms. For example, sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl, N-ethyl -N-phenylsulfamoyl, N-cyclohexylsulfamoyl), sulfo group, phosphonyl group (preferably phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms. For example, phenoxyphosphonyl, Octyloxyphosphonyl, phenylphosphonyl), a phosphinoylamino group (preferably a phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms. For example, diethoxyphosphinoylamino, Dioctyloxyphosphinoylamino).

When the substituent represented by R ₁ is a further substitutable group, it may have the substituent described above, and when it has two or more substituents, These substituents may be the same or different.

In general formula (I), R ₂ and R ₃ are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl Group represents a heterocyclic sulfonyl group.

The alkyl group, alkenyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, and heterocyclic sulfonyl group represented by R ₂ and R ₃ are the above R _1. These are groups having the same meaning as the alkyl group, alkenyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, and heterocyclic sulfonyl group described in the above. The same applies to the preferred range.

The alkyl group, alkenyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, and heterocyclic sulfonyl group represented by R ₂ and R ₃ are further described above. It may be substituted with the substituent described in R ₁ , and when it is substituted with two or more substituents, these substituents may be the same or different.

R ₂ and R ₃ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring together with the nitrogen atom, and the 5-membered, 6-membered or 7-membered ring formed is It may be substituted with the substituent described for R ₁ . Examples of the 5-membered ring formed by combining R ₂ and R ₃ include an imidazolidine ring and a pyrrolidine ring. Examples of the 6-membered ring include a piperidine ring, a piperazine ring, a hexahydropyrimidine ring, a morpholine ring, and a thiomorpholine ring. A seven-membered ring includes an azepan ring.

In the general formula (I), R ₄ and R ₅ each independently represents a hydrogen atom or a substituent, and the substituent represented by R ₄ and R ₅ has the same meaning as the substituent described for R ₁ above. The same applies to the preferred range. When the substituents represented by R ₄ and R ₅ are further substitutable groups, they may be substituted with the substituents described for R ₁ and are substituted with two or more substituents. In some cases, the substituents may be the same or different.

R ₄ and R ₅ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and the formed 5-membered, 6-membered, and 7-membered rings can be further substituted May be substituted with the substituent described in the above R ₁ . Examples of the 5-membered ring formed by combining R ₄ and R ₅ include 1,3-cyclopentanediene ring, 2,3-dihydropyrrole ring, pyrrole ring, imidazole ring, pyrazole ring, imidazolidinone. A ring, an imide ring, a pyrazolone ring, and the like. Examples of the 6-membered ring include a cyclohexene ring, a benzene ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, and a pyridone ring. A 7-membered ring includes a cycloheptene ring.

In general formula (I), X represents an oxygen atom, ═C (CN) ₂ , or ═N (R ₆ ), and R ₆ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, An acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group is represented.

Alkyl group, an alkenyl group represented by R _6, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic sulfonyl group, described for R ₁ It is a group having the same meaning as an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic sulfonyl group. The same applies to the preferred range.

The alkyl group, alkenyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, and heterocyclic sulfonyl group represented by R ₆ are further represented by R ₁ . The substituents described above may be substituted, and when substituted with two or more substituents, the substituents may be the same or different.

In the general formula (I), Y, -N (R ₇₎ -, an oxygen atom or a sulfur atom, R ₇ is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, Represents an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group;

Alkyl group, an alkenyl group represented by R _7, aryl group, heterocyclic group, acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic sulfonyl group, described for R ₁ It is a group having the same meaning as an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic sulfonyl group. The same applies to the preferred range.

The alkyl group, alkenyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, and heterocyclic sulfonyl group represented by R ₇ are further represented by R ₁ . The substituents described above may be substituted, and when substituted with two or more substituents, the substituents may be the same or different.

In general formula (I), Za and Zb each independently represent ═C (R ₈ ) — or ═N—, and R ₈ represents a hydrogen atom or a substituent.
The substituent represented by R ₈ represents a group having the same meaning as the substituent described for R ₁ , and the same applies to the preferred range. In the case where the substituent represented by R ₈ is a further substitutable group, it may be substituted with the substituent described in the above R ₁ , and when it is substituted with two or more substituents These substituents may be the same or different.

  The dye represented by the general formula (I) is preferably represented by the general formula (II) or the general formula (III).

In general formula (II) and general formula (III), R < ₁ >, R < ₂ >, R < ₃ >, R < ₄ >, R < ₅ >, X, and Y are R < ₁ >, R < ₂ >, R < ₃ >, R <R> in general formula (I). ₄ , R ₅ , X, and Y are synonymous, R ₉ represents a hydrogen atom or a substituent, and m represents 0, 1, or 2.

In general formula (II) and general formula (III), R ₉ represents a hydrogen atom or a substituent, and the substituent represented by R ₉ has the same meaning as the substituent described in R ₁ above, and a preferred range Is the same. In the case where the substituent represented by R ₉ is a further substitutable group, it may be substituted with the substituent described in the above R ₁ , and when it is substituted with two or more substituents These substituents may be the same or different.
In general formula (II), m represents 0, 1, or 2.

  The dye represented by the general formula (I) is more preferably represented by the general formula (IV) or the general formula (V).

In general formula (IV) and general formula (V), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₉ , m, and Y are the same as those in general formula (II) and general formula (III). Synonymous with R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₉ , m, and Y.

  The dye represented by the general formula (I) is more preferably represented by the general formula (VI) and the general formula (VII).

In the general formula (VI) and the general formula _{(VII), R 1, R} 2, R 3, R 9, and _{m, R 1, R 2, R} 3 in the general formula (IV) and the general formula (V) , R ₉ and m.

In general formula (VI) and general formula (VII), R ₁₀ is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group. Or a heterocyclic sulfonyl group.

Alkyl group, an alkenyl group represented by R _10, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic sulfonyl group, described for R ₁ It is a group having the same meaning as an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic sulfonyl group. The same applies to the preferred range.

Alkyl group, an alkenyl group represented by R _10, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic sulfonyl group, described for R ₁ It may be substituted with a substituent, and when substituted with two or more substituents, these substituents may be the same or different.

In General Formula (VI) and General Formula (VII), R ₁₁ represents a substituent, and n represents an integer of 0 to 4.
The substituent represented by R ₁₁ represents a group having the same meaning as the substituent represented by R ₁ . The same applies to the preferred range. When the substituent represented by R ₁₁ is a further substitutable group, it may be substituted with the substituent described for R ₁ . When substituted with two or more substituents, these substituents may be the same or different.

Most preferably, in general formula (VI) and general formula (VII), R ₂ and R ₃ are each independently represented by an alkyl group, alkenyl group, aryl group, or heterocyclic group, and R ₁₀ is an alkyl group. , An alkenyl group, an aryl group, or a heterocyclic group.

  Next, specific examples (Exemplary dyes Ia-1 to Ia-23, IIa) of the dyes represented by the general formula (I) (including the dyes represented by the general formulas (II) to (VII); the same shall apply hereinafter). -1 to IIa-18, Ib-1 to Ib-16, IIIa-1 to IIIa-18, IIIb-1 to IIIb-6), but the present invention is not limited thereto.

<Synthesis example>
Next, synthesis examples of the dye represented by the general formula (I) will be described in detail.

[Synthesis Example 1]
(Synthesis of Exemplified Dye Ia-1)
Synthesized according to Reaction Scheme A below.

-Synthesis of Intermediate B-
250 ml of methanol was added to 53.47 g (0.1 mol) of intermediate A obtained by the method described in JP-A-2002-371079, and the mixture was heated and stirred. To this dispersion, 30 g of zinc powder was added, and then 60 ml of acetic acid was added dropwise. After completion of the dropwise addition, the mixture was heated and stirred for 2 hours to complete the reaction. After completion of the reaction, the reaction solution was cooled to room temperature and then filtered to remove insoluble matters. The filtrate was extracted by adding 500 ml of ethyl acetate and 500 ml of water. The ethyl acetate solution was washed with water and dried over anhydrous magnesium sulfate. When ethyl acetate was concentrated under reduced pressure, crystals were precipitated. To this crystal, 250 ml of acetonitrile was added and stirred, and then the crystal was dispersed. The crystals were filtered and dried to obtain 28.5 g of intermediate B (yield: 76.0%).

-Synthesis of Exemplified Dye Ia-1-
100 ml of chloroform was added to 21.1 g (0.04 mol) of Intermediate C and 16.5 g (0.044 mol) of Intermediate B obtained by the above method, and the mixture was stirred at room temperature. To this solution was added 14 ml of triethylamine. Subsequently, 34.8 g of manganese dioxide was added. After completion of the addition, the mixture was stirred at room temperature for 8 hours and then left overnight. After completion of the reaction, the mixture was filtered to remove insoluble matters, and the chloroform solution was washed with saturated brine. This chloroform solution was separated and purified by silica gel column chromatography. When the fraction of the target product was concentrated, crystals were precipitated. The crystals were purified by recrystallization from ethyl acetate to obtain 20.5 g (yield: 57.1%) of Exemplified dye Ia-1. The melting point was 245 ° C. to 248 ° C.
When the maximum absorption wavelength (λmax) and molar absorption coefficient (ε) in ethyl acetate were measured with a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation), the maximum absorption wavelength λmax = 512.7 nm, the molar absorption coefficient ( ε) was 36500 [l · mol ⁻¹ · cm ⁻¹ ].

[Synthesis Example 2]
(Synthesis of Exemplified Dye Ia-2)
Synthesized according to Reaction Scheme A above.
30 ml of N-methylpyrrolidone was added to 9.1 g (0.01 mol) of “Exemplary dye Ia-1” obtained by the above method, 3 g of potassium carbonate, and 1 g of tetrabutylammonium bromide, followed by stirring at room temperature. To this solution, 5 g of methyl iodide was added dropwise. After completion of dropping, the mixture was heated to 40 ° C. to 45 ° C. and stirred for 8 hours. After completion of the reaction, 200 ml of ethyl acetate and 500 ml of water were added for extraction. The ethyl acetate solution was washed with brine and then dried over anhydrous magnesium sulfate. The ethyl acetate solution was concentrated under reduced pressure. The residue was separated and purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 1/1). The target fraction was concentrated and recrystallized from n-hexane for purification. 6.8g (yield: 74.6%) of exemplary pigment | dye Ia-2 was obtained. The melting point was 173 ° C. to 176 ° C.
When the maximum absorption wavelength (λmax) and molar extinction coefficient (ε) in ethyl acetate were measured with a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation), the maximum absorption wavelength λmax = 515.6 nm, the molar extinction coefficient ( ε) was 40300 [l · mol ⁻¹ · cm ⁻¹ ].

[Synthesis Example 3]
(Synthesis of Illustrative Dye IIa-1)
Synthesized according to Reaction Scheme B below.

-Synthesis of Intermediate E-
100 ml of methanol was added to 17.1 g (0.05 mol) of Intermediate D synthesized according to the method described in JP-A-2005-213357, and the mixture was cooled to 5 ° C. and stirred. To this solution, 12.9 ml of concentrated hydrochloric acid was added and stirred. Further, an aqueous solution in which 4.15 g (0.06 mol) of sodium nitrite was dissolved in 15 ml of water was dropped. The reaction temperature was kept below 10 ° C. After completion of dropping, the mixture was stirred at 10 to 15 ° C. for 2 hours. After completion of the reaction, the reaction solution was poured into 600 ml of water and 200 ml of ethyl acetate with stirring. Then, the mixture was neutralized with sodium hydrogen carbonate and extracted with ethyl acetate. The ethyl acetate solution was washed with brine and then dried over anhydrous magnesium sulfate. Ethyl acetate was concentrated under reduced pressure. 16.8 g (Yield = 90.8%) of Intermediate E was obtained.

-Synthesis of Exemplified Dye IIa-1-
50 ml of acetonitrile was added to 4.45 g (0.012 mol) of Intermediate E and 5.29 g (0.01 mol) of Intermediate C, followed by stirring at room temperature. To this solution, 1.7 ml of acetic anhydride was added and stirred for 24 hours. Subsequently, it heated at 40 degreeC and stirred for 3 hours. Next, after cooling to room temperature, 5 g of manganese dioxide was added. After completion of the addition, the mixture was stirred at room temperature for 3 hours. After completion of the reaction, the mixture was filtered to remove insoluble matters, and extracted with 100 ml of ethyl acetate and 200 ml of water. The ethyl acetate solution was washed with brine and then dried over anhydrous magnesium sulfate. Ethyl acetate was concentrated under reduced pressure, and the residue was separated and purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 1/1). After concentrating the fraction of interest, acetonitrile was added to precipitate crystals. The crystals were filtered and dried. 4.22g (yield: 48.0%) of exemplary pigment | dye IIa-1 was obtained. The melting point was 70-72 ° C.
When the maximum absorption wavelength (λmax) and molar extinction coefficient (ε) in ethyl acetate were measured with a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation), the maximum absorption wavelength λmax = 524.9 nm, the molar extinction coefficient ( ε) was 45700 [l · mol ⁻¹ · cm ⁻¹ ].

-Synthesis of Illustrative Dye IIa-2-
100 mL of N-methylpyrrolidone was added to 8.79 g (0.01 mol) of “Exemplary dye IIa-1” obtained by the above method and 2.84 g (0.02 mol) of methyl iodide, and the mixture was stirred at room temperature. An aqueous solution in which 0.5 g of lithium hydroxide was dissolved in 5 ml of water was added to this solution. The reaction was stirred at room temperature for 5 hours. After completion of the reaction, the mixture was poured into a mixed solution of 5% aqueous hydrochloric acid 300 ml and ethyl acetate 200 ml with stirring, and extracted. The ethyl acetate solution was washed with saturated brine and then dried over anhydrous magnesium sulfate. The ethyl acetate solution was concentrated to dryness under reduced pressure. Subsequently, the residue was separated and purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 2/1). The fraction of the target product was concentrated to obtain 4.71 g (yield: 52.7%) of amorphous exemplified dye IIa-2. The melting point was 78-82 ° C.
When the maximum absorption wavelength (λmax) and molar extinction coefficient (ε) in ethyl acetate were measured with a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation), the maximum absorption wavelength λmax = 531.2 nm, the molar extinction coefficient ( ε) was 48800 [l · mol ⁻¹ · cm ⁻¹ ].

[Synthesis Example 4]
(Synthesis of Exemplified Dye IIIa-13)
Exemplified dye IIIa-13 can be synthesized by the synthesis method described in JP-A-2-188854.

[Synthesis Example 5]
The exemplified dye IIIb-1 can be synthesized by the synthesis method described in JP-A No. 61-140588.

  The dye represented by the general formula (I) described above can be used in a color filter for recording and reproducing a color image used in a solid-state imaging device such as a CCD or a display such as an LCD or PDP. It can also be used as an ink for ink jet printing.

≪Colored curable composition≫
The colored curable composition of the present invention contains at least one dye represented by the aforementioned general formula (I), and if necessary, other dyes, an alkali-soluble binder, a crosslinking agent, a monomer, It contains a photopolymerization initiator, a radiation sensitive compound such as a naphthoquinonediazide compound, a solvent, and the like. In this case, when the colored curable composition of the present invention is constituted as a negative composition, a monomer and a photopolymerization initiator can be contained together with an alkali-soluble binder. Further, when the colored curable composition of the present invention is formed into a positive composition, a naphthoquinone diazide compound is contained together with an alkali-soluble binder, and a phenol resin such as a novolak resin is used as the alkali-soluble binder. Is preferred.

<Colorant>
In the colored curable composition of this invention, the pigment | dye represented by the said general formula (I) can be used individually or in combination as a coloring agent.
Here, the dye represented by the general formula (I) is used as a salt of an alkali metal salt (for example, lithium, sodium, potassium, calcium, magnesium) or an organic base (for example, triethylamine, trioctylamine, guanidine). May be.
Moreover, the pigment | dye represented by general formula (I) can be used in combination with another well-known pigment | dye. For example, as yellow dyes, pyrazolone azo dyes (for example, described in JP-B No. 7-111485), pyridone azo dyes (described in JP-A No. 2002-14223), methine dyes (for example, described in JP-A No. 2001-342364), quinophthalone dye And yellow dyes. Examples of the magenta dye include pyrazoloazole-based azomethine dyes and xanthene dyes (for example, described in JP-A No. 2002-14222). Examples of the cyan dye include phthalocyanine dyes, triarylmethane dyes (for example, described in JP-A No. 2002-14221), pyrroloazole azomethine dyes, and the like.

  The total concentration of the colorant of the present invention in the colored curable composition varies depending on the molecular weight and molar absorption coefficient with respect to the total solid content of the composition, but the film thickness, spectral absorption, and solubility of the color filter are different. From the viewpoint, 0.5 to 80% by mass is preferable, 0.5 to 60% by mass is more preferable, and 0.5 to 50% by mass is particularly preferable.

<Alkali-soluble binder>
The colored curable composition of the present invention preferably contains at least one alkali-soluble binder.
The alkali-soluble binder is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.
The alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid as described in the specifications of No. 25957, JP-A-59-53836, JP-A-59-71048, etc. There are a copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, and the like. Similarly, an acidic cellulose derivative having a carboxylic acid in the side chain is useful. In addition to this, an acid anhydride added to a polymer having a hydroxyl group, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. Is also useful.

  In addition, a monomer having a hydrophilic group may be copolymerized. Examples of this monomer include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N- Methylol acrylamide, secondary and tertiary alkyl acrylamide, dialkylaminoalkyl (meth) acrylate, morpholino (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl ( Examples include meth) acrylate, branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like.

Other monomers having a hydrophilic group include a tetrahydrofurfuryl group, a phosphoric acid group, a phosphoric ester group, a quaternary ammonium base, an ethyleneoxy chain, a propyleneoxy chain, a sulfonic acid or its base, a monomer containing a morpholinyl group, etc. Useful.
In order to improve the crosslinking efficiency, a polymerizable group may be included in the side chain, and a polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is also useful.

Examples of the polymer having these polymerizable groups include KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like.
In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  Among the various binders described above, alkali-soluble binders that can be used in the present invention include polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymers from the viewpoint of heat resistance. A coalesced resin is preferred. From the viewpoint of control of developability, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable. Examples of the acrylic resin include a copolymer composed of monomers selected from benzyl (meth) acrylate, (meth) acryl, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and KS-resist-106 (Osaka Organic Chemical). Kogyo Co., Ltd.) and Cyclomer P-series (Daicel Chemical Industries, Ltd.) are preferred.

Moreover, an alkali-soluble phenol resin can be used as the alkali-soluble binder. The alkali-soluble phenol resin can be suitably used when the colored curable composition of the present invention is formed into a positive composition. As said alkali-soluble phenol resin, a novolak resin or a vinyl polymer is mentioned, for example.
Examples of the novolac resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of the phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, and bisphenol A.
Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, and benzaldehyde.
The said phenols and aldehydes can be used individually or in combination of 2 or more types.

  Specific examples of the novolak resin include, for example, a condensation product of metacresol, paracresol or a mixture thereof and formalin. The novolak resin may be adjusted in molecular weight distribution by means of fractionation or the like. Moreover, you may mix the low molecular weight component which has phenolic hydroxyl groups, such as bisphenol C and bisphenol A, with the said novolak resin.

The alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene conversion value measured by GPC method) of 1000 to 2 × 10 ⁵ , more preferably 2000 to 1 × 10 ⁵ , and 5000 to ⁵ ×. 10 ⁴ polymers are particularly preferred.
The total amount of the alkali-soluble binder used in the colored curable composition of the present invention is based on the total solid content in the composition from the viewpoints of coatability, developability, color filter film thickness, solubility, and the like. 0-90 mass% is preferable and 0-50 mass% is still more preferable. 0-20 mass% is especially preferable.

<Crosslinking agent>
Next, the crosslinking agent will be described.
In the present invention, a film having better curability than the conventional one can be obtained by using the dye represented by the general formula (I), but additionally, the film is further cured to a higher degree using a crosslinking agent. It is possible to obtain a membrane.
The crosslinking agent that can be used in the present invention is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and acyloxymethyl. At least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, which is substituted with at least one substituent selected from the group A phenolic compound, a naphthol compound or a hydroxyanthracene compound substituted with Of these, polyfunctional epoxy resins are preferred.

  The epoxy resin (a) may be any epoxy resin as long as it has an epoxy group and has crosslinkability, for example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether. , Hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diphthalic acid diglycidyl ester, N, N-diglycidyl aniline and other divalent glycidyl group-containing low molecular weight compounds, as well as trimethylolpropane triglycidyl ether, Trivalent glycidyl group-containing low molecular weight compounds represented by methylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, etc., as well as pentaerythritol tetraglycidyl ether, tetramethylol vinyl Tetravalent glycidyl group-containing low molecular weight compounds typified by phenol A tetraglycidyl ether, polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether, dipentaerythritol hexaglycidyl ether, polyglycidyl ( And glycidyl group-containing polymer compounds represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like. .

The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in the crosslinking agent (b) is 2 to 6 for melamine compounds, 2 for glycoluril compounds, guanamine compounds, and urea compounds. Although it is -4, Preferably it is 5-6 in the case of a melamine compound, and is 3-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound.
Hereinafter, the melamine compound, guanamine compound, glycoluril compound and urea compound of (b) are collectively referred to as a compound according to (b) (methylol group-containing compound, alkoxymethyl group-containing compound, or acyloxymethyl group-containing compound).

  The methylol group-containing compound according to (b) can be obtained by heating the alkoxymethyl group-containing compound according to (b) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like. The acyloxymethyl group-containing compound according to (b) can be obtained by mixing and stirring the methylol group-containing compound according to (b) with acyl chloride in the presence of a basic catalyst.

Hereinafter, specific examples of the compound according to (b) having the substituent will be given.
Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 5 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol. Examples thereof include compounds in which 1 to 5 methylol groups of melamine are acyloxymethylated, or mixtures thereof.

  Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol guanamine or a mixture thereof, tetramethoxyethyl guanamine, tetraacyloxymethyl guanamine, tetramethylol. Examples thereof include compounds in which 1 to 3 methylol groups of guanamine are acyloxymethylated or a mixture thereof.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethylglycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolglycoluril, or a mixture thereof, or a methylol group of tetramethylolglycoluril. Examples thereof include compounds obtained by acylating 1 to 3 or a mixture thereof.

Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea.
These compounds according to (b) may be used alone or in combination.

  The crosslinking agent (c), that is, the phenol compound, naphthol compound or hydroxyanthracene compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group is the crosslinking agent (b). As in the case of, the thermal cross-linking suppresses intermixing with the overcoated photoresist and further increases the film strength. Hereinafter, these compounds may be collectively referred to as a compound according to (c) (a methylol group-containing compound, an alkoxymethyl group-containing compound, or an acyloxymethyl group-containing compound).

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the crosslinking agent (c) is at least 2 per molecule, and from the viewpoint of thermal crosslinkability and storage stability, phenol as a skeleton Compounds in which the 2nd and 4th positions of the compound are all substituted are preferred. Further, the naphthol compound and hydroxyanthracene compound as the skeleton are preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. The 3-position or 5-position of the phenol compound may be unsubstituted or may have a substituent.
The naphthol compound may be unsubstituted or substituted except for the ortho position of the OH group.

The methylol group-containing compound according to (c) is a compound in which the ortho-position or para-position (2-position or 4-position) of the phenolic OH group is a hydrogen atom, and this is used as sodium hydroxide, potassium hydroxide, It can be obtained by reacting with formalin in the presence of a basic catalyst such as ammonia or tetraalkylammonium hydroxide.
The alkoxymethyl group-containing compound according to (c) can be obtained by heating the methylol group-containing compound according to (c) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like.
The acyloxymethyl group-containing compound according to (c) can be obtained by reacting the methylol group-containing compound according to (c) with an acyl chloride in the presence of a basic catalyst.

  Examples of the skeletal compound in the crosslinking agent (c) include phenolic compounds, naphthols, hydroxyanthracene compounds in which the ortho-position or para-position of the phenolic OH group is unsubstituted, and examples thereof include phenol and cresol isomers, 2 , 3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol A, 4,4'-bishydroxybiphenyl, TrisP-PA (Honshu Chemical Industry) Naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, etc. are used.

  Specific examples of the crosslinking agent (c) include, as a phenol compound or a naphthol compound, for example, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, tri (methoxymethyl) phenol, trimethylolphenol, Trimethylol-3-cresol, tri (methoxymethyl) -3-cresol, compounds obtained by methoxymethylating 1 to 2 methylol groups of trimethylol-3-cresol, 2,6-dimethylol-4-cresol and the like Compounds obtained by methoxymethylating 1 to 3 methylol groups of methylol cresol, tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethyl A compound obtained by methoxymethylating 1 to 5 methylol groups of xymethyl-4,4′-bishydroxybiphenyl, hexamethylol of TrisP-PA, hexamethoxymethyl of TrisP-PA, hexamethylol of TrisP-PA, Bishydroxymethyl naphthalene diol, etc. are mentioned.

Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene.
Examples of the acyloxymethyl group-containing compound include compounds obtained by partially or fully acyloxymethylating the methylol group of the methylol group-containing compound.

Among these compounds, trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, trisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or a methylol group thereof is preferable. Examples thereof include an alkoxymethyl group and a phenol compound substituted with both a methylol group and an alkoxymethyl group.
These compounds according to (c) may be used alone or in combination.

  The colored curable composition of the present invention does not necessarily contain a crosslinking agent. When the cross-linking agent is contained in the colored curable composition of the present invention, the total content of the components (a) to (c) varies depending on the material of the compound contained in the composition. From a viewpoint of a film thickness and solubility, 1-70 mass% is preferable with respect to solid content of this composition, 5-50 mass% is more preferable, 7-30 mass% is especially preferable.

<Monomer>
Next, the monomer contained when the colored curable composition of the present invention is a negative composition will be described.
In addition, even if this monomer is a case where the colored curable composition of this invention is comprised by the positive type containing the naphthoquinone diazide compound mentioned later, it can contain with the photoinitiator mentioned later. In this case, the degree of cure of the pattern formed by the monomer can be further promoted. Hereinafter, the monomer will be described.

  As the monomer, a compound having at least one ethylenically unsaturated group and having a boiling point of 100 ° C. or higher under normal pressure is preferable. Examples thereof include polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate. , Monofunctional acrylates and methacrylates such as phenoxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate After adding ethylene oxide and propylene oxide to polyfunctional alcohols such as relates, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane, (meth) acrylated Urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191 Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof described in JP-B-52-30490 To give It can be.

  Furthermore, as a monomer that can be used in the present invention, the Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.

  From the viewpoint of curability and the film thickness of the color filter, the total content of the above monomers in the colored curable composition is preferably 0.1 to 90% by mass, and 1.0 to 80% by mass with respect to the solid content. Further preferred is 2.0 to 70% by mass.

<Radiation sensitive compounds>
The colored curable composition of this invention can be comprised suitably by containing at least 1 type of a radiation sensitive compound. The radiation-sensitive compound that may be used in the present invention is a compound that can cause a chemical reaction such as generation of a radical, generation of an acid, generation of a base, etc., against radiation such as UV, Deep UV, visible light, infrared light, or electron beam. However, the coating film can be made alkaline by insolubilizing the above binder by a reaction such as crosslinking, polymerization, decomposition of acidic groups, polymerization of polymerizable monomers and oligomers coexisting in the coating film, crosslinking of the crosslinking agent, etc. It is used for the purpose of insolubilizing with a developer.

  The colored curable composition preferably contains a photopolymerization initiator particularly when it is configured as a negative type, and preferably contains a naphthoquinone diazide compound when it is configured as a positive type. .

(Photopolymerization initiator)
Next, the photopolymerization initiator contained when the colored curable composition of the present invention is a negative composition will be described.
The photopolymerization initiator is not particularly limited as long as it can polymerize the monomer having a polymerizable group, but is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.
In addition, as above-mentioned, you may contain a photoinitiator in the positive type | system | group containing said naphthoquinone diazide compound, In this case, the hardening degree of the pattern formed can be promoted more.

  Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyl oxadiazole compound, a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, an acetophenone compound, and Examples thereof include cyclopentadiene-benzene-iron complexes and salts thereof, and oxime compounds.

  Examples of the halomethyloxadiazole compound include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compound described in JP-B-57-6096, 2-trichloromethyl-5-styryl- 1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1, 3,4-oxadiazole and the like can be mentioned.

  Examples of the photopolymerization initiator of the halomethyl-s-triazine compound include vinyl-halomethyl-s-triazine compounds described in Japanese Patent Publication No. 59-1281 and 2- (naphtho) described in JP-A-53-133428. -1-yl) -4,6-bis-halomethyl-s-triazine compounds and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compounds.

  Other examples include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,6-bis (trichloromethyl) -4- (3,4-methylenedioxyphenyl)- 1,3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (1- p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphth-1-yl) -4,6 -Bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-) Le) -4,6-bis - trichloromethyl -s- triazine, 2- (4-butoxy - naphth-1-yl) -4,6-bis - trichloromethyl -s- triazine,

2- [4- (2-methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2 -Methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6-bis-trichloromethyl- s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis -Trichloromethyl-s-triazi 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphth-2-yl) -4,6-bis- Trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl) ) Aminophenyl] -2,6-di (trichloromethyl) -s-triazine,

4- [o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, N-di (chloroethyl) Aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s -Triazine, 4- (p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (p-N-ethoxycarbonylmethylaminophenyl) -2,6-di ( Trichloromethyl) -s-triazine, 4- [p-N, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethyl cal Nylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl] -2,6-di (trichloromethyl) -s-triazine 4- [m-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine,

4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N- Di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6 -Di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [O-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (eth Cycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-p -N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (chloroethyl) aminophenyl] -2, 6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [ m Fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylaminophenyl) -2, 6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro -PN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di ( Trichloromethyl) -s-triazine,

4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl)- 2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m- Chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloro Methyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro- -N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl)- Examples thereof include s-triazine.

  Others, TAZ series, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123, PANCHIM T series, T-OMS , T-BMP, TR, TB, Irgacure series, Irgacure 369, Irgacure 784, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819, Irgacure 261, manufactured by Ciba Specialty Chemicals Darocur series, Darocur 1173, 4,4′-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2-benzene Dil-2-dimethylamino-4-morpholinobutyrophenone, 2,2-dimethoxy-2-phenylacetophenone, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2 -(P-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4 , 5-diphenylimidazolyl dimer, benzoin isopropyl ether and the like are also usefully used.

In addition to the photopolymerization initiator, other known photopolymerization initiators can be used in combination with the colored curable composition of the present invention.
Specifically, the vicinal polyketoaldonyl compounds disclosed in U.S. Pat. No. 2,367,660, U.S. Pat. Nos. 2,367,661 and 2,367,670 are described. Disclosed α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, α-hydrocarbons disclosed in US Pat. No. 2,772,512 Substituted aromatic acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, disclosed in US Pat. No. 3,549,367. Triarylimidazole dimer / p-aminophenylketone combination, benzothiazole compound / trihax disclosed in Japanese Patent Publication No. 51-48516 And lomethyl-s-triazine compounds.

  0.01-50 mass% is preferable with respect to the said polymerizable monomer solid content, as for the total content in the colored curable composition of the said photoinitiator, 1-30 mass% is more preferable, 1-20 mass % Is particularly preferred. When the content is less than 0.01% by mass, the polymerization is difficult to proceed. When the content exceeds 50% by mass, the polymerization rate increases, but the molecular weight may decrease and the film strength may be weakened.

These photopolymerization initiators can be used in combination with a sensitizer and a light stabilizer.
Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, and 2-ethyl-9-anthrone. 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2- Methoxyxanthone, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl ketone, p- (dimethyl Amino) phenyl-p-methylstyryl ketone Examples include benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, tinuvin 1130, 400, and the like. .

  In addition to the above, it is preferable to add a thermal polymerization inhibitor to the colored curable composition of the present invention. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol. Pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzo Imidazole and the like are useful.

(Naphthoquinonediazide compound)
In order to obtain a positive image, that is, when the colored curable composition of the present invention is configured as a positive type, the colored curable composition of the present invention preferably contains a naphthoquinonediazide compound.
Examples of the naphthoquinone diazide compound include o-naphthoquinone diazide-5-sulfonic acid esters, o-naphthoquinone diazide-5-sulfonic acid amides, o-naphthoquinone diazide-4-sulfonic acid esters, o-naphthoquinone diazide- 4-sulfonic acid amides etc. are mentioned. These ester compounds and amide compounds are produced by a known method using, for example, the phenol compound described in the general formula (I) in JP-A-2-84650 and JP-A-3-49437. Can do.

<Solvent>
In preparing the colored curable composition of the present invention, a solvent can generally be contained. The solvent to be used is not particularly limited as long as the solubility of each component of the composition and the coating property of the colored curable composition are satisfied, but particularly considering the solubility, coating property and safety of the binder. Are preferably selected.

  Specific examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy 2-oxypropionic acid alkyl esters such as methyl propionate, etc., methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, 2-methoxy Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy -2-methylpropi Methyl pyrate, ethyl 2-ethoxy-2-methylpropionate, etc.); methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. ;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone ; Aromatic hydrocarbons such as toluene and xylene are preferable.

  Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, acetic acid-n-butyl, isobutyl acetate, methyl 3-methoxypropionate, 2-heptanone, Cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like are more preferable.

<Various additives>
In the colored curable composition of the present invention, various additives such as a filler, a polymer compound other than the above, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, An anti-fading agent or the like can be blended.

  Specific examples of these additives include fillers such as glass and alumina; polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; nonionic, cationic And anionic surfactants: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimetoki Adhesion promoters such as silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl- 6-t-butylphenol), 2,6-di-t-butylphenol and other antioxidants: 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc. And an anti-aggregation agent such as sodium polyacrylate.

  Further, when the alkali solubility of the uncured portion is promoted and the developability of the colored curable composition of the present invention is further improved, the colored curable composition of the present invention is added with an organic carboxylic acid, preferably a molecular weight. Addition of 1000 or less low molecular weight organic carboxylic acid can be performed. Specifically, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, glutar Aliphatic dicarboxylic acids such as acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as carbaryl acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acid, merophanic acid, pyromellitic acid; phenylacetic acid, Doroatoropa acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

  When the colored curable composition of the present invention is a positive composition, from the viewpoint of curability and solubility, the alkali-soluble phenol resin and the crosslinking agent are usually 2 to 50% by mass in an organic solvent, respectively. It is preferable to dissolve at a ratio of about 2 to 30% by mass. The amount of the naphthoquinone diazide compound and the organic solvent used is usually 2 to 30% by mass and 2 to 50%, respectively, from the viewpoint of curability and solubility, with respect to the solution in which the alkali-soluble resin and the crosslinking agent are dissolved. It is preferable to add at a mass ratio.

  The colored curable composition of the present invention is used for forming a colored pixel such as a color filter used in a liquid crystal display element (LCD) or a solid-state imaging element (for example, CCD, CMOS, etc.), printing ink, inkjet ink, and It can be suitably used as a production application for paints and the like.

≪Color filter and manufacturing method≫
The color filter of the present invention comprises a dye represented by the above general formula (I). The preferable range of the dye represented by the general formula (I) is also as described above.
The color filter of the present invention may be produced by any method as long as it contains the dye represented by the general formula (I). It is preferable that it is what uses an adhesive composition.

Specifically, the colored curable composition of the present invention is applied on a support by a coating method such as spin coating, cast coating, roll coating, etc. to form a radiation sensitive composition layer, and a predetermined mask pattern is formed. And then developing with a developer to form a colored pattern (resist pattern). Moreover, the process of hardening the said resist pattern by heating and / or exposure as needed may be included. As radiation used at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used.
Moreover, when the colored curable composition is comprised by the positive type, the process of post-baking a colored pattern after the said pattern formation can also be provided.

In the production of a color filter when the colored curable composition of the present invention is configured as a negative type, a positive type is obtained by repeating the pattern formation step (and the curing step if necessary) according to the desired number of hues. In this case, a color filter having a desired number of hues can be produced by repeating the pattern forming step and the post-baking step according to the desired number of hues.
In the colored curable composition of the present invention, after the pattern formation process for the first color, there is no decrease in the density of the first color pattern (color loss) during application, exposure, and development of the second color, and the second color dye is the first color. This is excellent in so-called process color mixing, in which there is no color mixing due to mixing in the image area.

  Examples of the support include soda glass used for liquid crystal display elements and the like, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to them, photoelectric conversion element substrates used for imaging elements, For example, a silicon substrate, a complementary metal oxide semiconductor (CMOS), or the like can be given. These substrates may have black stripes that separate pixels.

  Further, if necessary, an undercoat layer may be provided on these supports in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

  As the developer used in the method for producing the color filter of the present invention, any developer can be used as long as it dissolves the uncured portion of the colored curable composition of the present invention and does not dissolve the cured portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. Examples of the organic solvent include the aforementioned solvents used in preparing the colored curable composition of the present invention.

  Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide. , Choline, pyrrole, piperidine, alkaline compounds such as 1,8-diazabicyclo- [5.4.0] -7-undecene, the concentration is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution so dissolved is used. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

  The color filter of the present invention can be used for a solid-state image pickup device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS device having more than 1 million pixels. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

  Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited thereto. In the examples, unless otherwise specified, “part” means “part by mass”, and “%” means “mass%”.

[Example 1]
(1) Preparation of resist solution for undercoat layer Propylene glycol monomethyl ether acetate 5.20 parts (PGMEA)
Cyclohexanone: 52.6 parts Binder (41% EL solution of benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (molar ratio = 60: 20: 20)) 5 parts dipentaerythritol hexaacrylate 10.2 parts Polymerization inhibitor (p-methoxyphenol) 0.006 parts Fluorosurfactant (F-475, Dainippon Ink & Chemicals, Inc. 0.80 part · Photopolymerization initiator (TAZ-107 (trihalomethyltriazine photopolymerization initiator) Midori Chemical Co., Ltd.)
... 0.58 parts were mixed and dissolved to prepare a resist solution for undercoat layer.

(2) Production of glass substrate with undercoat layer A glass substrate (Corning 1737) was ultrasonically washed with 0.5% NaOH water, and then washed with water and dehydrated (200 ° C./20 minutes).
Next, the above-mentioned resist solution for undercoat layer (1) was applied onto a washed glass substrate using a spin coater so as to have a film thickness of 2 μm, and dried by heating at 220 ° C. for 1 hour to obtain a cured film (undercoat layer). It was.

(3) Preparation of dye resist solution R-1 (colored curable composition [negative type]) The following composition R-1 was mixed and dissolved to prepare a dye resist solution R-1.
~ Composition R-1 ~
・ Cyclohexanone: 60 parts ・ Ethyl lactate: 20 parts ・ Binder: 3.0 parts (benzyl methacrylate / methacrylic acid = 70/30 (molar ratio))
Exemplified dye Ia-1 (colorant represented by general formula (I)) 4.3 parts Polymerization inhibitor (p-methoxyphenol) 0.005 parts Fluorosurfactant・ 0.005 part (F-475 manufactured by Dainippon Ink & Chemicals, Inc.)
・ Dipentaerythritol hexaacrylate 6.8 parts ・ Photopolymerization initiator CG-124 (manufactured by Ciba Specialty Chemicals)
... 3.2 parts

(4) Exposure and development of resist (pattern formation)
The undercoat layer of the glass substrate with an undercoat layer obtained in “(2) Production of glass substrate with an undercoat layer” obtained from the above-mentioned “(3) Preparation of dye resist solution R-1”. The film was coated on the substrate so as to have a film thickness of 1.0 μm using a spin coater, and prebaked at 100 ° C. for 120 seconds.
Next, using an exposure apparatus, the coating film was irradiated with an exposure dose of 500 mJ / cm ² through a mask having a wavelength of 365 nm and a line width of 20 μm. After the exposure, development was performed using a 60% CD-2000 (manufactured by FUJIFILM Electronics Materials) developer at 25 ° C. for 40 seconds. Then, after rinsing with running water for 30 seconds, spray drying was performed. As a result, a pattern suitable for a magenta color filter was obtained.

(5) Evaluation The storage stability of the dye resist solution R-1 prepared above, and the heat resistance and light resistance of the coating film coated on the glass substrate using the dye resist solution R-1 are as follows. And evaluated. The evaluation results are shown in Table 1 below.

<Storage stability>
After the dye resist solution R-1 was stored at room temperature for 1 month, the degree of visual precipitation of foreign matters was visually evaluated according to the following criteria.
~ Criteria ~
○: No precipitation was observed.
Δ: Slight precipitation was observed, but was practically acceptable.
X: Precipitation was recognized.

<Heat resistance>
After the glass substrate coated with the dye resist solution R-1 was heated at 200 ° C. for 1 hour with a hot plate, the ΔEab value of the color difference before and after the heat resistance test was measured with a chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics). The evaluation was made according to the following criteria. A smaller ΔEab value indicates better heat resistance (if Δ, it is practically acceptable).
~ Criteria ~
○: ΔEab value <5 or less Δ: 5 ≦ ΔEab value ≦ 10
×: 10 <ΔEab value

<Light resistance>
The glass substrate coated with the dye resist solution R-1 was irradiated with a xenon lamp at 50,000 lux for 10 hours (equivalent to 1 million lux · h), and then the ΔEab value of the color difference before and after the light resistance test was measured. The smaller the ΔEab value, the better the light resistance (if Δ, it is practically acceptable).
~ Criteria ~
○: ΔEab value <5
Δ: 5 ≦ ΔEab value ≦ 10
×: 10 <ΔEab value

[Examples 2 to 20]
The same procedure as in Example 1 was performed except that the equimolar amount of the exemplified dye Ia-1 was replaced with the exemplified dyes shown in Table 1 below in “(3) Preparation of dye resist solution R-1” in Example 1. . The results are shown in Table 1.

[Comparative Examples 1-3]
Example 1 is the same as Example 1 except that the example dye Ia-1 was changed to Comparative dye A to Comparative dye C shown in Table 1 below in “(3) Preparation of dye resist solution R-1” in Example 1. The same was done. The results are shown in Table 1.

From the results of Table 1, the colored curable compositions of Examples 1 to 20 using the dye represented by the general formula (I) are excellent in storage stability in a solution state, and furthermore, these colored curable compositions. The pattern formed using the composition was excellent in heat resistance and light resistance.
On the other hand, the colored curable compositions of Comparative Examples 1 to 3 using a dye other than the dye represented by the general formula (I) were inferior in heat resistance and light resistance.

Example 21
(1) Preparation of colored curable composition [positive type] The following compositions were mixed and dissolved to obtain a colored curable composition [positive type].
・ Ethyl lactate (EL) 30 parts ・ Resin P-1 below 3.0 parts ・ Naphthoquinonediazide compound N-1 below 1.8 parts ・ Crosslinking agent: hexamethoxymethylolated melamine・ 0.6 parts ・ Photoacid generator: TAZ-107 (manufactured by Midori Chemical Co., Ltd.) ・ ・ ・ 1.2 parts ・ Fluorosurfactant ・ ・ ・ 0.0005 parts (trade name: Megafac F- 475, manufactured by Dainippon Ink & Chemicals, Inc.)
Exemplified dye Ia-1 (dye represented by formula (I)) 1.2 parts

  The resin P-1 and the naphthoquinone diazide compound (N-1) were synthesized as follows.

-Synthesis of Resin P-1-
A three-necked flask was charged with 70.0 g of benzyl methacrylate, 13.0 g of methacrylic acid, 17.0 g of methacrylic acid-2-hydroxyethyl, and 600 g of 2-methoxypropanol. A reflux condenser and a thermometer were attached to the stirrer, and the temperature was 65 ° C. under a nitrogen stream. 1 g of a polymerization initiator (trade name: V-65, manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred for 10 hours. The obtained resin solution was added dropwise to 20 L of ion exchange water with vigorous stirring to obtain a white powder. This white powder was vacuum-dried at 40 ° C. for 24 hours to obtain 145 g of resin P-1. When the molecular weight was measured by GPC, the weight average molecular weight Mw = 28,000 and the number average molecular weight Mn = 11,000.

-Synthesis of naphthoquinonediazide compound N-1-
TrisP-PA (manufactured by Honshu Chemical Co., Ltd.) 42.45 g, o-naphthoquinonediazide-5-sulfonyl chloride 61.80 g, and acetone 300 ml were charged into a three-necked flask, and 24.44 g of triethylamine was added dropwise at room temperature over 1 hour. . After completion of the dropwise addition, the mixture was further stirred for 2 hours, and then the reaction solution was poured into a large amount of water while stirring. Subsequently, the precipitated naphthoquinone diazide sulfonic acid ester was collected by suction filtration and dried in vacuo at 40 ° C. for 24 hours to obtain naphthoquinone diazide compound N-1.

(2) Exposure and development of colored curable composition [positive type] (pattern formation)
In the same manner as in Example 1, the colored curable composition [positive type] prepared as described above was applied to a glass substrate with an undercoat layer, and pre-baked, irradiated, developed, rinsed and dried to form a magenta pattern. Thereafter, the pattern was heated at 180 ° C. for 5 minutes (post-bake). The formed magenta pattern showed a good rectangular profile.

  The storage stability of the colored curable composition using the coloring matter (dye) in the present invention, and the heat resistance and light resistance of the coated color curable composition of the present invention were evaluated in the same manner as in Example 1. However, it was found that the storage stability was excellent and the heat resistance and light resistance were good.

[Examples 22 to 41]
Except having changed the glass substrate of Examples 1-20 into the silicon wafer substrate, operation similar to Examples 1-20 was performed and the dye resist solution was apply | coated on the silicon wafer with undercoat.
Next, using a i-line reduction projection exposure apparatus, a 2 μm square pattern is exposed with an exposure amount of 500 mJ / cm ² , and a developer (trade name: CD-2000 (60%), manufactured by Fuji Film Electronics Materials, Inc.) ) And developed at 23 ° C. for 60 seconds. Subsequently, after rinsing with running water for 30 seconds, spray drying was performed. As a result, a pattern suitable as a CCD color filter having a square shape and a rectangular cross section was obtained.

Claims (7)

The coloring curable composition characterized by containing the pigment | dye represented by the following general formula (I).

[In General Formula (I), R ₁ represents a hydrogen atom or a substituent, and R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, Represents an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group; R ₂ and R ₃ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. R ₄ and R ₅ each independently represents a hydrogen atom or a substituent. R ₄ and R ₅ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. X represents an oxygen atom, ═C (CN) ₂ , or ═N (R ₆ ), and R ₆ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, It represents a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group. Y represents —N (R ₇ ) —, an oxygen atom, or a sulfur atom, and R ₇ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, An alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group is represented. Za and Zb each independently represent ═C (R ₈ ) — or ═N—, and R ₈ represents a hydrogen atom or a substituent. ] The coloring curable composition characterized by containing the pigment | dye represented by the following general formula (II) or general formula (III).

[In General Formula (II) and General Formula (III), R ₁ represents a hydrogen atom or a substituent, and R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, hetero A cyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group is represented. R ₂ and R ₃ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. R ₄ and R ₅ each independently represents a hydrogen atom or a substituent. R ₄ and R ₅ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. X represents an oxygen atom, ═C (CN) ₂ , or ═N (R ₆ ), and R ₆ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, It represents a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group. Y represents —N (R ₇ ) —, an oxygen atom, or a sulfur atom, and R ₇ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, An alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group is represented. R ₉ represents a hydrogen atom or a substituent, and m represents 0, 1, or 2. ] The coloring curable composition characterized by containing the pigment | dye represented by the following general formula (IV) or general formula (V).

[In General Formula (IV) and General Formula (V), R ₁ represents a hydrogen atom or a substituent, and R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, hetero A cyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group is represented. R ₂ and R ₃ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. R ₄ and R ₅ each independently represents a hydrogen atom or a substituent. R ₄ and R ₅ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. Y represents —N (R ₇ ) —, an oxygen atom, or a sulfur atom, and R ₇ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, An alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group is represented. R ₉ represents a hydrogen atom or a substituent, and m represents 0, 1, or 2. ] The coloring curable composition characterized by containing the pigment | dye represented by the following general formula (VI) or general formula (VII).

[In General Formula (VI) and General Formula (VII), R ₁ represents a hydrogen atom or a substituent, and R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, hetero A cyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group is represented. R ₂ and R ₃ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. R ₉ represents a hydrogen atom or a substituent, and m represents 0, 1, or 2. R ₁₀ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group. R ₁₁ represents a substituent, and n represents an integer of 0 to 4. ] The color filter characterized by containing the pigment | dye represented by the following general formula (I).

[In General Formula (I), R ₁ represents a hydrogen atom or a substituent, and R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, Represents an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group; R ₂ and R ₃ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. R ₄ and R ₅ each independently represents a hydrogen atom or a substituent. R ₄ and R ₅ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. X represents an oxygen atom, ═C (CN) ₂ , or ═N (R ₆ ), and R ₆ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, It represents a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group. Y represents —N (R ₇ ) —, an oxygen atom, or a sulfur atom, and R ₇ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, An alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic sulfonyl group is represented. Za and Zb each independently represent ═C (R ₈ ) — or ═N—, and R ₈ represents a hydrogen atom or a substituent. ]   A color filter comprising the colored curable composition according to claim 1.   A color filter comprising the steps of: applying a colored curable composition according to any one of claims 1 to 4 on a support; exposing the film through a mask; and developing to form a pattern image. Production method.