JP5710568B2 - Colored curable composition, colored cured film, color filter, method for producing color filter, display device, solid-state imaging device, and compound - Google Patents

Description

  The present invention relates to a colored curable composition, a colored cured film, a color filter, a method for producing a color filter, a display device, a solid-state imaging device, and a compound.

Conventionally, a color filter is a colored curable composition containing a pigment dispersion composition in which an organic pigment or an inorganic pigment as a colorant is dispersed, and a polymerizable compound, a polymerization initiator, an alkali-soluble resin, and other components. These are used to form a colored pattern by a pattern forming method such as a photolithography method or an ink jet method.
In recent years, the use of color filters for display elements such as liquid crystal display elements (LCDs) tends to expand not only to monitors but also to televisions (TVs). Along with this expanded use, color filters are required to have high color characteristics in terms of chromaticity and contrast. Similarly, color filters for use in image sensors (solid-state imaging devices) are also required to have high color characteristics such as reduction in color unevenness and improvement in color resolution.
In a colored curable composition containing a conventional pigment dispersion composition, problems such as scattering due to coarse pigment particles and an increase in viscosity due to poor dispersion stability are likely to occur, and it is difficult to further improve contrast and brightness. .
Then, using dye instead of a pigment as a coloring agent is examined (for example, refer patent document 1). The use of a dye is advantageous in that the hue and brightness of the displayed image can be increased by virtue of the color purity of the dye itself and the vividness of the hue, and the contrast can be improved because coarse particles are eliminated. It is.
It is desired that the dye that can be used for the above-mentioned purposes has the following properties. That is, it has a preferable hue for color reproduction, an optimum spectral absorption, a fastness such as heat resistance and light resistance, and a good solubility in a solvent.
For example, Patent Document 2 describes a dipyrromethene dye having excellent color purity, a high molar extinction coefficient, and excellent fastness, which is useful for a colored curable composition for a color filter. Patent Document 3 describes a dipyrromethene-based dye that is useful for a colored curable composition for color filters and has a high molar extinction coefficient and is excellent in developability. .

JP-A-6-75375 JP 2008-292970 A JP 2010-85454 A

However, as a pigment contained in a colored curable composition used for the production of a color filter of a display element or a solid-state imaging element, it has a high molar extinction coefficient as well as further solubility and heat resistance. There is currently a need for improved dyes.
Furthermore, compared with the colored curable composition containing the above-mentioned known dye, the color filter is excellent in storage stability, and also produced using the same, stability against heat (heat resistance), brightness, contrast, and What has an excellent pattern shape is desired.

The present invention has been made in view of the above circumstances, and provides a colored curable composition in which a colored cured film having excellent storage stability and excellent heat resistance, luminance, contrast, and pattern shape is formed. Is an issue.
Furthermore, the present invention is to provide a colored cured film using the colored curable composition, a color filter including the colored cured film, a manufacturing method thereof, a display device using the color filter, and a solid-state imaging device. And
Furthermore, this invention makes it a subject to provide the compound which is useful for the colored curable composition used for preparation of a color filter, has a high molar extinction coefficient, and is excellent in solubility and heat resistance.

The present invention that achieves the above-described objects is as follows.
<1> A colored curable composition containing a polymerizable compound and at least one selected from the group consisting of a compound represented by the following general formula ( II ) and a tautomer thereof.

[In General Formula (II), R ³ and R ⁴ each independently represents a hydrogen atom or a monovalent substituent. X ¹ represents a group necessary for neutralizing the charge of Zn. R ^{8 to} R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent. However, at least two of R ^{8 to} R ¹⁰ represent a monovalent substituent. R ^{11 to} R ¹⁴ each independently represents a hydrogen atom or a monovalent substituent. X ² represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or sulfur. Represents an atom. R ¹⁶ represents a hydrogen atom or a monovalent substituent. ]
< 2 > The colored curable composition according to <1 >, further comprising a photopolymerization initiator.
< 3 > The colored curable composition according to <1> or <2> , further containing at least one selected from the group consisting of a pigment and an anthraquinone compound.
< 4 > The colored curable composition according to < 3 >, wherein the anthraquinone compound is a compound represented by the following general formula (IX).

[In General Formula (IX), R ^11a and R ^12a each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, but R ^11a and R ^12a may simultaneously represent a hydrogen atom. Absent. n ¹¹ represents an integer of 1 to 4. ]
< 5 > At least one content selected from the group consisting of the compound represented by the general formula ( II ) and tautomers thereof is 0.1% by mass or more and 30% by mass or more based on the total solid content of the composition. The colored curable composition as described in any one of <1>-< 4 > which is the range of the mass% or less.
< 6 > A colored cured film obtained by curing the colored curable composition according to any one of <1> to < 5 >.
< 7 > A color filter comprising the colored cured film according to < 6 >.
< 8 > The step of applying the colored curable composition according to any one of <1> to < 5 > on a support to form a colored curable composition layer, and the colored curable composition layer. A step of exposing the film to a pattern and developing to form a colored pattern.
< 9 > A display device comprising the color filter according to < 7 > or the color filter produced by the method for producing a color filter according to < 8 >.
<10> The color filter, or a solid-state imaging element having a color filter manufactured by the method for producing a color filter according to <8> according to <7>.

<11 > A compound selected from the group consisting of compounds represented by the following general formula (II) and tautomers thereof.

[In General Formula (II), R ³ and R ⁴ each independently represents a hydrogen atom or a monovalent substituent. X ¹ represents a group necessary for neutralizing the charge of Zn. R ^{8 to} R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent. However, at least two of R ^{8 to} R ¹⁰ represent a monovalent substituent. R ^{11 to} R ¹⁴ each independently represents a hydrogen atom or a monovalent substituent. X ² represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or sulfur. Represents an atom. R ¹⁶ represents a hydrogen atom or a monovalent substituent. ]

ADVANTAGE OF THE INVENTION According to this invention, while being excellent in storage stability, the colored curable composition in which the colored cured film excellent in heat resistance, a brightness | luminance, contrast, and a pattern shape is formed is provided.
Furthermore, according to the present invention, a colored cured film using the colored curable composition, a color filter including the colored cured film, a manufacturing method thereof, a display device using the color filter, and a solid-state imaging device are provided. .
Furthermore, according to the present invention, there is provided a pigment having a high molar extinction coefficient and excellent in solubility and heat resistance, which is useful for a colored curable composition used for producing a color filter.

Hereinafter, a colored curable composition, a colored cured film, a color filter, a method for producing a color filter, a liquid crystal display device, a solid-state imaging device, and a pigment according to the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, the total solid content is the total content of all components of the colored curable composition excluding the solvent constituting the colored curable composition.

In the present specification, for example, an “alkyl group” represents a “straight chain, branched and cyclic” alkyl group. In addition, in the notation of a group (atomic group) in the present specification, the notation that does not indicate substitution or unsubstituted means that it includes not only a substituent but also a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). The same applies to groups other than alkyl groups.
Further, in this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, “(meth) acryl” represents both and / or acryl and “meth”. ) "Acryloyl" represents both and / or acryloyl and methacryloyl.

In the present specification, “monomer” and “monomer” are synonymous. The monomer in this specification is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound refers to a compound having a polymerizable functional group, and may be a monomer, an oligomer, or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
In the present invention, “radiation” means a substance containing visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like.

≪Colored curable composition≫
The colored curable composition according to the present invention is also referred to as at least one selected from the group consisting of a compound represented by the following general formula (I) and tautomers thereof (hereinafter also referred to as “specific dipyrromethene metal complex”). ), And preferably comprises a polymerizable compound and a photopolymerization initiator.
Moreover, the said colored curable composition may be further comprised including an alkali-soluble binder and an organic solvent as needed, and may be comprised using various additives.
Furthermore, the colored curable composition may further include at least one colorant selected from the group consisting of a dye having a different structure from the specific dipyrromethene metal complex and a pigment.

<< Compounds Represented by Formula (I) and Tautomers thereof >>
The specific dipyrromethene metal complex according to the present invention is at least one compound selected from the compound represented by the following general formula (I) and its tautomers.

[In General Formula (I), R ^{2 to} R ⁵ each independently represents a hydrogen atom or a monovalent substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. M represents a metal or a metal compound, X ¹ represents a group necessary for neutralizing the charge of M, and a represents 1 or 2. When a is 2, X ¹ may be the same or different. R ^{8 to} R ¹⁰ each independently represents a hydrogen atom or a monovalent substituent. However, at least two of R ^{8 to} R ¹⁰ represent a monovalent substituent. R ^{11 to} R ¹⁴ each independently represents a hydrogen atom or a monovalent substituent. X ² represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or a sulfur atom. , R ¹⁶ represents a hydrogen atom or a monovalent substituent. )]

The compound represented by the general formula (I) may be a tautomer.
In the present invention, the tautomer may be any compound having a structure that can be formed by movement of one hydrogen atom in the molecule. For example, from the following general formulas (a) to (f) The structure etc. are included.

In the general formulas (a) to (f), R ^{2 to} R ⁵ , R ^{7 to} R ¹⁴ , R ¹⁶ , X ¹ , X ² , M, and a have the same meanings as those in the general formula (I). is there.
The above structure is an example of a tautomeric structure, and can take various isomeric structures depending on the structures of R ^{2 to} R ⁵ , R ^{7 to} R ¹⁴ , R ¹⁶ , X ¹ , X ² , and M. .
For example, when X ¹ is a monovalent group derived from succinimide, two types of isomer structures represented by the following general formulas (g) and (h) can be considered.

In the general formula (g) and ^{(h), R 2 ~R 5} , R 7 ~R 14, R 16, X 1, X 2, and M have the same meanings as those in formula (I).

The chemical structure of the specific dipyrromethene metal complex according to the present invention is that it has two groups of -CR ⁸ R ⁹ R ¹⁰ and -X ² -R ¹⁶ at the same time. Having these two groups at the same time provides excellent properties of high solubility and heat resistance.
Hereinafter, the specific dipyrromethene metal complex according to the present invention will be described below using a compound having a structure represented by the general formula (I) as a representative.

<Regarding R ^{2 to} R ⁵ in General Formula (I)>
As the monovalent substituent according to R ^{2 to} R ⁵ in the general formula (I), a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably having 1 to 48 carbon atoms, more preferably Is a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group, heptyl Group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group), alkenyl group (preferably having 2 to 48 carbon atoms, more preferably). Is an alkenyl group having 2 to 18 carbon atoms, for example, vinyl group, allyl group, 3-buten-1-yl group), aryl group (preferably having 6 to 6 carbon atoms). 8, more preferably an aryl group having 6 to 24 carbon atoms, for example, a phenyl group, a naphthyl group),

Heterocyclic group (preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1- A pyridyl group, a 2-benzothiazolyl group, a 1-imidazolyl group, a 1-pyrazolyl group, a benzotriazol-1-yl group), a silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms). , For example, trimethylsilyl group, triethylsilyl group, tributylsilyl group, t-butyldimethylsilyl group, t-hexyldimethylsilyl group), hydroxy group, cyano group, nitro group, alkoxy group (preferably having 1 to 48 carbon atoms) Preferably it is a C1-C24 alkoxy group, for example, a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, an isopropyl group. In the case of a xy group, a t-butoxy group, a dodecyloxy group, or a cycloalkyloxy group, for example, a cyclopentyloxy group or a cyclohexyloxy group, an aryloxy group (preferably having 6 to 48 carbon atoms, more preferably a carbon number). 6 to 24 aryloxy groups such as phenoxy group and 1-naphthoxy group, heterocyclic oxy groups (preferably having 1 to 32 carbon atoms, more preferably having 1 to 18 carbon atoms, 1-phenyltetrazole-5-oxy group, 2-tetrahydropyranyloxy group),

A silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as a trimethylsilyloxy group, a t-butyldimethylsilyloxy group, a diphenylmethylsilyloxy group), an alkylcarbonyloxy group ( Preferably it is C2-C48, More preferably, it is C2-C24 alkylcarbonyloxy group, for example, acetoxy group, pivaloyloxy group, dodecanoyloxy group), arylcarbonyloxy group (preferably C7-32, More preferably, it is an arylcarbonyloxy group having 7 to 24 carbon atoms, such as a benzoyloxy group, an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably an alkoxycarbonyloxy group having 2 to 24 carbon atoms, For example, ethoxycarbonyloxy , T-butoxycarbonyloxy group and cycloalkyloxycarbonyloxy group, for example, cyclohexyloxycarbonyloxy group, aryloxycarbonyloxy group (preferably having 7 to 32 carbon atoms, more preferably having 7 to 32 carbon atoms). 24 aryloxycarbonyloxy groups, for example, phenoxycarbonyloxy group),

A carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group). Group, N-ethyl-N-phenylcarbamoyloxy group), sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N, N- A diethylsulfamoyloxy group, an N-propylsulfamoyloxy group), an alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, such as methylsulfonyloxy group). Group, hexadecylsulfonyloxy group, cyclohexylsulfonyloxy group Group), an arylsulfonyl group (preferably having a carbon number of 6 to 32, more preferably arylsulfonyloxy group having 6 to 24 carbon atoms, e.g., phenylsulfonyl group),

Alkylcarbonyl group (preferably an alkylcarbonyl group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as formyl group, acetyl group, pivaloyl group, tetradecanoyl group, cyclohexanoyl group), arylcarbonyl A group (preferably an arylcarbonyl group having 7 to 32 carbon atoms, more preferably an arylcarbonyl group having 7 to 24 carbon atoms, such as a benzoyl group), an alkoxycarbonyl group (preferably having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms). Alkoxycarbonyl group, for example, methoxycarbonyl group, ethoxycarbonyl group, octadecyloxycarbonyl group, cyclohexyloxycarbonyl group, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group), aryloxycarbonyl group (preferably 7 to 3 carbon atoms More preferably an aryloxycarbonyl group having 7 to 24 carbon atoms, such as a phenoxycarbonyl group, and a carbamoyl group (preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as carbamoyl group). Group, N, N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methylN-phenylcarbamoyl group, N , N-dicyclohexylcarbamoyl group),

An amino group (preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as an amino group, a methylamino group, an N, N-dibutylamino group, a tetradecylamino group, or a 2-ethylhexylamino group; , A cyclohexylamino group), an anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, for example, an anilino group or an N-methylanilino group), a heterocyclic amino group (preferably having 1 to 3 carbon atoms). 32, more preferably a 1-18 heterocyclic amino group, such as a 4-pyridylamino group, a carbonamido group (preferably a C2-48, more preferably 2-24 carbonamido group, such as acetamide Group, benzamide group, tetradecanamide group, pivaloylamide group, cyclohexaneamide group), ureido group (preferred) Or a ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as a ureido group, N, N-dimethylureido group, or N-phenylureido group), an imide group (preferably having 36 or less carbon atoms). More preferably, it is an imide group having 24 or less carbon atoms, for example, an N-succinimide group or an N-phthalimide group), an alkoxycarbonylamino group (preferably having 2 to 48 carbon atoms, more preferably an alkoxycarbonyl having 2 to 24 carbon atoms). Amino group, for example, methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group), aryloxycarbonylamino group (preferably having 7 to 32 carbon atoms, More preferably, the aryloxy having 7 to 24 carbon atoms In carbonylamino group, for example, phenoxycarbonylamino group),

Sulfonamide group (preferably a sulfonamide group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methanesulfonamide group, butanesulfonamide group, benzenesulfonamide group, hexadecanesulfonamide group, cyclohexanesulfone, An amide group), a sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dipropylsulfamoylamino group, N-ethyl). -N-dodecylsulfamoylamino group), an azo group (preferably an azo group having 1 to 32 carbon atoms, more preferably an azo group having 1 to 24 carbon atoms, such as a phenylazo group or a 3-pyrazolylazo group), an alkylthio group ( Preferably it is a C1-C48, More preferably, it is a C1-C24 alkylthio group, for example, A thiol group, an ethylthio group, an octylthio group, a cyclohexylthio group), an arylthio group (preferably an arylthio group having 6 to 48 carbon atoms, more preferably an arylthio group having 6 to 24 carbon atoms, such as a phenylthio group), a heterocyclic thio group (preferably Is a heterocyclic thio group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group), alkylsulfinyl group ( Preferably, it is an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as dodecanesulfinyl group), an arylsulfinyl group (preferably having 6 to 32 carbon atoms, more preferably having 6 to 24 carbon atoms). An arylsulfinyl group, for example a phenylsulfinyl group),

An alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropylsulfonyl group, 2- An ethylhexylsulfonyl group, a hexadecylsulfonyl group, an octylsulfonyl group, a cyclohexylsulfonyl group), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as a phenylsulfonyl group, 1-naphthylsulfonyl group), sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as sulfamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N- Dodeci A sulfamoyl group, an N-ethyl-N-phenylsulfamoyl group, an N-cyclohexylsulfamoyl group), a sulfo group, and a phosphonyl group (preferably having 1 to 32 carbon atoms, more preferably having 1 to 24 carbon atoms). For example, a phenoxyphosphonyl group, an octyloxyphosphonyl group, a phenylphosphonyl group), a phosphinoylamino group (preferably a phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, For example, it represents a diethoxyphosphinoylamino group or a dioctyloxyphosphinoylamino group).

When the above-described monovalent group is a further substitutable group, it may be further substituted with any of the above-described groups. In addition, when it has two or more substituents, those substituents may be the same or different.
When the above monovalent substituent further has a substituent, examples of the substituent include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a silyl group, a cyano group, a nitro group, an alkoxy group, an aryloxy group, Heterocyclic oxy group, alkylcarbonyloxy group, alkoxycarbonyloxy group, arylcarbonyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, alkylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, hetero It is preferably selected from a ring thio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, and an arylsulfonyl group, and further, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, B-ringoxy group, alkylcarbonyloxy group, alkoxycarbonyloxy group, arylcarbonyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, alkylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, hetero It is more preferably a substituent selected from a ring thio group, an alkylsulfonyl group, and an arylsulfonyl group.

R ³ and R ⁴ in the general formula (I) are preferably an alkyl group, an aryl group, or a heterocyclic group, and more preferably an alkyl group or an aryl group.
As an alkyl group in said R < ³ > and R < ⁴ >, a C1-C12 alkyl group is preferable, for example, a methyl group, an ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group I-butyl group, t-butyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and benzyl group.
Among them, a branched chain having 1 to 12 carbon atoms or a cyclic alkyl group is preferable, and examples thereof include i-propyl group, cyclopropyl group, i-butyl group, t-butyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group. It is done. Further, a secondary or tertiary alkyl group having 1 to 12 carbon atoms is particularly preferable, and examples thereof include an isopropyl group, a cyclopropyl group, an i-butyl group, a t-butyl group, a cyclobutyl group, and a cyclohexyl group.
The aryl group in R ³ and R ⁴ preferably includes a phenyl group and a naphthyl group, and among them, a phenyl group is more preferable.
The heterocyclic group in R ³ and R ⁴ is preferably a 2-thienyl group, 4-pyridyl group, 3-pyridyl group, 2-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 2-benzothiazolyl. Group, 1-imidazolyl group, 1-pyrazolyl group and benzotriazol-1-yl group, among which 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group and 1-pyridyl group are further included. preferable.

R ² and R ⁵ in the general formula (I) are preferably an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitrile group, an imide group, or a carbamoylsulfonyl group. A carbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, a nitrile group, an imide group, or a carbamoylsulfonyl group is more preferable, and an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a nitrile group, an imide group, or a carbamoylsulfonyl group. A group is still more preferred, and an alkoxycarbonyl group, an aryloxycarbonyl group, or a carbamoyl group is particularly preferred. Specific examples of these groups are as described above.

<Regarding R ⁷ in Formula (I)>
When R ⁷ in general formula (I) is a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, these groups include the halogen atom, alkyl group, and aryl group in R ^{2 to} R ⁵ described above. Or the same as the heterocyclic group, and preferred examples thereof are also the same.
Preferable R ^{7 in} the general formula (I) is a hydrogen atom, a halogen atom, or an alkyl group, and more preferably a hydrogen atom.

<About M in General Formula (I)>
M in the general formula (I) represents a metal atom or a metal compound. M may be any metal atom or metal compound capable of forming a complex, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. Things are included. For example, in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ Further, metal chlorides such as GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ are also included.
Among these, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B from the viewpoints of stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex Or VO is preferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferable, and Fe, Zn, Cu, Co, B, or VO (V = O) is preferable. Even more preferred is Zn, and most preferred is Zn.

<About “(X ¹ ) _a ” in General Formula (I)>
X ¹ in the general formula (I) represents a group necessary for neutralizing the charge of M. Examples of X ¹ include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxyl group, A monovalent group derived from an aliphatic imide (for example, succinimide, maleimide, glutarimide, diacetamide, etc., preferably succinimide, maleimide), an aromatic imide group or a heterocyclic imide (for example, , Phthalimide, naphthalimide, 4-bromophthalimide, 4-methylphthalimide, 4-nitrophthalimide, naphthalenecarboximide, tetrabromophthalimide, etc., preferably phthalimide, 4-bromophthalimide, 4-methylphthalimide) A monovalent group derived from an aromatic carboxylic acid (eg, benzoic acid, 2-methyl Xylbenzoic acid, 3-methoxybenzoic acid, 4-methoxybenzoic acid, 4-chlorobenzoic acid, 2-naphthoic acid, salicylic acid, 3,4,5-trimethoxybenzoic acid, 4-heptyloxybenzoic acid, 4-t- Butylbenzoic acid and the like, preferably monovalent group derived from benzoic acid, 4-methoxybenzoic acid, salicylic acid and the like,

Aliphatic carboxylic acids (eg, formic acid, acetic acid, acrylic acid, methacrylic acid, ethanoic acid, propanoic acid, lactic acid, pivalic acid, hexanoic acid, octanoic acid, 2-ethylhexanoic acid, neodecanoic acid, lauric acid, myristic acid, palmitic acid Acid, stearic acid, oleic acid, isostearic acid, 2-hexadecyloctadecanoic acid, 2-hexyldecanoic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, 5-norbornene-2-carboxylic acid, 1-adamantanecarboxylic acid, etc. A monovalent group derived from acetic acid, methacrylic acid, lactic acid, pivalic acid, 2-ethylhexanoic acid, stearyl acid, etc., dithiocarbamic acid (for example, dimethyldithiocarbamic acid, diethyldithiocarbamic acid, dibenzyldithiocarbamic acid) Mentioned Monovalent group derived from a sulfonamide (for example, benzenesulfonamide, 4-chlorobenzenesulfonamide, 4-methoxybenzenesulfonamide, 4-methylbenzenesulfonamide, 2-methylbenzenesulfonamide, and methanesulfonamide). Monovalent group derived from benzenesulfonamide and methanesulfonamide), monovalent group derived from hydroxamic acid (for example, acetohydroxamic acid, octanohydroxamic acid, benzohydroxamic acid) Group, nitrogen-containing ring compound (hydantoin, 1-benzyl-5-ethoxyhydantoin, 1-allylhydantoin, 5,5-diphenylhydantoin, 5,5-dimethyl-2,4-oxazolidinedione, barbituric acid, imidazole, pyrazole 4 Examples include 5-dicyanoimidazole, 4,5-dimethylimidazole, benzimidazole, diethyl 1H-imidazole-4,5-dicarboxylate, and the like, preferably 1-benzyl-5-ethoxyhydantoin, 5,5-dimethyl-2, And monovalent groups derived from 4-oxazolidinedione, 4,5-dicyanoimidazole, and 1H-imidazole-4,5-dicarboxylate).

Among these, halogen atoms, aliphatic carboxylic acid groups, aromatic carboxylic acid groups, aliphatic imide groups, aromatic imide groups, sulfonic acid groups, and nitrogen-containing ring compounds are preferable in terms of production. An acid group, an aromatic imide group, or a group derived from a nitrogen-containing ring compound is more preferable.
a represents 0, 1 or 2.

<Regarding ^R 8 ^{to R 10} in the general formula (I)>
In general formula (I), R < ⁸ > -R < ¹⁰ > represents a hydrogen atom or a monovalent substituent each independently. However, at least two of R ^{8 to} R ¹⁰ represent a monovalent substituent. The monovalent substituent represents the group described as the substituent for R ^{2 to} R ⁵ , and among them, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a silyl group, an alkoxy group, an aryloxy group, a hetero group A ring oxy group, an alkylthio group, an arylthio group, or a heterocyclic thio group is preferable, and a halogen atom, an alkyl group, an aryl group, an alkoxy group, or an alkylthio group is more preferable.

When R ^{8 to} R ¹⁰ are a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a silyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, or a heterocyclic thio group, Specific examples thereof include the halogen atom, alkyl group, aryl group, heterocyclic group, silyl group, alkoxy group, aryloxy group, heterocyclic oxy group described for the substituent represented by R ^{2 to} R ⁵ , The same group as the specific example of an alkylthio group, an arylthio group, or a heterocyclic thio group is mentioned. Furthermore, those preferable things are also the same.

<Regarding ^R 11 ^{to R 14} in the general formula (I)>
Examples of the monovalent substituent according to R ^{11 to} R ¹⁴ in the general formula (I) include the same monovalent substituents as those described as the monovalent substituent according to R ^{2 to} R ⁵ .
R ^{11 to} R ¹⁴ are a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, silyl group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, alkylcarbonyloxy group, alkoxy Carbonyloxy group, arylcarbonyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, alkylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfinyl group, arylsulfinyl group An alkylsulfonyl group or an arylsulfonyl group, preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group. Group, or more preferably a heterocyclic thio group, a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, or a heterocyclic group are particularly preferable.

<For ^{X 2} in the general formula (I)>
X ² in the general formula (I) is NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group or an arylsulfonyl group). Represents an oxygen atom or a sulfur atom.
The alkyl group according to R is preferably a linear, branched, or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, such as a methyl group, an ethyl group, or a propyl group. Isopropyl group, butyl group, isobutyl group, t-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group and the like.
The alkenyl group according to R is preferably an alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and examples thereof include a vinyl group, an allyl group, and a 3-buten-1-yl group. It is done.

The aryl group according to R is preferably an aryl group having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.
The heterocyclic group according to R is preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and at least selected from a nitrogen atom, an oxygen atom, and a sulfur atom as a hetero atom. Those containing one element are preferred.
Specifically, for example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazole- 1-yl group etc. are mentioned.
The alkylcarbonyl group according to R is preferably an alkylcarbonyl group having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, such as an acetyl group, a pivaloyl group, a 2-ethylhexyl group, and a cyclohexanoyl group. Can be mentioned.
The arylcarbonyl group according to R is an alkylcarbonyl group having 7 to 22 carbon atoms, more preferably 7 to 16 carbon atoms, and examples thereof include a benzoyl group.
The alkylsulfonyl group according to R is preferably an alkylsulfonyl group having 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, such as a methylsulfonyl group, an ethylsulfonyl group, an isopropylsulfonyl group, and a cyclohexylsulfonyl group. Etc.
The alkylsulfonyl group according to R is preferably an arylsulfonyl group having 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, and examples thereof include a phenylsulfonyl group and a naphthylsulfonyl group.

In addition, the monovalent substituent according to R may be further substituted with a substituent, and when substituted with a plurality of substituents, these substituents may be the same or different. Good.
When the above monovalent substituent further has a substituent, the substituent includes a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, and an alkylcarbonyloxy group. , Arylcarbonyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, alkylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, and arylsulfonyl group In addition, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyl group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, And ants And more preferably a substituent selected from Rusuruhoniru group.
X ² is preferably an oxygen atom or a sulfur atom, and particularly preferably an oxygen atom.

<Regarding R ¹⁶ in General Formula (I)>
Examples of the monovalent substituent related to R ¹⁶ in the general formula (I) include the same monovalent substituents as those described as the monovalent substituent related to R ^{2 to} R ⁵ . Among them, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, a carbamoyl group, a ureido group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group. Preferably, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group are more preferable, and an alkyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an aryl More preferred is a carbonyl group.

  The monovalent substituent may be unsubstituted or may further have a substituent. In the case of further having a substituent, the substituent includes a halogen atom, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, heterocyclic oxy group, alkylcarbonyloxy group, arylcarbonyloxy group, alkylsulfonyl. It is preferably selected from an oxy group, an arylsulfonyloxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, and an arylsulfonyl group. Atoms, alkyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, heterocyclic oxy groups, alkylcarbonyl groups, alkylthio groups, arylthio groups, heterocyclic thio groups, alkylsulfonyl groups, and arylsulfurs. And more preferably a substituent selected from the group.

Preferred examples of the compound represented by formula (I) will be described below.
Preferred specific dipyrromethene metal complexes according to the present invention are those wherein R ^{2 to} R ⁵ , R ^{7 to} R ¹⁴ , R ¹⁶ , X ¹ , a, X ² and M according to the general formula (I) are as follows: It is a compound which is. R ² and R ⁵ : each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, hydroxyl group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, Alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkoxycarbonylamino group, sulfonamido group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, An arylsulfonyl group or a sulfamoyl group;
R ³ and R ⁴ : each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, Alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, carbamoyl group, anilino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, sulfonamido group, azo group, alkylthio group, arylthio group, heterocyclic thio group An alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, or a phosphinoylamino group.
R ⁷ : a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. A metal atom or a metal compound,
R ^{8 to} R ¹⁰ : each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a silyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, or a heterocyclic ring A thio group, and at least two of R ^{8 to} R ¹⁰ are groups other than a hydrogen atom;
R ^{11 to} R ¹⁴ : each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, hydroxyl group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, Acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkoxycarbonylamino group, sulfonamide group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, or Examples include a sulfamoyl group.
X ² : an oxygen atom or a sulfur atom.
R ¹⁶ : hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, alkylcarbonyl group, arylcarbonyl group, carbamoyl group, ureido group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, or Sulfamoyl group.
M: Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B, or VO.
X ¹ : a group derived from a halogen atom, an aliphatic carboxylic acid group, an aromatic carboxylic acid group, an aliphatic imide group, an aromatic imide group, a sulfonic acid group, or a nitrogen-containing ring compound.
a: 0, 1, or 2.

More preferable specific dipyrromethene metal complexes according to the present invention include R ^{2 to} R ⁵ , R ^{7 to} R ¹⁴ , R ¹⁶ , X ¹ , a, X ² , and M according to the general formula (I): It is a compound that is a thing.
R ² and R ⁵ : each independently an alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkyl A sulfonyl group, an arylsulfonyl group, or a sulfamoyl group.
R ³ and R ⁴ : each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, carbamoyl group, carbonamido group, ureido group , An imide group, an alkoxycarbonylamino group, a sulfonamido group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group,
R ⁷ : a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group.
R ^{8 to} R ^{10 are} each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, or an alkylthio group, and at least two of R ^{8 to} R ¹⁰ are groups other than a hydrogen atom.
R ^{11 to} R ¹⁴ : each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, alkylcarbonyl group, aryl Carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkoxycarbonylamino group, sulfonamido group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, or Sulfamoyl group.
X ² : an oxygen atom or a sulfur atom.
R ¹⁶ : hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, alkylcarbonyl group, arylcarbonyl group, carbamoyl group, ureido group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, or Sulfamoyl group.
M: Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO.
X ¹ : A group derived from a halogen atom, an aliphatic carboxylic acid group, an aromatic carboxylic acid group, an aliphatic imide group, an aromatic imide group, a sulfonic acid group, or a nitrogen-containing ring compound.
a: 0, 1, or 2.

Even more preferred of the specific dipyrromethene metal complex according to the present invention are R ^{2 to} R ⁵ , R ^{7 to} R ¹⁴ , R ¹⁶ , X ¹ , a, X ² , and M according to the general formula (I): It is a compound that is.
R ² and R ⁵ : each independently an alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkyl A sulfonyl group, an arylsulfonyl group, or a sulfamoyl group.
R ³ and R ⁴ : each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, carbamoyl group, carbonamido group, ureido group , An imide group, an alkoxycarbonylamino group, a sulfonamido group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group,
R ⁷ : a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group.
R ^{8 to} R ^{10 are} each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, or an alkylthio group, and at least two of R ^{8 to} R ¹⁰ are groups other than a hydrogen atom.
R ^{11 to} R ¹⁴ : each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, alkylcarbonyl group, aryl Carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkoxycarbonylamino group, sulfonamido group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, or Sulfamoyl group.
X ² : an oxygen atom or a sulfur atom.
R ¹⁶ : an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group.
M: Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B, or VO.
X ¹ : a group derived from a halogen atom, an aliphatic carboxylic acid group, an aromatic carboxylic acid group, an aliphatic imide group, an aromatic imide group, a sulfonic acid group, or a nitrogen-containing ring compound.
a: 0, 1, or 2.

  The compound represented by the general formula (I) and the tautomer in the present invention are represented by the following general formula (II) (from the viewpoint of the stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex). More preferably.

[In General Formula (II), R ³ and R ⁴ each independently represents a hydrogen atom or a monovalent substituent. X ¹ represents a group necessary for neutralizing the charge of Zn. R ^{8 to} R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent. However, at least two of R ^{8 to} R ¹⁰ represent a monovalent substituent. R ^{11 to} R ¹⁴ each independently represents a hydrogen atom or a monovalent substituent. X ² represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or sulfur. Represents an atom. R ¹⁶ represents a hydrogen atom or a monovalent substituent. ]

The preferred range of each group of the compound represented by the general formula (II) is the same as that of the general formula (I).
The molar extinction coefficient of the dipyrromethene metal complex or its tautomer in the present invention is preferably as high as possible from the viewpoint of film thickness. The maximum absorption wavelength λ _max is preferably 520 nm to 580 nm, and more preferably 530 nm to 570 nm, from the viewpoint of improving color purity. The maximum absorption wavelength and molar extinction coefficient are measured with a spectrophotometer UV-1800PC (manufactured by Shimadzu Corporation).

Next, specific examples of the specific dipyrromethene metal complex according to the present invention are shown below. However, it is not necessarily limited to these. In addition, exemplary compounds A-104 to 106 are reference examples.

  In addition to the specific dipyrromethene metal complex, a dye or pigment having another structure may be used in combination with the colored curable composition according to the present invention as long as the effects of the present invention are not impaired.

<< Dyes with other structures >>
There is no restriction | limiting in particular as dye which has the said other structure, A well-known dye can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, JP-A-6-230210, and the like.

  The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene, squarylium, phthalocyanine, benzopyran, and indigo dyes can be used. Of these, xanthene series and squarylium series are preferable in terms of hue.

  The above dyes having other structures may be used alone or in combination of two or more dyes. The content of the dye in the colored curable composition is preferably 0.1% by mass to 30% by mass, and preferably 0.5% by mass to 20% by mass based on the total solid content of the colored curable composition. % Is more preferable. By setting the content of the dye within the above range, it is advantageous in that a good density (for example, a color density suitable for liquid crystal display) can be obtained and the patterning of the pixels becomes good.

≪Pigment≫
A pigment may be used in combination with the above-described dye in the colored curable composition.
As the pigment, a pigment having an average primary particle size of 10 nm to 30 nm is preferable. A colored curable composition having excellent hue and contrast is obtained in the above embodiment.

Conventionally known various inorganic pigments or organic pigments can be used as the pigment, but organic pigments are preferably used from the viewpoint of reliability. In the present invention, examples of the organic pigment include organic pigments described in paragraph 0093 of JP-A-2009-256572.
In particular,
C. I. Pigment Red 177, 224, 242, 254, 255, 264,
C. I. Pigment Yellow 138, 139, 150, 180, 185,
C. I. Pigment Orange 36, 38, 71,
C. I. Pigment Green 7, 36, 58,
C. I. Pigment Blue 15: 6,
C. I. Pigment Violet 23
Is preferable from the viewpoint of color reproducibility, but the present invention is not limited thereto. These organic pigments can be used alone or in various combinations in order to increase color purity.

  When using a pigment, the content in the colored curable composition of the present invention is preferably 0.5 to 50% by weight, more preferably 1 to 30% by weight, based on the total solid content of the composition. preferable. When the pigment content is within the above range, it is effective to ensure excellent color characteristics.

≪Pigment dispersant≫
When the colored curable composition of the present invention contains a pigment together with the compound represented by the general formula (I) or a tautomer thereof, it can contain a pigment dispersant.
Examples of the pigment dispersant include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic. -Based copolymers, naphthalenesulfonic acid formalin condensates], surfactants such as polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, pigment derivatives, and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

  Examples of the terminal-modified polymer having an anchor site to the pigment surface include a polymer having a phosphate group at the terminal described in JP-A-3-112992, JP-A-2003-533455, and the like. Examples thereof include a polymer having a sulfonic acid group at the terminal end described in JP-A-273191, and a polymer having a partial skeleton of an organic dye or a heterocyclic ring described in JP-A-9-77994. In addition, a polymer in which two or more anchor sites (acid group, basic group, partial skeleton of organic dye, heterocycle, etc.) to the surface of the pigment described in JP-A-2007-277514 are introduced. It is preferable because of excellent dispersion stability.

Examples of the graft polymer having an anchor site to the pigment surface include a polyester-based dispersant, specifically, JP-A-54-37082, JP-A-8-507960, Reaction products of poly (lower alkyleneimine) and polyester described in JP-A-2009-258668, etc., reaction products of polyallylamine and polyester described in JP-A-9-169821, and JP-A-10-339949 A copolymer of a macromonomer described in JP-A-2004-37986 and a nitrogen atom monomer, JP-A-2003-238837, JP-A-2008-9426, JP-A-2008-81732, etc. A graft type polymer having a partial skeleton or a heterocyclic ring of the organic dye described in JP 2010-106268 A Like copolymer of a macromonomer and acid group-containing monomer and the like. In particular, the amphoteric dispersion resin having a basic group and an acidic group described in JP-A-2009-203462 exhibits dispersibility of the pigment dispersion, dispersion stability, and a colored curable composition using the pigment dispersion. Particularly preferred from the viewpoint of developability.
As the macromonomer used when the graft polymer having an anchor site to the pigment surface is produced by radical polymerization, a known macromonomer can be used. Macromonomer AA-6 (terminal) manufactured by Toa Gosei Co., Ltd. Polymethyl methacrylate whose group is a methacryloyl group), AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S (a copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 ( Polybutyl acrylate whose end group is a methacryloyl group), PLACEL FM5 manufactured by Daicel Chemical Industries, Ltd. (5 molar equivalent addition product of ε-caprolactone of 2-hydroxyethyl methacrylate), FA10L (2-hydroxyethyl acrylate) ε-caprolactone 10 molar equivalent addition product), and JP-A-2-2720 Polyester macromonomer described in No. 09 publication. Among these, polyester-based macromonomers that are particularly flexible and have good solvophilic properties are particularly preferred from the viewpoint of the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the colored curable composition using the pigment dispersion. The polyester macromonomer represented by the polyester macromonomer described in JP-A-2-272009 is most preferable.

As the block polymer having an anchor site to the pigment surface, block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.
The pigment dispersant is also available as a commercial product. Specific examples thereof include “DA-7301” manufactured by Kashiwagi Kasei Co., Ltd., “Disperbyk-101 (polyamidoamine phosphate)” manufactured by BYK Chemie, 107 (carvone). Acid ester), 110 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high Molecular weight unsaturated polycarboxylic acid), “EFKA 4047, 4050 to 4010 to 4165 (polyurethane type), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyesteramide), 5765, manufactured by EFKA (High molecular weight polycarboxylate), 6220 (fatty acid polymer) Esters), 6745 (phthalocyanine derivatives), 6750 (azo pigment derivatives), “Ajisper PB821, PB822, PB880, PB881” manufactured by Ajinomoto Fan Techno Co., Ltd., “Floren TG-710 (urethane oligomer)” manufactured by Kyoeisha Chemical Co., Ltd., “Polyflow” No. 50E, No. 300 (acrylic copolymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester), DA, manufactured by Enomoto Kasei Co., Ltd. -703-50, DA-705, DA-725 "," Demol RN, N (naphthalene sulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "manufactured by Kao Corporation. "Homogenol L-18 (polymeric polycarboxylic acid)", "Emulgen 9 0, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative) ”manufactured by Nippon Lubrizol Co., Ltd., 13240 (Polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) "," Nikkor T106 (polyoxyethylene sorbitan mono) manufactured by Nikko Chemical Co., Ltd. Olate), MYS-IEX (polyoxyethylene monostearate) ", Kawaken Fine Chemical Co., Ltd. Hinoact T-8000E, Shin-Etsu Chemical Co., Ltd., Organosiloxane Polymer KP341, Yusho Co., Ltd. W001: Cationic surfactant ", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate Nonionic surfactants such as sorbitan fatty acid esters, anionic surfactants such as “W004, W005, W017”, “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100 manufactured by Morishita Sangyo Co., Ltd.” EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 "," Disperse Aid 6, Disperse Aid 8, Disperse Aid 15 manufactured by San Nopco Co., Ltd. , Disperse Aid 9100 ", etc., ADEKA Co., Ltd." Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103 , F108, L121, P-123 ”,“ Ionet (trade name) S-20 ”manufactured by Sanyo Chemical Co., Ltd., and the like.

  These pigment dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant. The pigment dispersant of the present invention may be used in combination with an alkali-soluble resin together with a terminal-modified polymer, a graft polymer, or a block polymer having an anchor site to the pigment surface. Alkali-soluble resins include (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and carboxylic acid in the side chain. Examples of the acid cellulose derivative include a resin having a hydroxyl group modified with an acid anhydride, and a (meth) acrylic acid copolymer is particularly preferable. Further, N-substituted maleimide monomer copolymers described in JP-A-10-300902, ether dimer copolymers described in JP-A-2004-300204, and polymerizable groups described in JP-A-7-319161. An alkali-soluble resin containing is also preferred.

As content of the pigment dispersant in a colored curable composition, it is preferable that it is 1-80 mass parts with respect to 100 mass parts of pigments, 5 mass parts-70 mass parts is more preferable, 10 mass parts-60 mass parts. More preferably, it is part by mass.
Specifically, when a polymer dispersant is used, the amount used is preferably in the range of 5 to 100 parts in terms of mass with respect to 100 parts by mass of the pigment, and in the range of 10 to 80 parts. It is more preferable that
Moreover, when using a pigment derivative together, it is preferable that it is in the range of 1 part-30 parts in conversion of mass as a usage-amount of a pigment derivative with respect to 100 mass parts of pigments, and exists in the range of 3-20 parts. More preferably, it is in the range of 5 to 15 parts.

≪Anthraquinone compound≫
The colored curable composition according to the present invention may further contain an anthraquinone compound.
By containing an anthraquinone compound, a color filter having a more effectively enhanced contrast can be obtained.
The anthraquinone compound is preferably a compound having an absorption maximum at 400 nm to 700 nm, more preferably having an absorption maximum at 500 nm to 700 nm, and particularly preferably having an absorption maximum at 550 nm to 700 nm. Any anthraquinone compound having such an absorption maximum is not particularly limited in terms of structure, and is excellent in a contrast improving effect.

Among the anthraquinone compounds in the present invention, a diaminoanthraquinone compound represented by the following general formula (IX) is preferable.
Among these diaminoanthraquinone compounds, a compound represented by the following general formula (X) is more preferable from the viewpoint of absorption characteristics, and a compound represented by the following general formula (XI) is more preferable from the viewpoint of thermal stability. Furthermore, from the viewpoint of achieving both absorption characteristics and thermal stability, a compound represented by the following general formula (XII) or the following general formula (XIII) is particularly preferable.
First, the aminoanthraquinone compound represented by the following general formula (IX) will be described.

In the general formula (IX), R ^11a and R ^12a each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, but R ^11a and R ^12a do not represent a hydrogen atom at the same time. . n ¹¹ represents an integer of 1 to 4.

The alkyl group according to R ^11a and R ^12a is preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms. For example, methyl, ethyl, iso -Propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like.
The aryl group according to R ^11a and R ^12a is preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms. For example, phenyl, o-methyl Examples include phenyl, p-methylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenylbiphenyl, 2,6-dibromophenyl, naphthyl, anthranyl, phenanthryl and the like.
The heterocyclic group according to R ^11a and R ^12a is preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. including. Examples of the heterocyclic group include imidazolyl, pyridyl, quinolyl, furyl, thienyl, benzoxazolyl, benzimidazolyl, benzthiazolyl, naphthothiazolyl, benzoxazolyl, carbazolyl group, azepinyl group, and the like.

The alkyl group, aryl group, and heterocyclic group according to R ^11a and R ^12a may further have a substituent.
Examples of the substituent in the case of having a substituent include an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, And ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably carbon An alkenyl group having 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as vinyl, allyl, 2-butenyl, 3-pentenyl, and the like, and an alkynyl group (preferably having 2 to 30 carbon atoms). An alkynyl group having 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, is preferable, for example, propargyl, 3- Ntinyl and the like), an aryl group (preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, Biphenyl, naphthyl, anthranyl, phenanthryl, etc.),

An amino group (preferably an amino group having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, and includes an alkylamino group, an arylamino group, or a heterocyclic amino group. Specific examples include amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino and the like, an alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 carbon atom). -20, particularly preferably an alkoxy group having 1 to 10 carbon atoms, such as methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc.), an aryloxy group (preferably having 6 to 30 carbon atoms, and more). An aryloxy group having 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms is preferable. Nyloxy, 1-naphthyloxy, 2-naphthyloxy, etc.), an aromatic heterocyclic oxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms). An aromatic heterocyclic oxy group of, for example, pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy and the like.

An acyl group (preferably an acyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include acetyl, benzoyl, formyl, and pivaloyl). An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonyl and ethoxycarbonyl). An aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonyl). An acyloxy group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, Is preferably an acyloxy group having 2 to 10 carbon atoms such as acetoxy and benzoyloxy), an acylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably An acylamino group having 2 to 10 carbon atoms, for example, acetylamino, benzoylamino, etc.), an alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, particularly preferably An alkoxycarbonylamino group having 2 to 12 carbon atoms, such as methoxycarbonylamino).

An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino group. ), A sulfonylamino group (preferably a sulfonylamino group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfonylamino and benzenesulfonylamino. ), A sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfa Examples include moyl and phenylsulfamoyl. ,

A carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like. ), An alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methylthio, ethylthio and the like), arylthio. A group (preferably an arylthio group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as phenylthio).

An aromatic heterocyclic thio group (preferably an aromatic heterocyclic thio group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimid Zolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio, etc.), a sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to carbon atoms). A sulfonyl group having 12 carbon atoms such as mesyl and tosyl), a sulfinyl group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, and particularly preferably having 1 to 12 carbon atoms). For example, methanesulfinyl, benzenesulfinyl, etc.), ureido group (preferably having 1 to 30 carbon atoms, more preferably A ureido group having 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include ureido, methylureido, phenylureido, and the like, and a phosphoric acid amide group (preferably having 1 to 30 carbon atoms). Preferred is a phosphoric acid amide group having 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include diethyl phosphoric acid amide and phenyl phosphoric acid amide).

Hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, An imino group or a heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. Examples include imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, azepinyl group, etc., silyl group (preferably having 3 carbon atoms). To 40, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 3 carbon atoms. A 4 silyl groups such as trimethylsilyl, etc. triphenylsilyl and the like.) And the like. These substituents may be further substituted.

In the general formula (IX), n ¹¹ represents an integer of 1 to 4, and when n ¹¹ is an integer of 2 to 4, the plurality of NR ^11a R ^12a may be the same or different.
Next, the diaminoanthraquinone compound represented by the general formula (X) will be described.

In the general formula (X), R ^21a and R ^22a each independently represents an alkyl group or an aryl group.
The alkyl group according to R ^21a and R ^22a is preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms. For example, methyl, ethyl, iso -Propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like.
The aryl group according to R ^21a and R ^22a is preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl and o-methyl. Examples include phenyl, p-methylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenylbiphenyl, 2,6-dibromophenyl, naphthyl, anthranyl, phenanthryl and the like.

The alkyl group and aryl group according to R ^21a and R ^22a may further have a substituent, and examples of the substituent are represented by R ^11a and R ^12a in the general formula (IX). Examples described above as substituents for alkyl groups, aryl groups, and heterocyclic groups are mentioned. Among them, examples of the substituent are preferably an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, and a sulfonylamino group. Sulfamoyl group, sulfonyl group, ureido group, hydroxy group, halogen atom, sulfo group, carboxyl group and the like. These details and preferred embodiments are as described above.
Next, the diaminoanthraquinone compound represented by the general formula (XI) will be described.

In the general formula (XI), R ^31a , R ^32a , R ^33a , and R ^34a each independently represent an alkyl group or a halogen atom.
The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 2 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl. , N-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like.
As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A chlorine atom and a bromine atom are preferable.

In the general formula (XI), R ^35a and R ^36a each independently represents an alkyl group, an alkoxy group, an aryloxy group, a sulfo group or a salt thereof, an aminosulfonyl group, an alkoxysulfonyl group, or a phenoxysulfonyl group.
Preferable, more preferable, and particularly preferable as the alkyl group are the same as the alkyl groups in R ^31a , R ^32a , R ^33a , and R ^34a .
The alkoxy group according to R ^35a and R ^36a is preferably an alkoxy group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methoxy, ethoxy, Examples include butoxy and 2-ethylhexyloxy.
The aryloxy group according to R ^35a and R ^36a is preferably an aryloxy group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms. , 1-naphthyloxy, 2-naphthyloxy and the like.
As the sulfo group and salts thereof according to R ^35a and R ^36a , groups derived from alkylsulfonic acid, arylsulfonic acid, and salts thereof are preferable. The sulfonate is preferably a quaternary ammonium salt or an amine salt, an alkyl sulfonate having 4 to 30 carbon atoms (preferably 10 to 30, more preferably 15 to 30), or 6 to 30 carbon atoms (preferably 10-30, more preferably 15-30) aryl sulfonates are particularly preferred.

The aminosulfonyl group according to R ^35a and R ^36a is preferably an alkylaminosulfonyl group having 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably an alkylaminosulfonyl group having 2 to 15 carbon atoms, or An arylaminosulfonyl group having 6 to 30 carbon atoms, more preferably an arylaminosulfonyl group having 6 to 20 carbon atoms, and particularly preferably an arylaminosulfonyl group having 6 to 15 carbon atoms. Specific examples include an ethylaminosulfonyl group, a propylaminosulfonyl group, Isopropylaminosulfonyl group, butylaminosulfonyl group, isobutylaminosulfonyl group, sec-butylaminosulfonyl group, pentylaminosulfonyl group, isopentylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, 2-ethylhexyl And minosulfonyl group, decylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group and the like. Dialkylaminosulfonyl group includes dimethylaminosulfonyl group, diethylaminosulfonyl group, dipropylaminosulfonyl group, diisopropylaminosulfonyl group, Dibutylaminosulfonyl group, disec-butylaminosulfonyl group, disec-propylaminosulfonyl group, dihexylaminosulfonyl group, methylethylaminosulfonyl group, methylbutylaminosulfonyl group, ethylbutylaminosulfonyl group, phenylmethylaminosulfonyl group, etc. Is mentioned. Among these, a dialkylaminosulfonyl group having 4 to 15 carbon atoms in the alkyl moiety is particularly preferable.

The alkoxysulfonyl group according to R ^35a and R ^36a is preferably an alkoxysulfonyl group having 1 to 30 carbon atoms, more preferably 2 to 20, more preferably 2 to 15 and particularly preferably 4 to 15 carbon atoms. Butylsulfonyl group, hexanesulfonyl group, decylsulfonyl group, dodecylsulfonyl group and the like.
The phenoxysulfonyl group according to R ^35a and R ^36a is preferably a phenoxysulfonyl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 15 carbon atoms. Specific examples thereof include a phenoxysulfonyl group and tolylsulfonyl group. Group and the like.

Each group according to R ^35a and R ^36a may further have a substituent. Examples of the substituent include alkyl groups represented by R ^11a and R ^12a in the general formula (IX), aryl Examples described above as substituents for groups and heterocyclic groups.
In the general formula (XI), n ³¹ and n ³² represent an integer of 0 to 2, and when n ³¹ and n ³² are 2, a plurality of R ^35a and R ^36a may be the same or different.

  Among the above anthraquinone compounds, compounds selected from the following general formula (XII) and diaminoanthraquinone compounds represented by the following general formula (XIII) are particularly preferable.

In the general formula (XII), R ^41a , R ^42a , R ^43a , and R ^44a each independently represents an alkyl group or a halogen atom, and details thereof include R ^31a in the general formula (XI), This is the same as the case of the alkyl group and halogen atom according to R ^32a , R ^33a and R ^34a , and the preferred embodiment is also the same.
In the general formula (XII), R ^45a , R ^46a , R ^47a , and R ^48a each independently represent an alkyl group, a sulfo group or a salt thereof, or an aminosulfonyl group. One of R ^45a and R ^47a and one of R ^46a and R ^48a represent a sulfo group or a salt thereof, or an aminosulfonyl group. Details of the alkyl group, sulfo group or salt thereof, and aminosulfonyl group related to R ^45a , R ^46a , R ^47a , and R ^48a are the same as those related to R ^35a and R ^36a in the general formula (XI). The preferred embodiments are also the same.

In the general formula (XIII), R ^51a , R ^52a , R ^53a , and R ^54a each independently represents an alkyl group or a halogen atom, and the details thereof include R ^31a in the general formula (XI), This is the same as the case of the alkyl group and halogen atom according to R ^32a , R ^33a and R ^34a , and the preferred embodiment is also the same.
In the general formula (XIII), R ^55a and R ^56a each independently represent a hydrogen atom or an alkyl group. Details of the alkyl group are R ^31a , R ^32a and R ^{33a in the} general formula (XI). , R ^34a is the same as in the case of the alkyl group, and preferred embodiments are also the same.
R ^57a and R ^58a each independently represent a hydrogen atom or an alkyl group, and the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms. Particularly preferred is a methyl group.
In the general formula (XIII), L ^51a and L ^52a each independently represent a divalent linking group, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, —O—, —S. _{-, - NR -, - SO} 2 -, - CO-, or a divalent linking group is preferably formed by combining a plurality of these. L ^51a and L ^52a are more preferably an alkylene group having 1 to 10 carbon atoms, a phenylene group having 6 to 12 carbon atoms, a sulfonylamino group, or a divalent linking group formed by combining a plurality of these, and particularly preferable. Is a C1-C10 alkylene group, a sulfonylamino group, or a divalent linking group formed by combining a plurality of these.

The divalent linking group formed by combining the alkylene group having 1 to 10 carbon atoms or —O— or the like may be unsubstituted or substituted, and examples thereof include ethylene, propylene, butylene groups, Examples thereof include an ethyleneoxy group, a propyleneoxy group, an ethyleneaminosulfonyl group, a propyleneaminosulfonyl group, a butyleneaminosulfonyl group, a pentyleneaminosulfonyl group, and a 1-methylethylenesulfonyl group. Among these, an alkyleneaminosulfonyl group having 2 to 10 carbon atoms (eg, ethyleneaminosulfonyl group, propyleneaminosulfonyl group, butyleneaminosulfonyl group, pentyleneaminosulfonyl group) is preferable.
The divalent linking group formed by combining the arylene group having 6 to 20 carbon atoms or —O— and the like may be unsubstituted or substituted, and examples thereof include phenylene, biphenylene, and phenyleneaminosulfonyl. Among them, an aryleneaminosulfonyl group having 6 to 12 carbon atoms (e.g., a phenyleneaminosulfonyl group) is preferable.
R in —NR— represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isobutyl group, a butyl group, an isobutyl group, a sec-butyl group, and a 2-ethylhexyl group.
In the general formula (XIII), L ^53a and L ^54a each independently represent an oxygen atom or a —NH— group.

Among the above, a preferable anthraquinone compound in the present invention is a compound selected from the diaminoanthraquinone compounds represented by the general formula (XII) or the general formula (XIII), and the following cases are particularly preferable. That is,
In the general formula (XII), R ^41a , R ^42a , R ^43a , and R ^44a are a methyl group, an ethyl group, or a bromine atom, and R ^45a and R ^46a are aminosulfonyl groups having 2 to 15 carbon atoms. And R ^47a and R ^48a are preferably methyl groups,
In the general formula (XIII), R ^51a , R ^52a , R ^53a , and R ^54a are a methyl group, an ethyl group, or a bromine atom, and R ^55a and R ^56a are a hydrogen atom or a methyl group. , R ^57a and R ^58a are a hydrogen atom or a methyl group, and L ^51a and L ^52a are an alkyleneaminosulfonyl group having 1 to 10 carbon atoms, an aralkyleneaminosulfonyl group having 7 to 12 carbon atoms, or 2 to 2 carbon atoms 10 alkyleneoxy groups, and L ^53a and L ^54a are preferably oxygen atoms.
In this case, among the following dye compounds, the compound represented by the general formula (I) or a tautomer thereof is used in combination with a metal atom or a dipyrromethene metal complex coordinated to a metal compound. This is preferable in that the effect is more effectively exhibited.
Hereinafter, the specific example of the anthraquinone compound in this invention is shown. However, the present invention is not limited to these.

  The amount of the anthraquinone compound contained in the colored curable composition is 50% by mass or less based on the total amount of all the dye compounds including the compound represented by the general formula (I) or a tautomer thereof. Preferably, the range is 2% by mass to 50% by mass, more preferably 10% by mass to 50% by mass. When the ratio of the anthraquinone compound is 50% by mass or less, the hue of the colored image is good and the contrast can be more effectively enhanced while maintaining fastness.

≪Polymerizable compound≫
The colored curable composition according to the present invention contains at least one polymerizable compound.
The polymerizable compound is, for example, a polymerizable compound having at least one ethylenically unsaturated double bond, and can be selected and used from components constituting a known composition, as disclosed in JP-A-2006-23696. Examples include the components described in Paragraph Nos. 0010 to 0020 and the components described in Paragraph Nos. 0027 to 0053 of JP-A No. 2006-64921.
Also suitable are urethane addition polymerizable compounds produced by the addition reaction of isocyanate and hydroxyl group, as described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Urethane acrylates such as those described above, and urethane having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 Compounds are also suitable.
Other examples include polyester acrylates, epoxy resins and (meth) described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reacting with acrylic acid. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

Specific examples of the polymerizable compound include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri ((meth) acryloyloxy Ethyl) isocyanurate, pentaerythritol tetra (meth) acrylate EO modified product, dipentaerythritol hexa (meth) acrylate EO modified product, etc., and commercially available products include NK ester A-TMMT, NK ester A-TMM-3. , NK Oligo UA-32P, NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix M-305, Aronix M-306, Aronix M-309, Aronix M-450, Ronikkusu M-402, TO-1382 (manufactured by Toagosei Co.), V # 802 (manufactured by Osaka Organic Chemical Industry Ltd.) can be cited as a preferred example.
These polymerizable compounds can be used alone or in combination of two or more.
The content of the polymerizable compound in the total solid content of the colored curable composition (in the case of 2 or more types, the total content) is preferably 10% by mass to 80% by mass, more preferably 15% by mass to 75% by mass. Preferably, 20% by mass to 60% by mass is particularly preferable.

≪Photopolymerization initiator≫
The colored curable composition of the present invention preferably contains at least one photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.
The photopolymerization initiator is a compound that is exposed to exposure light and starts and accelerates polymerization of the polymerizable compound. A compound that responds to actinic rays having a wavelength of 300 nm or longer and initiates and accelerates polymerization of the polymerizable compound is preferable. In addition, a photopolymerization initiator that does not directly respond to actinic rays having a wavelength of 300 nm or longer can also be preferably used in combination with a sensitizer.
Specifically, for example, oxime ester compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxides, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexa Examples thereof include arylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, onium salt compounds, acylphosphine (oxides), benzophenone compounds, acetophenone compounds, and derivatives thereof. Among these, oxime ester compounds and hexaarylbiimidazole compounds are preferable from the viewpoint of sensitivity.

Examples of the oxime ester compound include JP 2000-80068 A, JP 2001-233842 A, JP 2004-534797 A, International Publication No. 2005/080337, International Publication No. 2006/018933, and JP 2007-2007 A. The compounds described in Japanese Patent No. 210991, Japanese Patent Application Laid-Open No. 2007-231000, Japanese Patent Application Laid-Open No. 2007-267979, Japanese Patent Application Laid-Open No. 2009-191061, and International Publication No. 2009/131189 can be used.
Specific examples include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio). Phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4 -(Phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyloxime)- 1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1, -Butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9- Ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl) Such as 9H- carbazol-3-yl] ethanone and the like. However, it is not limited to these.
Moreover, in this invention, the compound represented by following General formula (1) is suitable as an oxime type compound from a viewpoint of a sensitivity, the stability at the time of diameter, and the coloring at the time of post-heating.

  In the general formula (1), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 1-5.

Specific examples of the organic halogenated compounds include Wakabayashi et al., “Bull Chem. Soc. Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605. JP, 48-34881, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP-A 62-212401, JP-A 63-70243, JP-A 63-298339, M.S. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970), and in particular, oxazole compounds substituted with a trihalomethyl group and s-triazine compounds.

  Examples of hexaarylbiimidazole compounds include, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, and 4,622,286. Various compounds described in the specification, specifically 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o- Bromophenyl)) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2, 2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) biimidazole, 2,2′-bis (o, o′-dichlorophenyl) -4,4 ′, 5,5'-tetraphenyl Imidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

A photoinitiator can be used 1 type or in combination of 2 or more types. Further, when using an initiator that does not absorb at the exposure wavelength, it is necessary to use a sensitizer.
The total content of the photopolymerization initiator is preferably 0.5 to 30% by weight, more preferably 2 to 20% by weight, based on the total solid content in the colored photosensitive resin composition, 5 mass%-18 mass% are the most preferable. Within this range, the sensitivity during exposure is high and the color characteristics are also good.

≪Alkali-soluble binder≫
The alkali-soluble binder is not particularly limited except that it has alkali solubility, and can be preferably selected from the viewpoints of heat resistance, developability, availability, and the like.
The alkali-soluble binder is preferably a linear organic high molecular polymer that is soluble in an organic solvent and can be developed 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-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

  In addition to the above, the alkali-soluble binder in the present invention includes a polymer having a hydroxyl group added with an acid anhydride, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth)), and the like. Acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like are also useful. Further, the linear organic high molecular polymer may be a copolymer of hydrophilic monomers. Examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth). Acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or straight Examples include butyl (meth) acrylate of a chain, phenoxyhydroxypropyl (meth) acrylate, and the like. Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, sulfonic acid group and groups derived from salts thereof, morpholinoethyl group, etc. Monomers comprising it are also useful.

  The alkali-soluble binder may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and includes, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain. Polymers and the like are also useful. Examples of the polymer containing the above-described polymerizable group include commercially available KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.), and the like. In addition, 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 these various alkali-soluble binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.
Examples of the acrylic resin include a copolymer made of a monomer selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and a commercially available KS resist 106 ( Osaka Organic Chemical Industry Co., Ltd.) and Cyclomer P Series (Daicel Chemical Industries, Ltd.) are preferred.

The alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 × 10 ⁵ from the viewpoint of developability, liquid viscosity, and the like, and a weight of 2000 to 1 × 10 ⁵ A coalescence is more preferable, and a polymer of 5000 to 5 × 10 ⁴ is particularly preferable.
An alkali-soluble binder may be contained independently or may contain 2 or more types.

<< Photosensitizer >>
A photosensitizer can also be added to the composition of the present invention. Typical sensitizers used in the present invention include Krivello [J. V. Crivello, Adv. in Polymer Sci, 62, 1 (1984)]. Specific examples include pyrene, perylene, acridine, thioxanthone, 2-chlorothioxanthone, benzoflavine, N-vinylcarbazole, 9,10. -Dibutoxyanthracene, anthraquinone, benzophenone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives and the like. The photosensitizer is preferably added in a proportion of 50 to 200% by weight with respect to the photopolymerization initiator.

≪Chain transfer agent≫
Chain transfer agents can also be added to the compositions of the present invention. Examples of the chain transfer agent used in the present invention include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercapto. Benzimidazole, N-phenylmercaptobenzimidazole, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, etc. And an aliphatic polyfunctional mercapto compound such as pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, and the like.
A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.
The addition amount of the chain transfer agent is preferably in the range of 0.01 wt% to 15 wt% with respect to the total solid content of the composition of the present invention, from the viewpoint of reducing sensitivity variation, % By weight to 10% by weight is more preferable, and 0.5% by weight to 5% by weight is particularly preferable.

≪Polymerization inhibitor≫
The colored photosensitive resin composition of the present invention may contain a polymerization inhibitor.
The polymerization inhibitor means hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation to radicals or other polymerization initiation species generated in the colored photosensitive resin composition by light or heat ( Or a substance that plays a role of suppressing the initiation of polymerization unintentionally by deactivating the polymerization initiation species. The polymerization inhibitors described in paragraphs 0154 to 0173 of JP 2007-334322 A can be used. Among these, p-methoxyphenol is preferably exemplified as the polymerization inhibitor.
The content of the polymerization inhibitor in the colored photosensitive resin composition of the present invention is preferably 0.0001 to 5% by weight, more preferably 0.001 to 5% by weight, based on the total weight of the ethylenically unsaturated compound. 0.001 to 1% by weight is particularly preferable.

≪Organic solvent≫
The colored curable composition of the present invention can contain an organic solvent.
The organic solvent is basically not particularly limited as long as it can satisfy the solubility of each side-by-side component and the coating property when a colored curable composition is used, and in particular, the solubility and coating property of the solid content. In view of safety, it is preferably selected.
Examples of organic solvents 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, methyl lactate, and ethyl lactate. Oxyacetic acid alkyl esters (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specific examples include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate). )), 3-oxypropionic acid alkyl esters, 2-oxypropionic acid alkyl esters, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate Propylpyruvate, a DOO methyl acetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.
Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve 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 and the like.
Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
Preferable examples of aromatic hydrocarbons include toluene and xylene.

  It is also preferable to mix two or more of these organic solvents from the viewpoints of the solubility of each of the above-mentioned components, and the solubility and the improvement of the coating surface state when an alkali-soluble binder is included. In this case, particularly preferably, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol It is a mixed solution composed of two or more selected from acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

  The content of the organic solvent in the colored curable composition is preferably such that the total solid concentration in the composition is 10% by mass to 80% by mass, and more preferably 15% by mass to 60% by mass. .

≪Surfactant≫
The colored photosensitive resin composition of the present invention may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant. Specific examples include nonionic surfactants described in paragraph 0058 of JP-A-2009-098616, and among these, fluorosurfactants are preferable.
Other surfactants that can be used in the present invention include, for example, commercially available products such as MegaFuck F142D, F172, F173, F176, F177, F183, F479, F482, and F554. F780, F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (made by DIC Corporation), Florard FC-135, FC -170C, FC-430, FC-431, Novec FC-4430 (manufactured by Sumitomo 3M), Asahi Guard AG7105, 7000, 950, 7600, Surflon S-112, S-113, S-131 S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), F-top EF351, 352, 801, 802 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Footgent 250 (manufactured by Neos Co., Ltd.), etc. Is mentioned.
Further, as the surfactant, the structural unit A and the structural unit B represented by the following formula (1) are included, and the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography using THF as a solvent is 1, A copolymer having a molecular weight of 000 or more and 10,000 or less can be given as a preferred example.

In the above formula (1), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or carbon. Represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are weight percentages representing a polymerization ratio, and p is a numerical value of 10 wt% to 80 wt%. Q represents a numerical value of 20% to 90% by weight, r represents an integer of 1 to 18, and n represents an integer of 1 to 10.

  L in the formula (1) is preferably a branched alkylene group represented by the following formula (2).

In the above formula (2), R ⁵ represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. Two or three alkyl groups are more preferred.
The sum (p + q) of p and q in the formula (1) is preferably p + q = 100, that is, 100% by weight.
The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

  Surfactant can be used individually by 1 type or in mixture of 2 or more types. The addition amount of the surfactant in the colored curable composition of the present invention is preferably 0.01% by weight to 2.0% by weight, particularly preferably 0.02% by weight to 1.0% by weight in the solid content. Within this range, the coatability and the uniformity of the cured film are good.

≪Adhesion improver≫
The colored photosensitive resin composition of the present invention may contain an adhesion improving agent.
The adhesion improver is a compound that improves the adhesion between a cured film and an inorganic substance serving as a substrate, for example, a silicon compound such as glass, silicon, silicon oxide, or silicon nitride, gold, copper, aluminum, or the like. Specific examples include silane coupling agents and thiol compounds. The silane coupling agent as the adhesion improving agent is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.
As the silane coupling agent, a silane coupling agent described in paragraph 0048 of JP-A-2009-98616 is preferable, and among them, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable. These can be used alone or in combination of two or more.
The content of the adhesion improving agent in the colored photosensitive resin composition of the present invention is preferably 0.1% by weight to 20% by weight and more preferably 0.2% by weight to 5% by weight with respect to the total solid content.

≪Crosslinking agent≫
The colored curable composition of the present invention can be supplemented with a crosslinking agent to further increase the hardness of the colored cured film obtained by curing the colored curable composition.
The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, at least selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Substituted with 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, substituted with one substituent, Phenol compounds, naphthol compounds or hydroxyanthracene compounds are mentioned. Of these, polyfunctional epoxy resins are preferred.
For details such as specific examples of the crosslinking agent, the description in paragraphs [0134] to [0147] of JP-A No. 2004-295116 can be referred to.

≪Development accelerator≫
A development accelerator can be added in order to promote alkali solubility in the non-exposed area and further improve the developability of the colored curable composition. The development accelerator is preferably a low molecular weight organic carboxylic acid compound having a molecular weight of 1000 or less and a low molecular weight phenol compound having a molecular weight of 1000 or less.
Specifically, for example, 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, Aliphatic dicarboxylic acids such as glutaric 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 tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, and umbellic acid.

≪Other additives≫
If necessary, the colored curable composition of the present invention may contain various additives such as fillers, polymer compounds other than those described above, UV absorbers, antioxidants, anti-aggregation agents, and the like. . Examples of these additives include those described in paragraphs [0155] to [0156] of JP-A No. 2004-295116.
The colored curable composition of the present invention can contain the light stabilizer described in paragraph [0078] of JP-A No. 2004-295116 and the thermal polymerization inhibitor described in paragraph [0081] of the same publication. .

≪Preparation of colored curable composition≫
The colored curable composition of the present invention is prepared by mixing the above-described components and optional components as necessary.
In preparing the colored curable composition, the components constituting the colored curable composition may be combined at once, or may be sequentially added after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.
The colored curable composition prepared as described above is preferably filtered after using a filter having a pore size of 0.01 μm to 3.0 μm and the like, and can be used.

  The colored curable composition of the present invention includes a compound represented by the above general formula (I), which is excellent in solubility in a solvent (polymerizable compound or an organic solvent optionally contained) contained in the colored curable composition, and its At least one selected from the group consisting of tautomers is contained as a colorant. Therefore, even if the content rate of a coloring agent is made high, what is excellent in storage stability is obtained. And even if the colored cured film obtained by curing the colored curable composition is a thin layer, a colored cured film having a high optical density and excellent hue and contrast can be formed. Therefore, for forming colored pixels such as color filters used in display devices such as liquid crystal display devices (LCDs) and solid-state imaging devices (for example, CCDs, CMOSs, etc.), printing inks, inkjet inks, paints, etc. It can be suitably used as a production application. In particular, it is suitable for use in forming colored pixels for display devices.

≪Color filter and manufacturing method≫
The color filter of the present invention is configured by providing a substrate and a colored region made of the colored curable composition of the present invention on the substrate. The colored region on the substrate is composed of colored films such as red (R), green (G), and blue (B) that form each pixel of the color filter.

In the method for producing a color filter of the present invention, the above-described colored curable composition is coated on a support to form a colored layer (also referred to as a colored curable composition layer) and a step ( The colored curable composition layer formed in A) is exposed to a pattern and developed to form a colored region (colored pattern) (B). In the method for producing a color filter of the present invention, in particular, the step (C) of irradiating the colored pattern formed in the step (B) with ultraviolet rays and the colored pattern irradiated with the ultraviolet rays in the step (C) are applied. On the other hand, the aspect which further provided the process (D) which heat-processes is preferable.
Hereinafter, the manufacturing method of the color filter of the present invention will be described more specifically.

-Process (A)-
In the method for producing a color filter of the present invention, first, the above-described colored curable composition of the present invention is applied onto a support by spin coating, slit coating, cast coating, roll coating, bar coating, ink jet, or the like. Is applied to form a colored curable composition layer, and then the colored curable composition layer is dried by heating (prebaking) or vacuum drying.

  Examples of the support include soda glass, alkali-free glass, borosilicate glass, quartz glass, a silicon substrate, and a resin substrate used for display devices and the like. Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the surface.

Examples of the pre-baking condition include a condition of heating at 70 ° C. to 130 ° C. for about 0.5 minutes to 15 minutes using a hot plate or an oven.
The thickness of the colored curable composition layer formed from the colored curable composition is appropriately selected according to the purpose. In the color filter for display devices, the range of 0.2 μm to 5.0 μm is preferable, and the range of 1.0 μm to 4.0 μm is more preferable. Moreover, in the color filter for solid-state image sensors, the range of 0.2 micrometer-5.0 micrometers is preferable, and the range of 0.3 micrometer-2.5 micrometers is still more preferable. In addition, the thickness of a colored curable composition layer is a film thickness after drying.

-Process (B)-
Then, in the manufacturing method of the color filter of this invention, pattern exposure is performed with respect to the colored curable composition layer formed on the support body. As light or radiation applicable to exposure, g-line, h-line, i-line and various laser beams are preferable, and i-line is particularly preferable. When using the i-line to the irradiation light is ^preferably irradiated at an exposure dose of ^{5mJ / cm 2 ~500mJ / cm 2} .

  In addition, as other exposure light sources, ultra-high pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various laser light sources, and the like can be used.

-Exposure process using laser light source-
In the exposure method using a laser light source, the irradiation light is preferably an ultraviolet laser having a wavelength range of 300 nm to 410 nm, and more preferably a wavelength of 300 nm to 360 nm. Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. . The pattern exposure, from the viewpoint of ^{productivity,} preferably in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , the range of 1mJ / cm ² ~50mJ / cm 2 is more preferable.

  There are no particular restrictions on the exposure apparatus, but commercially available devices such as Callisto (buoy technology), EGIS (buoy technology), and DF2200G (Dainippon Screen) can be used. In addition, devices other than those described above are also preferably used.

Subsequently, the colored curable composition layer after exposure is developed with a developer. Thereby, a colored pattern can be formed. As long as the developing solution dissolves the uncured portion of the colored curable composition layer and does not dissolve the cured portion, a combination of various organic solvents or an alkaline aqueous solution can be used. When the developer is an alkaline aqueous solution, the alkali concentration is preferably adjusted to pH 10-13. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl. Examples include alkaline aqueous solutions such as ammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo- [5,4,0] -7-undecene.
The development time is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 120 seconds. The development temperature is preferably 20 ° C to 40 ° C, more preferably 23 ° C.
Development can be performed by a paddle method, a shower method, a spray method, or the like.
Moreover, after developing using alkaline aqueous solution, it is preferable to wash | clean with water.

-Step (C)-
In the method for producing a color filter of the present invention, in particular, a post-exposure by ultraviolet irradiation can be performed on a colored pattern (pixel) formed using a colored curable composition.

-Process (D)-
It is preferable to further heat-treat the colored pattern that has been post-exposed by ultraviolet irradiation as described above. By heating the formed color pattern (so-called post-bake process), the color pattern can be further cured. This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, or the like.
As temperature in the case of heat processing, it is preferable that it is 100 to 300 degreeC, More preferably, it is 150 to 250 degreeC. The heating time is preferably about 10 minutes to 120 minutes.

The colored pattern thus obtained constitutes a pixel in the color filter. In the production of a color filter having a plurality of hue pixels, the above steps (A), (B), and if necessary, the steps (C) and (D) may be repeated according to the desired number of colors. Good.
The process (C) and / or the process (D) may be performed each time the formation, exposure, and development of a monochromatic colored curable composition layer is completed (for each color), or a desired color. You may perform the said process (C) and / or a process (D) collectively after formation, exposure, and image development of all the colored curable composition layers of a number are complete | finished.

  The color filter obtained by the method for producing a color filter of the present invention (the color filter of the present invention) is excellent in hue and contrast because the colored curable composition of the present invention is used. When used in a display device, it is possible to display an image with excellent spectral characteristics and contrast while achieving a good hue.

≪Display device≫
The display device of the present invention includes the above-described color filter of the present invention.
When the color filter of the present invention is used in a display device, it contains a metal complex dye excellent in spectral characteristics and heat resistance as a colorant, without reducing the voltage holding ratio when a voltage is applied, There are few alignment defects of liquid crystal molecules due to a decrease in specific resistance, the color of the display image is good, and the display characteristics are excellent.
For this reason, the display device provided with the color filter of the present invention can display a high-quality image having a good display image color tone and excellent display characteristics.

  For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issued in the first year). The display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of display devices described in the “next-generation liquid crystal display technology”.

  The color filter in the present invention may be used for a color TFT display device. The color TFT type display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention can be applied to a display device with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. .

In addition, the color filter in the present invention can be used for a bright and high-definition COA (Color-filter On Array) system. In the COA type display device, the required characteristics for the color filter layer require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the peeling liquid, in addition to the normal required characteristics as described above. Sometimes. In the color filter of the present invention, since a dye multimer excellent in hue is used, the color purity, light transmittance, etc. are good and the color pattern (pixel) is excellent in hue, so the resolution is high and the long-term durability is excellent. A COA display device can be provided. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-Technology and latest trends in the market (issued by Toray Research Center Research Division 2001)".

The display device including the color filter according to the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film in addition to the color filter according to the present invention. The color filter of the present invention can be applied to a display device composed of these known members. Regarding these materials, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
Regarding the backlight, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Have been described.

  When the color filter according to the present invention is used in a display device, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube. Further, red, green, and blue LED light sources (RGB-LED) are used. By using a backlight, a display device with high luminance and high color purity and good color reproducibility can be provided.

≪Solid-state imaging device≫
The solid-state imaging device of the present invention includes the above-described color filter of the present invention. The configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter of the present invention, and is not particularly limited as long as it is a configuration that functions as a solid-state imaging device. .

A transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) is provided on a support, and a photo is formed on the photodiode and the transfer electrode. A device having a light-shielding film made of tungsten or the like that is opened only in the light-receiving portion of the diode, and a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving portion; The color filter of the present invention is provided on the protective film.
Furthermore, it has a condensing means (for example, a microlens etc. The same shall apply hereinafter) on the device protective layer and below the color filter (on the side close to the support), or a condensing means on the color filter It may be a configuration or the like.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.

[Example 1]: Synthesis of specific dipyrromethene metal complex The specific dipyrromethene metal complex according to the present invention can be synthesized by, for example, the following scheme A or scheme B.

  According to the above scheme A, exemplary compounds A-41 and A-55 of the specific dipyrromethene metal complex according to the present invention were synthesized, and according to the above scheme B, exemplary compounds A-7 and A-1 were synthesized.

(Synthesis of Intermediate 1)
Intermediate 1 was synthesized by the method described in US Patent Application Publication No. 2008/0076044.
(Synthesis of Intermediate 2)
To 60 ml of N, N-dimethylacetamide, 30.6 g (0.3 mol) of pivalic acid was added and stirred in an ice bath. To this solution, 35.7 g (0.3 mol) of thionyl chloride was added dropwise, followed by stirring in an ice bath for 1 hour and at room temperature for 1 hour to obtain an acid halide solution.
To 200 ml of N, N-dimethylacetamide, 82.1 g (0.2 mol) of Intermediate 1 was added and stirred under ice cooling, and then the above solution was added dropwise. Thereafter, the mixture was stirred for 1 hour under ice cooling and 3 hours at room temperature.
After completion of the reaction, 700 ml of acetonitrile was added to the reaction solution and stirred for 1 hour, followed by filtration and drying of the resulting solid. In this way, 92 g (yield: 93%) of Intermediate 2 was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 11.02 (s, 1H), 10.82 (s, 1H), 7.92 (d, 1H), 7.37 to 7.25. (M, 5H), 6.28 (s, 1H), 5.87 (s, 1H), 5.56 (s, 1H), 1.36 (s, 9H), 1.25 to 0.97 ( m, 5H), 0.83 (s, 18H), 0.71 to 0.69 (d, 3H), and 0.58 to 0.46 (q, 2H).

(Synthesis of Intermediate 3)
120 ml of tetrahydrofuran and 150 ml of dimethylformamide (DMF) were stirred in an ice bath, and 18.6 g of phosphorus oxychloride was added dropwise. After completion of dropping, the mixture was stirred at 5 ° C. or lower for 1 hour. Intermediate 2 was added in small portions to this solution. Thereafter, the mixture was stirred for 1 hour in an ice bath and for 2 hours at room temperature. After completion of the reaction, the reaction solution was poured into 300 ml of water and 300 ml of ethyl acetate and extracted. The ethyl acetate solution was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated. The obtained solid was washed with 500 ml of methanol, filtered and dried. In this way, 36 g (yield: 86%) of Intermediate 3 was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 11.35 (s, 1H), 11.14 (s, 1H), 8.98 (s, 1H), 7.45 to 7.40. (M, 3H), 7.35 to 7.26 (m, 2H), 5.90 (s, 1H), 1.37 (s, 9H), 1.27 to 0.98 (m, 5H), 0.82 (s, 18H), 0.71 to 0.69 (d, 3H), and 0.45 to 0.33 (q, 2H).

(Synthesis of Intermediate 4)
To 250 ml of N-methylpyrrolidone, 76.1 g (0.5 mol) of methyl salicylate, 56.7 g (0.6 mol) of 2-chloromethyl ethyl ether, 8.3 g (0.05 mol) of potassium iodide, 82. 9 g (0.6 mol) was added and stirred at 120 ° C. for 16 hours.
The reaction solution was cooled, extracted by adding 300 ml of water and 300 ml of ethyl acetate, and the ethyl acetate solution was washed with saturated brine, and then the solvent was distilled off. Thereafter, 40 g of 50% NaOH aqueous solution, 40 ml of water and 40 ml of ethanol were added and stirred at 100 ° C. for 1 hour.
After completion of the reaction, the reaction mixture was neutralized with aqueous hydrochloric acid, and extracted with ethyl acetate. This ethyl acetate solution was washed with saturated brine, and the solvent was distilled off. Thereafter, the residue was purified by silica gel column chromatography to obtain 59 g of intermediate 4 (yield 60%).
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 8.18-8.14 (m, 1H), 7.58-7.52 (m, 1H), 7.17-7.14 ( m, 1H), 7.07 to 7.04 (m, 1H), 4.39 to 4.36 (t, 2H), 3.83 to 3.79 (t, 2H), 3.46 (s, 3H).

(Synthesis of Intermediate 5)
19.6 g (0.1 mol) of Intermediate 4 was added to 20 ml of N, N-dimethylacetamide and stirred in an ice bath. To this solution, 11.9 g (0.1 mol) of thionyl chloride was added dropwise and stirred for 1 hour in an ice bath and 1 hour at room temperature to obtain an acid halide solution.
27.4 g (0.07 mol) of Intermediate 1 was added to 70 ml of N, N-dimethylacetamide and stirred under ice-cooling, and then the above solution was added dropwise. Thereafter, the mixture was stirred for 1 hour under ice cooling and 3 hours at room temperature.
After completion of the reaction, 200 ml of acetonitrile was added to the reaction solution and stirred for 1 hour, followed by filtration and drying of the resulting solid. In this way, 33 g (yield: 85%) of Intermediate 5 was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 12.47 (s, 1H), 11.29 (s, 1H), 8.23 to 8.20 (m, 1H), 7.54 -7.48 (m, 1H), 7.36-7.08 (m, 6H), 6.35 (s, 1H), 5.90 (s, 1H), 4.58-4.54 (t 2H), 3.96 to 3.92 (t, 2H), 3.39 (s, 3H), 1.26 to 0.97 (m, 5H), 0.86 (s, 18H),. 71 to 0.69 (d, 3H) and 0.64 to 0.47 (q, 2H).

(Synthesis of Intermediate 6)
In 45 ml of acetic anhydride, 7.8 g (15 mmol) of Intermediate 3 and 8.8 g (15 mmol) of Intermediate 5 were added and stirred in an ice bath. Thereafter, 17.1 g (150 mmol) of trifluoroacetic acid was added, and the mixture was stirred for 1 hour in an ice bath and for 1 hour at room temperature. 25.2 g of sodium bicarbonate was added to 40 ml of ethyl acetate and 300 ml of water and stirred. The above reaction solution was added to the mixed solution and stirred for 2 hours. The precipitated solid was then filtered, washed with ethyl acetate and dried. In this way, 12.5 g (yield 76%) of Intermediate 6 was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are δ: 12.50 (s, 1H), 10.96 (s, 1H), 8.48 to 8.45 (d, 1H), 7.53. -7.47 (m, 1H), 7.29-7.09 (m, 8H), 6.03 (s, 1H), 5.88 (s, 1H), 4.58-4.54 (t 2H), 3.92 to 3.89 (t, 2H), 3.39 (s, 3H), 1.44 (s, 9H), 1.21 to 0.95 (m, 10H),. 81 (s, 36H), 0.65 to 0.63 (d, 6H), and 0.43 to 0.31 (q, 4H).

(Synthesis of Exemplified Compound A-41)
To 35 ml of tetrahydrofuran, 10.9 g (10 mmol) of Intermediate 6 and 2.3 g (11 mmol) of zinc acetate dihydrate were added and stirred at 50 ° C. for 5 hours. After completion of the reaction, the solvent was distilled off. The obtained solid was stirred in a methanol / water mixed solvent at 60 ° C. for 1 hour, filtered and dried. In this way, 11.3 g (yield 92%) of Exemplary Compound A was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 12.97 (s, 1H), 11.47 (s, 1H), 8.41-8.38 (m, 1H), 7.57 To 7.51 (m, 1H), 7.28 to 7.12 (m, 8H), 6.24 (s, 1H), 5.86 (s, 1H), 4.64 to 4.61 (t 2H), 3.88-3.84 (t, 2H), 3.38 (s, 3H), 1.93 (s, 3H), 1.47 (s, 9H), 1.26-0. 94 (m, 10H), 0.81 (m, 36H), 0.65 to 0.63 (d, 6H), and 0.43 to 0.38 (m, 4H).

(Synthesis of Intermediate 7)
To 60 ml of N, N-dimethylacetamide, 34.8 g (0.3 mol) of 2,2-dimethylbutyric acid was added and stirred in an ice bath. To this solution, 35.7 g (0.3 mol) of thionyl chloride was added dropwise, followed by stirring in an ice bath for 1 hour and at room temperature for 1 hour to obtain an acid halide solution.
To 200 ml of N, N-dimethylacetamide, 82.1 g (0.2 mol) of Intermediate 1 was added and stirred under ice cooling, and then the above solution was added dropwise. Thereafter, the mixture was stirred for 1 hour under ice cooling and 3 hours at room temperature.
After completion of the reaction, 700 ml of acetonitrile was added to the reaction solution and stirred for 1 hour, followed by filtration and drying of the resulting solid. In this way, 91.6 g (yield: 90%) of Intermediate 7 was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 10.98 (s, 1H), 10.80 (s, 1H), 7.37-7.25 (m, 5H), 6.28. (M, 1H), 5.87 (s, 1H), 1.73 to 1.66 (q, 2H), 1.32 (s, 6H), 1.25 to 0.90 (m, 8H), 0.83 (s, 18H), 0.70 to 0.68 (d, 3H), and 0.58 to 0.46 (q, 2H).

(Synthesis of Intermediate 8)
70 ml of tetrahydrofuran and 100 ml of dimethylformamide (DMF) were stirred in an ice bath, and 11.8 g (77 mmol) of phosphorus oxychloride was added dropwise. After completion of dropping, the mixture was stirred at 5 ° C. or lower for 1 hour. To this solution, Intermediate 7 was added in small portions. Thereafter, the mixture was stirred for 1 hour in an ice bath and for 2 hours at room temperature. After completion of the reaction, the reaction solution was poured into 300 ml of water and 200 ml of ethyl acetate and extracted. The ethyl acetate solution was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated. The obtained solid was washed with 500 ml of methanol, filtered and dried. In this way, 22.9 g (yield: 83%) of Intermediate 8 was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 11.36 (s, 1H), 11.10 (s, 1H), 8.98 (s, 1H), 7.43 to 7.31. (M, 3H), 5.90 (s, 1H), 1.75 to 1.67 (q, 2H), 1.32 (s, 6H), 1.25 to 0.87 (m, 8H), 0.82 (s, 18H), 0.71 to 0.69 (d, 3H), and 0.45 to 0.33 (q, 2H).

(Synthesis of Intermediate 9)
To 300 ml of N-methylpyrrolidone were added 73.3 g (0.6 mol) of salicylaldehyde, 173.8 g (0.9 mol) of 2-ethylhexyl bromide, and 36 g (0.9 mol) of sodium hydroxide, and the mixture was stirred at 120 ° C. for 4 hours. did. The reaction solution was cooled, extracted by adding 360 ml of water and 360 ml of ethyl acetate, and the ethyl acetate solution was washed with saturated brine.
To this ethyl acetate solution, tetrabutylammonium hydrogen sulfate 2.0 g (0.006 mol), sodium dihydrogen phosphate dihydrate 18.7 g (0.12 mol), 30% hydrogen peroxide water 74.8 g (0 .66 mol) was added and stirred in a water bath. Thereafter, 25 wt% sodium hypochlorite was added dropwise and stirred at 50 ° C. for 9 hours. After completion of the reaction, the reaction mixture was extracted into ethyl acetate, and the ethyl acetate solution was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The obtained solid was recrystallized with a mixed solvent of ethyl acetate / hexane and dried.
In this way, 112 g (yield: 67%) of Intermediate 4 was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 10.99 (br, 1H), 8.21 to 8.19 (m, 1H), 7.59 to 7.53 (m, 1H) 7.26-7.05 (m, 2H), 4.17-4.15 (d, 2H), 1.89-1.79 (m, 1H), 1.55-1.29 (m, 8H), 1.00 to 0.89 (m, 6H).

(Synthesis of Intermediate 10)
90.1 g (0.36 mol) of Intermediate 9 was added to 100 ml of N, N-dimethylacetamide and stirred in an ice bath. To this solution, 42.8 g (0.36 mol) of thionyl chloride was added dropwise and stirred for 1 hour in an ice bath and 1 hour at room temperature to obtain an acid halide solution.
After adding 123.1 g (0.3 mol) of intermediate 1 to 300 ml of N, N-dimethylacetamide and stirring under ice cooling, the above solution was added dropwise. Thereafter, the mixture was stirred for 1 hour under ice cooling and 3 hours at room temperature.
After completion of the reaction, 450 ml of acetonitrile was added to the reaction solution and stirred for 1 hour, followed by filtration and drying of the resulting solid. In this way, 179.0 g (yield: 93%) of Intermediate 10 was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 12.35 (s, 1H), 11.34 (s, 1H), 8.22 to 8.18 (m, 1H), 7.52 ˜7.46 (m, 1H), 7.35 to 7.28 (m, 5H), 7.10 to 7.04 (m, 2H), 6.34 (s, 1H), 5.89 (s) 1H), 4.31 to 4.29 (d, 2H), 2.19 to 2.09 (m, 1H), 1.54 to 1.16 (m, 11H), 1.04 to 0.82 (M, 26H), 0.71 to 0.69 (d, 3H), and 0.59 to 0.46 (m, 2H).

(Synthesis of Intermediate 11)
In 45 ml of acetic anhydride, 8.1 g (15 mmol) of Intermediate 8 and 9.6 g (15 mmol) of Intermediate 10 were added and stirred in an ice bath. Thereafter, 17.1 g (150 mmol) of trifluoroacetic acid was added, and the mixture was stirred for 1 hour in an ice bath and for 1 hour at room temperature. 25.2 g of sodium bicarbonate was added to 40 ml of ethyl acetate and 300 ml of water and stirred. The above reaction solution was added to the mixed solution and stirred for 2 hours. The precipitated solid was then filtered, washed with ethyl acetate and dried. In this way, 13.3 g (yield 76%) of intermediate 11 was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 12.39 (s, 1H), 10.87 (s, 1H), 8.45 to 8.42 (d, 1H), 7.51 ~ 7.46 (m, 1H), 7.30-7.02 (m, 13H), 6.04 (s, 1H), 5.88 (s, 1H), 5.86 (s, 1H), 4.29 to 4.27 (d, 2H), 2.15 (m, 1H), 1.83 to 1.75 (q, 2H), 1.51 to 0.79 (m, 69H),. 65 to 0.62 (m, 6H) and 0.43 to 0.31 (q, 4H).

(Synthesis of Exemplified Compound A-55)
11 g (9.4 mmol) of intermediate 11 and 2.5 g (11.3 mmol) of zinc acetate dihydrate were added to 35 ml of tetrahydrofuran, and the mixture was stirred at 50 ° C. for 4 hours. After completion of the reaction, the solvent was distilled off. The obtained solid was stirred in a methanol / water mixed solvent at 60 ° C. for 1 hour, filtered and dried. In this way, 12.0 g (yield 98%) of Exemplary Compound B was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 12.82 (s, 1H), 11.43 (s, 1H), 8.41-8.37 (m, 1H), 7.55 -7.50 (m, 1H), 7.26-7.03 (m, 13H), 6.24 (s, 1H), 5.86 (s, 1H), 4.37 (m, 2H), 2.08 (m, 1H), 1.93 (s, 3H), 1.84-1.77 (q, 2H), 1.58-0.80 (m, 69H), 0.65-0. 63 (d, 6H), 0.43 to 0.20 (m, 4H).

(Synthesis of Intermediate 12)
The intermediate 12 was synthesized according to the method described in JP2012-140586A.
(Synthesis of Intermediate 13)
Intermediate 12 of 40 ml of toluene and 6.4 g of 25% aqueous sodium hydroxide (20 mmol) was stirred in a water bath, and 3.2 g (20 mmol) of 2-ethylhexanoyl chloride was added and stirred for 6 hours. Thereafter, 2.5 g of methanol was added and stirred for 30 minutes. The aqueous layer was removed by a liquid separation operation, and the organic layer was washed with a 5% aqueous sodium hydroxide solution and a 15% aqueous acetic acid solution to obtain a toluene solution 1.
To 6.4 ml of toluene, 5.0 g (20 mmol) of intermediate 4, 2.4 g (20 mmol) of thionyl chloride, and 0.1 g of N, N-dimethylformamide were added, stirred at 40 ° C. for 30 minutes, cooled, A halide solution 1 was obtained.
To the above toluene solution 1, 43.2 g of 25% aqueous sodium hydroxide solution was added and stirred in a water bath. Thereafter, the acid halide solution 1 was added dropwise and stirred for 3 hours. Thereafter, 20 g of methanol was added and stirred for 30 minutes, and then the aqueous layer was removed by a liquid separation operation. The organic layer was washed with 5% aqueous sodium hydroxide and 15% aqueous acetic acid, and then the solvent was distilled off. The resulting solid was washed with ethyl acetate, filtered and dried. In this way, 8.3 g (yield 70%) of Intermediate 13 was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 12.45 (s, 1H), 10.53 (s, 1H), 8.38-8.34 (m, 1H), 7.53 To 7.47 (m, 1H), 7.26 to 7.03 (m, 13H), 6.01 (s, 1H), 5.88 (s, 2H), 4.30 to 4.28 (d , 2H), 2.18 to 2.08 (m, 1H), 1.94 to 0.80 (m, 75H), 0.67 to 0.62 (m, 6H), 0.41 to 0.34. (M, 4H).

(Synthesis of Exemplary Compound A-7)
To 35 ml of tetrahydrofuran, 10.5 g (8.9 mmol) of intermediate 13 and 2.4 g (10.7 mmol) of zinc acetate dihydrate were added and stirred at 50 ° C. for 4 hours. After completion of the reaction, the solvent was distilled off. The obtained solid was stirred in a methanol / water mixed solvent at 60 ° C. for 1 hour, filtered and dried. In this way, 10.7 g (yield 91%) of Exemplary Compound C was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 12.82 (s, 1H), 11.16 (s, 1H), 8.40-8.38 (m, 1H), 7.55 -7.50 (m, 1H), 7.26-7.03 (m, 12H), 6.25 (s, 1H), 5.86 (s, 2H), 4.37 (br, 2H), 2.66 (m, 1H), 2.01 (m, 1H), 1.91-0.80 (m, 77H), 0.65-0.63 (d, 6H), 0.43-0. 20 (m, 4H).

(Synthesis of Intermediate 14)
4.3 g (20 mmol) of 2-phenoxybenzoic acid, 2.4 g (20 mmol) of thionyl chloride and 0.1 g of N, N-dimethylformamide were added to 6.4 ml of toluene, and the mixture was stirred at 40 ° C. for 30 minutes and then cooled. An acid halide solution 2 was obtained.
To the toluene solution 1 obtained in the same manner as in the synthesis of the intermediate 13, 43.2 g of 25% aqueous sodium hydroxide solution was added and stirred in a water bath. Thereafter, the acid halide solution 2 was added dropwise and stirred for 3 hours. Thereafter, 20 g of methanol was added and stirred for 30 minutes, and then the aqueous layer was removed by a liquid separation operation. The organic layer was washed with 5% aqueous sodium hydroxide and 15% aqueous acetic acid, and then the solvent was distilled off. The resulting solid was washed with ethyl acetate, filtered and dried. In this way, 8.3 g (yield 72%) of intermediate 14 was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 12.72 (s, 1H), 10.56 (s, 1H), 8.44 to 8.41 (d, 1H), 7.45. To 7.11 (m, 18H), 6.89 to 6.87 (m, 1H), 6.03 (s, 1H), 5.88 (s, 1H), 5.65 (s, 1H), 2.24 (m, 1H), 1.97 to 0.80 (m, 60H), 0.70 to 0.63 (m, 6H), 0.41 to 0.29 (m, 4H). .

(Synthesis of Exemplified Compound A-1)
To 20 ml of tetrahydrofuran, 6.0 g (5.2 mmol) of intermediate 13 and 1.4 g (6.2 mmol) of zinc acetate dihydrate were added and stirred at 50 ° C. for 4 hours. After completion of the reaction, the solvent was distilled off. The obtained solid was stirred in a methanol / water mixed solvent at 60 ° C. for 1 hour, filtered and dried. In this way, 6.4 g (yield 96%) of Exemplary Compound C was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 13.14 (s, 1H), 11.18 (s, 1H), 8.48 to 8.44 (m, 1H), 7.45. To 7.11 (m, 17H), 6.82 to 6.79 (m, 1H), 6.28 (s, 1H), 5.86 (s, 1H), 5.56 (s, 1H), 2.49 (m, 1H), 1.97 (s, 3H), 1.78-0.79 (m, 60H), 0.67-0.62 (m, 6H), 0.43-0. 31 (m, 4H).

About each obtained exemplary compound, the molar absorption coefficient ((epsilon)) in a chloroform solution was measured using spectrophotometer UV-1800PC (made by Shimadzu Corp.). Illustrative compound A-7 had a maximum absorption wavelength λmax of 560.5 nm and a molar extinction coefficient (ε) of 128,000.
Moreover, the solubility with respect to the propylene glycol monomethyl ether acetate of the obtained compound and the weight decreasing rate when the solid of the obtained compound was heated to 230 degreeC were evaluated.
The results of maximum absorption wavelength λmax, molar extinction coefficient (ε), solubility in propylene glycol monomethyl ether acetate, and weight loss rate are shown in Table 1 described later.

[Example 2]
In addition to the synthesis of the exemplified compounds shown in the following Table 1 (compounds represented by the general formula (I) or tautomers thereof) by a method similar to the reaction scheme in Example 1, the same method as in Example 1 And the measurement of the maximum absorption wavelength λmax and molar extinction coefficient (ε), the solubility in propylene glycol monomethyl ether acetate, and the weight loss rate were evaluated. The results are shown in Table 1 below.

―Evaluation―
(Solubility in propylene glycol monomethyl ether acetate)
The sample was weighed, and propylene glycol monomethyl ether acetate was added to each of the following concentrations. After stirring at room temperature for 30 minutes, the dissolved state was visually confirmed.
* Determination method 5wt% or more dissolution: A
1 wt% to less than 5 wt%: B
Less than 1 wt%: C

(Weight reduction rate)
The sample was heated from 35 ° C. to 230 ° C. at a rate of 10 ° C. per minute, and the weight reduction rate (%) when heated at 230 ° C. for 30 minutes was evaluated.
* Judgment method less than 5%: A
5% to less than 10%: B
10% or more: C

Details of Comparative Compounds 1, 2, and 3 are as follows. The structural formula of each comparative compound is shown below.
Comparative compound C1 (Compound III-61 described in JP 2008-292970 A)
Comparative compound C2 (Compound A-29 described in JP 2010-85454 A)
Comparative compound C3 (Compound III-45 described in JP-A-2008-292970)

From the results in Table 1, it was found that the compound of the present invention was a compound having a high molar extinction coefficient and excellent solubility and heat resistance.
Hereinafter, specific examples of producing a colored curable composition and a color filter are shown.

Example 3
First, each component used for preparation of a colored curable composition is shown below.
(S-1): C.I. I. Pigment Blue 15: 6 (12.8 parts) and acrylic pigment dispersant (7.2 parts) are mixed with propylene glycol monomethyl ether acetate (80.0 parts), and the pigment is sufficiently dispersed using a bead mill. Pigment dispersion (T-1): Polymerizable compound: Kayalad DPHA (manufactured by Nippon Kayaku Co., Ltd .; dipentaerythritol hexaacrylate)
(U-1): Alkali-soluble binder: benzyl methacrylate / methacrylic acid (75/25 [mass ratio] copolymer (weight average molecular weight: 12,000) in propylene glycol monomethyl ether acetate solution (solid content: 40.0%)
(V-1): Photopolymerization initiator: 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone (V-2): Photopolymerization initiator: 2- (acetoxyimino) -4- (4-Chlorophenylthio) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1-butanone (W-1): sensitizer: 4, 4'-bis (diethylamino) benzophenone (X-1): Organic solvent: Propylene glycol monomethyl ether acetate (X-2): Organic solvent: Ethyl 3-ethoxypropionate (Y-1): Surfactant: Megafac F781 -F (DIC Chemical Industry Co., Ltd.)

-B1. Preparation of colored curable composition (coating solution)
The component in the following composition was mixed and the colored curable composition 1 was prepared.
<Composition>
-Exemplified compound A-1 6.9 parts (specific dipyrromethene metal complex)
Pigment dispersion: (S-1) 43.0 parts Polymerizable compound: (T-1) 103.4 parts Alkali soluble binder: (U-1)
... 212.2 parts (solid content conversion value: 84.9 parts) Photopolymerization initiator: (V-1) above ... 21.2 parts Sensitizer: (W-1) above 3.5 parts organic solvent: (X-1) 71.9 parts organic solvent: (X-2) 3.6 parts Surfactant: (Y-1)... 0.06 part

-B2. Preparation and evaluation of color filters using colored curable compositions
B1. The colored curable composition (color resist solution) obtained in 1 above was applied on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) so that the x value serving as an index of color density was 0.150. , And dried in an oven at 90 ° C. for 60 seconds (pre-baking). Thereafter, the film was exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ) with a high-pressure mercury lamp through a photomask having a mask hole width of 10 μm to 100 μm for resolution evaluation, and the coated film after exposure was subjected to alkali developer CDK- Developed with a 1% aqueous solution of No. 1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) and sprayed with pure water in a shower form to wash away the developer. Then, the coating film exposed and developed as described above is heat-treated in an oven at 220 ° C. for 1 hour (post-baking) to form a patterned colored cured film (colored layer) for the color filter on the glass substrate. Then, a colored filter substrate 1 (color filter 1) was produced.

-Evaluation-
The obtained color filter 1 was evaluated as follows. The evaluation results are shown in Table 2 below.
<1. Storage stability>
After the colored resist solution was stored in a refrigerator (5 ° C.) for one month, the degree of precipitation of foreign matters was visually evaluated according to the following criteria.
-Criteria-
A: No precipitation was observed.
B: Slight precipitation was observed.
C: Precipitation was observed.
<2. Heat resistance>
The color filter 1 was heated with a hot plate at 230 ° C. for 30 minutes as a heat resistance test, and a color difference ΔE ^* ab value before and after the heat resistance test was measured with a chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics). Evaluation was made according to criteria. A smaller ΔE ^* ab value has better heat resistance and better performance as a color filter.
-Criteria-
5: ΔE ^* ab value <3
4: 3 ≦ ΔE ^* ab value <5
3: 5 ≦ ΔE ^* ab value <10
2: 10 ≦ ΔE ^* ab value <20
1: 20 ≦ ΔE ^* ab value <3. Luminance>
The luminance of the color filter 1 was measured using a microspectrophotometer OSP-SP200 manufactured by Olympus Corporation and evaluated based on the Y value. The higher the Y value, the better the performance as a color filter for a liquid crystal display.

<4. Contrast>
When the obtained color filter 1 is sandwiched between two polarizing films, the luminance value in the case where the polarizing axes of the two polarizing films are parallel and perpendicular is measured by a color luminance meter (manufactured by Topcon Corporation, model number). : BM-5A), the luminance when the polarization axes of the two polarizing films were parallel was divided by the luminance when vertical, and the obtained value was obtained as the contrast. A higher contrast indicates better performance as a color filter for a liquid crystal display.
-Criteria-
5: Contrast is 20,000 or more 4: Contrast is 15,000 or more and less than 20,000 3: Contrast is 10,000 or more and less than 15,000 2: Contrast is 5,000 or more and less than 10,000 1: Contrast is Less than 5,000

<5. Pattern shape>
A colored film is prepared in the same manner as in Example 1, and then the entire surface of the coating film is exposed through a mask at 50 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film is subjected to an alkaline developer. Development was performed by spraying a 1% aqueous solution of CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) in the form of a shower. Thereafter, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been subjected to the photo-curing treatment and the development treatment as described above is heat-treated in an oven at 220 ° C. for 30 minutes (post-baking), and a colored resin film for constituting a color filter is formed on the glass substrate, A substrate having a colored resin film (colored substrate) was produced.

The colored substrate was cut out by glass cutting, and the cross section was observed at 15,000 times using a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.). The evaluation criteria are as follows.
[Evaluation criteria]
A: The end of the pattern has a gentle slope shape.
B: The pattern end is rectangular.
C: The cut | notch has generate | occur | produced in the pattern edge part.

[Examples 4 to 18]
In the preparation of the colored curable composition 1 of Example 3, Exemplified Compound A-1 was replaced with the aforementioned Exemplified Compound (specific dipyrromethene metal complex) shown in Table 1, and the Exemplified Compound and Pigment so that the chromaticity matched. A colored curable composition 2 to a colored curable composition 16 are prepared in the same manner as in Example 3 except that the ratio with the dispersion liquid (S-1) is adjusted, and then the color filter 2 to the color filter 16 are prepared. Produced.
Evaluation was performed in the same manner as in Example 3 using the colored curable composition 2 to the colored curable composition 16 and the color filter 2 to the color filter 16. The results are shown in Table 2 below.

Example 19
In Example 3, the components in the following composition were mixed to prepare a colored curable composition 17, and Example 3 was used except that the colored curable composition 17 was used instead of the colored curable composition 1. Similarly, a color filter 17 was obtained.
Evaluation was performed in the same manner as in Example 3 using the colored curable composition 17 and the color filter 17. The results are shown in Table 2.
-Composition-
-Exemplified Compound A-7 ... 6.9 parts-Pigment Dispersion: (S-1) ... 43.0 parts-Polymerizable Compound: (T-1) ... 103 .4 parts alkali-soluble binder: (U-1)
... 212.2 parts (converted to solids: 84.9 parts)
-Photopolymerization initiator: (V-2)-21.2 parts-Sensitizer: (W-1)-3.5 parts-Organic solvent: (X-1) ··· 71.9 parts · Organic solvent: (X-2) ··· 3.6 parts · Surfactant: (Y-1) ··· 0.06 parts

[Examples 20 to 23]
In the preparation of the colored curable composition 17 of Example 19, Exemplified Compound A-7 was replaced with the aforementioned Exemplified Compound (specific dipyrromethene metal complex) shown in Table 2, respectively, and the Exemplified Compound and the pigment dispersion were adjusted so that the chromaticity matched. A colored curable composition 18 to a colored curable composition 20 were prepared in the same manner as in Example 19 except that the ratio of the liquid (S-1) was replaced, and then color filters 18 to 20 were obtained.
Evaluation was performed in the same manner as in Example 3 using the colored curable composition 17 to the colored curable composition 20 and the color filter 17 to the color filter 20. The results are shown in Table 2.

Example 24
In Example 3, the components in the following composition were mixed to prepare a colored curable composition 18, and Example 3 was used except that the colored curable composition 21 was used instead of the colored curable composition 1. Similarly, the color filter 21 was obtained.
Evaluation was performed in the same manner as in Example 3 using the colored curable composition 21 and the color filter 21. The results are shown in Table 2.
-Composition-
-Exemplified Compound A-7 ... 4.7 parts-Pigment Dispersion: (S-1) ... 42.1 parts-Compound (5) below ... 2.3 parts Polymerizable compound: (T-1) 103.4 parts Alkali-soluble binder: (U-1)
... 212.2 parts (converted to solids: 84.9 parts)
-Photopolymerization initiator: (V-2)-21.2 parts-Sensitizer: (W-1)-3.5 parts-Organic solvent: (X-1) ··· 71.9 parts · Organic solvent: (X-2) ··· 3.6 parts · Surfactant: (Y-1) ··· 0.06 parts

  The compound (5) is a diaminoanthraquinone compound represented by the general formula (X) described above.

Example 25
In the preparation of the colored curable composition 21 of Example 24, the colored compound curable composition 22 was prepared by replacing the exemplified compound A-7 with A-41, and the colored curable composition 21 was replaced with the colored curable composition 21. A color filter 22 was obtained in the same manner as Example 21 except that 22 was used.
Evaluation was performed in the same manner as in Example 3 using the colored curable composition 19 and the color filter 19. The results are shown in Table 2.

[Comparative Examples 1 to 5]
In the preparation of the colored curable composition 1 of Example 3, Exemplified Compound A-1 was replaced with Comparative Compound 1 to Comparative Compound 5 shown in Table 2, respectively, and the comparative compound and the pigment dispersion (S- A colored curable composition 101 to a colored curable composition 104 were prepared in the same manner except that the ratio to 1) was changed. Further, color filters 101 to 105 were obtained in the same manner as in Example 3 except that the colored curable composition 101 to the colored curable composition 104 were used instead of the colored curable composition 1.
Evaluation was performed in the same manner as in Example 3 using the colored curable composition 101 to the colored curable composition 105 and the color filter 101 to the color filter 105. The results are shown in Table 2.
Comparative compounds C1 to C3 are as described above, and comparative compounds C and C5 are as follows.
Comparative compound C4 ... C. I. Acid Violet 17
Comparative compound C5 ... C. I. Acid Violet 49

From the above results, the colored curable composition prepared using the specific dipyrromethene metal complex according to the present invention has high storage stability, and the prepared color filter has excellent heat resistance, hue, contrast, and improved pattern shape. Therefore, the specific dipyrromethene metal complex according to the present invention can be said to be a highly versatile dye.

Claims (11)

A colored curable composition containing a polymerizable compound and at least one selected from the group consisting of a compound represented by the following general formula ( II ) and a tautomer thereof.

[In General Formula (II), R ³ and R ⁴ each independently represents a hydrogen atom or a monovalent substituent. X ¹ represents a group necessary for neutralizing the charge of Zn. R ^{8 to} R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent. However, at least two of R ^{8 to} R ¹⁰ represent a monovalent substituent. R ^{11 to} R ¹⁴ each independently represents a hydrogen atom or a monovalent substituent. X ² represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or sulfur. Represents an atom. R ¹⁶ represents a hydrogen atom or a monovalent substituent. ] Further, the colored curable composition according to claim 1 comprising a photopolymerization initiator. The colored curable composition according to claim 1 or 2 , further comprising at least one selected from the group consisting of a pigment and an anthraquinone compound. The colored curable composition according to claim 3 , wherein the anthraquinone compound is a compound represented by the following general formula (IX).

[In General Formula (IX), R ^11a and R ^12a each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, but R ^11a and R ^12a may simultaneously represent a hydrogen atom. Absent. n ¹¹ represents an integer of 1 to 4. ] The content of at least one selected from the group consisting of the compound represented by the general formula ( II ) and tautomers thereof is 0.1% by mass or more and 30% by mass or less based on the total solid content of the composition. The colored curable composition according to any one of claims 1 to 4 , which is a range of The colored cured film obtained by hardening | curing the colored curable composition of any one of Claims 1-5 . A color filter comprising the colored cured film according to claim 6 . A step of applying the colored curable composition according to any one of claims 1 to 5 on a support to form a colored curable composition layer, and the colored curable composition layer in a pattern shape. A step of exposing to light and developing to form a colored pattern. The color filter according to claim 7, or a display device having a color filter manufactured by the method for producing a color filter according to claim 8. The color filter according to claim 7, or a solid-state imaging device having a color filter manufactured by the method for producing a color filter according to claim 8. A compound selected from the group consisting of compounds represented by the following general formula (II) and tautomers thereof.

[In General Formula (II), R ³ and R ⁴ each independently represents a hydrogen atom or a monovalent substituent. X ¹ represents a group necessary for neutralizing the charge of Zn. R ^{8 to} R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent. However, at least two of R ^{8 to} R ¹⁰ represent a monovalent substituent. R ^{11 to} R ¹⁴ each independently represents a hydrogen atom or a monovalent substituent. X ² represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or sulfur. Represents an atom. R ¹⁶ represents a hydrogen atom or a monovalent substituent. ]