JP2012077026A - Dipyrromethene-based metal complex compound and tautomer thereof, colored composition, color filter and method for producing the same, image display, and solid-state imaging device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dipyrromethene-based metal complex compound and its tautomer, and a colored composition.SOLUTION: There is provided the dipyrromethene-based metal complex compound represented by general formula (I) or the tautomer of the compound. In the formula, Rto Reach represents H or a monovalent substituent; Rrepresents H, a halogen atom, an alkyl group or the like; Ma represents a metal or a metal compound; Xand Xeach represents NRa, N, O or S; Yand Yeach represents NRb, N or C; Rand Reach represents an alkyl group or the like; Xrepresents -L-(D)n; and L represents a single bond or a group having a valence of (n+1), which can be bonded to Ma; D represents Br, I, -S-R- or -Se-R (where R represents a hydrogen atom or a monovalent substituent; n is from 1 to 20; and (a) represents 1 or 2).

Description

  The present invention relates to a dipyrromethene-based metal complex compound and a tautomer thereof, a coloring composition, a color filter and a method for producing the same, an image display device, and a solid-state imaging device.

  Conventionally, a color filter contains a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed, a polyfunctional monomer, a polymerization initiator, an alkali-soluble resin, and other components to form a colored photosensitive composition. It is manufactured by forming a colored pattern using a photolithography method, an inkjet method, or the like.

  In recent years, color filters tend to be used not only for monitors but also for televisions (TVs) in liquid crystal display (LCD) applications. Along with this trend of expanding applications, 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.

However, in conventional pigment dispersion systems, problems such as the occurrence of scattering due to coarse pigment particles and the increase in viscosity due to poor dispersion stability tend to occur, and it is often difficult to further improve contrast and brightness.
Therefore, conventionally, as a colorant, it has been studied to use not only a pigment but also a dye (for example, see Patent Document 1). When a dye is used as a colorant, the hue and brightness of a display image when an image is displayed can be increased due to the color purity of the dye itself and the vividness of the hue, and contrast can be improved because coarse particles are eliminated. It is useful in terms.

  In particular, dipyrromethene dyes are known as dyes having high color purity and excellent heat resistance and light resistance (Patent Document 2).

JP-A-6-75375 JP 2008-292970 A

  Although the above-described dipyrromethene dyes are excellent in spectral characteristics, the conventional dipyrromethene dyes emit fluorescence, and when this dye is used for a color filter for display, the contrast is lowered.

An object of the present invention is to provide a dipyrromethene-based metal complex compound, a tautomer thereof, and a coloring composition capable of forming an image with high contrast, and an object thereof is to achieve the object.
Furthermore, the present invention aims to provide a color filter formed using the colored composition and having a high contrast, a method for producing the same, an image display device, and a solid-state imaging device, and to achieve the object. Let it be an issue.

Specific means for achieving the above object are as follows.
<1> A dipyrromethene metal complex compound represented by the following general formula (I) or a tautomer thereof.

In general formula (I), R ² , R ³ , R ⁴ and R ⁵ each independently represent 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. Ma represents a metal or a metal compound, and X ³ and X ⁴ each independently represent NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group) A nitrogen atom, an oxygen atom, or a sulfur atom. Y ¹ and Y ² each independently represent NRb (Rb represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, or Represents a carbon atom. R ⁸ and R ⁹ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. R ⁸ and Y ¹ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. A ring may be formed. X ⁵ represents -L- (D) n, L represents a single bond or an n + 1 valent group that can be bonded to Ma, and D represents a bromine atom, an iodine atom, -S-R or -Se- R (wherein R represents a hydrogen atom or a monovalent substituent). n is 1-20. When n is 2 or more, D may be the same or different. a represents 1 or 2. When a is 2, X ⁵ may be the same or different.

<2> A colored composition containing a dipyrromethene metal complex compound represented by the following general formula (I) or a tautomer thereof.

In general formula (I), R ² , R ³ , R ⁴ and R ⁵ each independently represent 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. Ma represents a metal or a metal compound, and X ³ and X ⁴ each independently represent NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group) A nitrogen atom, an oxygen atom, or a sulfur atom. Y ¹ and Y ² each independently represent NRb (Rb represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, or Represents a carbon atom. R ⁸ and R ⁹ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. R ⁸ and Y ¹ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. A ring may be formed. X ⁵ represents -L- (D) n, L represents a single bond or an n + 1 valent group that can be bonded to Ma, and D represents a bromine atom, an iodine atom, -S-R or -Se- R (wherein R represents a hydrogen atom or a monovalent substituent). n is 1-20. When n is 2 or more, D may be the same or different. a represents 1 or 2. When a is 2, X ⁵ may be the same or different.

<3> The colored composition according to <2>, further including a polymerizable compound and a photopolymerization initiator.

<4> The colored composition according to <2> or <3>, further including an anthraquinone compound.

<5> The colored composition according to <4>, wherein the anthraquinone compound is a diaminoanthraquinone compound represented by the general formula (X).

[In the general formula (X), R ^21a and R ^22a each independently represents an alkyl group or an aryl group. ]

<6> A color filter formed using the colored composition according to any one of <3> to <5>.

<7> The step of applying the colored composition according to any one of <3> to <5> above on a support to form a colored layer, and exposing the formed colored layer in a pattern And a step of developing to form a colored region.

<8> An image display device comprising the color filter according to <6> or the color filter produced by the method for producing a color filter according to <7>.

<9> A solid-state imaging device provided with the color filter according to <6> or the color filter produced by the method for producing a color filter according to <7>.

ADVANTAGE OF THE INVENTION According to this invention, the dipyrromethene type metal complex compound in which an image with high contrast is formed, its tautomer, and a coloring composition can be provided.
Furthermore, according to the present invention, it is possible to provide a color filter with high contrast, a method for manufacturing the same, an image display device, and a solid-state imaging device.

  Further, the dipyrromethene-based metal complex compound of the present invention and its tautomer, and the colored composition of the present invention solve the problems that could not be achieved with a color resist using a conventionally known dye, so that solid-state imaging is possible. It is particularly useful for color filters used in elements and display elements (for example, image display devices such as liquid crystal display elements and organic EL display elements).

  Hereinafter, the dipyrromethene-based metal complex compound of the present invention and its tautomer, and the imaged liquid crystal display device and solid-state imaging device of the present invention will be described in detail.

<Dipyrromethene-based metal complex compound and tautomer thereof>
The dipyrromethene-based metal complex compound and the tautomer thereof according to the present invention include, among the dipyrromethene-based metal complex compounds, a group (X ⁵ ) bonded to the metal of the dipyrromethene-based metal complex compound or the metal compound (Ma) is bromine. A compound having an atom, an iodine atom, -S-R or -Se-R (wherein R is a hydrogen atom or a monovalent substituent). With such a structure, when the dipyrromethene series metal complex compound of the present invention is applied to a color filter, an image with high contrast is formed. In addition to the high color purity, heat resistance, and light resistance of conventional dipyrromethene-based metal complex compounds, it is excellent in contrast.
The dipyrromethene-based metal complex compound and the tautomer thereof of the present invention are represented by the following general formula (I).

In general formula (I), R ² , R ³ , R ⁴ and R ⁵ each independently represent 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. Ma represents a metal or a metal compound, and X ³ and X ⁴ each independently represent NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group) A nitrogen atom, an oxygen atom, or a sulfur atom. Y ¹ and Y ² each independently represent NRb (Rb represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, or Represents a carbon atom. R ⁸ and R ⁹ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. R ⁸ and Y ¹ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. A ring may be formed. X ⁵ represents -L- (D) n, L represents a single bond or an n + 1 valent group that can be bonded to Ma, and D represents a bromine atom, an iodine atom, -S-R or -Se- R (wherein R represents a hydrogen atom or a monovalent substituent). n is 1-20. When n is 2 or more, D may be the same or different. a represents 1 or 2. When a is 2, X ⁵ may be the same or different.

In the general formula (I), X ⁵ represents -L- (D) n, L represents a single bond or an n + 1 valent group that can be bonded to Ma, D represents a bromine atom, an iodine atom,- S—R or —Se—R (wherein R represents a hydrogen atom or a monovalent substituent) is represented. n is 1-20. When n is 2 or more, D may be the same or different. a represents 1 or 2. When a is 2, X ⁵ may be the same or different.
Hereinafter, in X ⁵ in the general formula (I), “bromine atom, iodine atom, —S—R or —Se—R” is also referred to as “specific heavy substituent”. That is, D represents a specific heavy substituent.

In the general formula (I), in —S—R or —Se—R represented by D, R represents a hydrogen atom or a monovalent substituent.
Here, the monovalent substituent represented by R is an alkyl group (preferably a linear, branched, or cyclic alkyl having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms. Groups such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl Group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group), alkenyl group (preferably C2-C48, more preferably C2-C18 alkenyl group such as vinyl group, Allyl group, 3-buten-1-yl group) and aryl group (preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, In example, a phenyl group, a naphthyl group),

A heterocyclic group (preferably a C1-C32, more preferably a C1-C18 heterocyclic group such as a 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), acyl group (preferably 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms) For example, formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexanoyl group), anilino group (preferably having 6 to 32 carbon atoms, more preferably 6 to 24 anilino group). Group, for example, anilino group, N-methylanilino group), aminothiocarbonyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms). Nothiocarbonyl group, for example, N, N-dimethylaminothiocarbonyl group, N, N-diethylaminothiocarbonyl group, N, N-dibutylaminothiocarbonyl group, N, N-dibenzylaminothiocarbonyl group) It is done.

When the monovalent substituent represented by R is a further substitutable group, it is further substituted with a monovalent substituent represented by R ^{2 to} R ⁵ in formula (I) described later. It may be. In addition, when the monovalent substituent represented by R further has two or more monovalent substituents, these substituents may be the same or different. .
Hereinafter, in —S—R, a group in which R is an alkyl group is also referred to as an alkylthio group, in —S—R, a group in which R is an aryl group is also referred to as an arylthio group, and in —Se—R, R is an alkyl group. And the group in which R is an aryl group in -Se-R is also referred to as an arylseleno group.

The specific heavy substituent is a bromine atom, an iodine atom, an alkylthio group having 1 to 30 carbon atoms, an arylthio group having 6 to 30 carbon atoms, an alkylseleno group having 1 to 30 carbon atoms, or an arylseleno group having 6 to 30 carbon atoms. It is preferably a group.
More preferred are bromine atom, iodine atom, alkylthio group having 1 to 20 carbon atoms, arylthio group having 6 to 20 carbon atoms, alkylseleno group having 1 to 20 carbon atoms, and arylseleno group having 6 to 20 carbon atoms.
Particularly preferred are a bromine atom, an iodine atom, an alkylthio group having 1 to 15 carbon atoms, and an arylthio group having 6 to 15 carbon atoms.
The specific heavy substituent is most preferably a bromine atom.
In the above preferred embodiment of the specific heavy substituent, when the specific heavy substituent is represented by -S-R or -Se-R, -S-R and -Se-R may be further substituted. It may be a substitution.

  In the general formula (I), L represents a single bond or an n + 1 valent group that can be bonded to Ma (n is 1 to 20). That is, when L is an n + 1 valent group capable of binding to Ma, the group capable of binding to Ma has (n + 1) bonds, one of which binds to Ma and the remaining n Are attached to a specific heavy substituent which is D. At this time, when n is 2 or more, that is, when the group capable of binding to Ma has two or more specific heavy substituents, the specific heavy substituents may be the same or different.

Here, examples of the group capable of binding to Ma include the following groups. In addition, all the groups shown below do not contain a specific heavy substituent and are in a state having a hydrogen atom instead.
For example, a hydroxyl group, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, R′-CONHCO-R ′ (R ′ each independently represents an alkyl group, an aryl group, or a heterocyclic group. R ′ is bonded to each other. A 5-membered, 6-membered, or 7-membered ring may be formed, and the 5-membered, 6-membered, and 7-membered ring formed may be a saturated ring or an unsaturated ring. The 5-membered, 6-membered, and 7-membered rings are heterocycles having at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom, which may be composed of only carbon and hydrogen atoms. And R′—CONHSO ₂ —R ′ (R ′ each independently represents an alkyl group, an aryl group, or a heterocyclic group, and R ′ is bonded to each other to form a 5-, 6-, or 7-membered group). The 5-membered, 6-membered, and 7-membered rings formed may be saturated or unsaturated. The 5-membered, 6-membered, and 7-membered rings may contain at least an atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom, which may be composed of only a carbon atom and a hydrogen atom. It may be a heterocycle having one).
Among these, from the viewpoint of production of the dipyrromethene-based metal complex compound of the present invention, a hydroxyl group, a carboxylic acid group, a sulfonic acid group, R′-CONHCO-R ′, and R′-CONHSO ₂ —R ′ are preferable. The group, and R′—CONHCO—R ′ are more preferred.

In general formula (I), n is preferably 1 to 15, and more preferably 1 to 5.
In general formula (I), a represents 1 or 2.

In the general formula (I), R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent substituent.
Examples of the monovalent substituent represented by R ^{2 to} R ⁵ in the general formula (I) include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group (preferably a carbon atom). A linear, branched, or cyclic alkyl group having 1 to 48, more preferably 1 to 24 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or a 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 An alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, such as a vinyl group, an allyl group, or a 3-buten-1-yl group. , An aryl group (preferably 6 to 48 carbon atoms, more preferably an aryl group having 6 to 24 carbon atoms, for example, a phenyl group, a naphthyl group),

A heterocyclic group (preferably a C1-C32, more preferably a C1-C18 heterocyclic group such as a 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), silyl group (preferably having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms) Silyl group of, for example, trimethylsilyl group, triethylsilyl group, tributylsilyl group, t-butyldimethylsilyl group, t-hexyldimethylsilyl group), hydroxyl group, cyano group, nitro group,

An alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, an isopropoxy group, t- If it is a butoxy group, a dodecyloxy group, or a cycloalkyloxy group, for example, a cyclopentyloxy group or a cyclohexyloxy group) or an aryloxy group (preferably having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms). For example, a phenoxy group, 1-naphthoxy group), a heterocyclic oxy group (preferably a C1-C32, more preferably a C1-C18 heterocyclic oxy group, for example, 1 -Phenyltetrazol-5-oxy group, 2-tetrahydropyranyloxy group), silyloxy group (preferably having 1 to 32 carbon atoms) More preferably, it is a silyloxy group having 1 to 18 carbon atoms, for example, trimethylsilyloxy group, t-butyldimethylsilyloxy group, diphenylmethylsilyloxy group), acyloxy group (preferably having 2 to 48 carbon atoms, more preferably An acyloxy group having 2 to 24 carbon atoms, for example, an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a dodecanoyloxy group), an alkoxycarbonyloxy group (preferably having 2 to 48 carbon atoms, more preferably 2 carbon atoms). To 24 alkoxycarbonyloxy groups, for example, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, and a cycloalkyloxycarbonyloxy group such as a cyclohexyloxycarbonyloxy group), an aryloxycarbonyloxy group ( Like Or an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as a phenoxycarbonyloxy group, and a carbamoyloxy group (preferably having 1 to 48 carbon atoms, more preferably Is a carbamoyloxy group having 1 to 24 carbon atoms, for example, N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy 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, such as N, N-diethylsulfamoyloxy group, N-propylsulfa group). Moyloxy group), alkylsulfonyloxy group (preferably having 1 to 38 carbon atoms, more preferably , An alkylsulfonyloxy group having 1 to 24 carbon atoms, for example, a methylsulfonyloxy group, a hexadecylsulfonyloxy group, a cyclohexylsulfonyloxy group, an arylsulfonyloxy group (preferably having a carbon number of 6 to 32, more preferably, An arylsulfonyloxy group having 6 to 24 carbon atoms, such as a phenylsulfonyloxy group),

Acyl group (preferably an acyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexanoyl group) An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, 2 , 6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group), aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, Phenoxycarbonyl group), carbamoyl group (preferably A carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a carbamoyl group, an N, N-diethylcarbamoyl group, an N-ethyl-N-octylcarbamoyl group, or an N, N-dibutylcarbamoyl group. Group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methylN-phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group), amino group (preferably having 32 or less carbon atoms, more preferably carbon An amino group having a number of 24 or less, for example, an amino group, a methylamino group, an N, N-diethylamino group, a tetradecylamino group, a 2-ethylhexylamino group, a cyclohexylamino group), an anilino group (preferably having 6 carbon atoms) To 32, more preferably 6 to 24 anilino groups such as anilino group, N-methylanily Group), a heterocyclic amino group (preferably a heterocyclic amino group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as a 4-pyridylamino group), a carbonamido group (preferably 2 to 48 carbon atoms). , More preferably a carbonamide group having 2 to 24 carbon atoms such as an acetamido group, a benzamide group, a tetradecanamide group, a pivaloylamide group, and a cyclohexaneamide group), a ureido group (preferably having 1 to 32 carbon atoms, more preferably a carbon atom). The ureido group having 1 to 24, for example, ureido group, N, N-dimethylureido group, N-phenylureido group), imide group (preferably having 36 or less carbon atoms, more preferably imide having 24 or less carbon atoms). Group, for example, N-succinimide group, N-phthalimide group),

An alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as a methoxycarbonylamino group, an ethoxycarbonylamino group, a t-butoxycarbonylamino group, octadecyl; An oxycarbonylamino group, a cyclohexyloxycarbonylamino group), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as a phenoxycarbonylamino group). ), A sulfonamide group (preferably a sulfonamide group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methanesulfonamide group, a butanesulfonamide group, a benzenesulfonamide group, hexadecanesulfone, An amide group, a cyclohexanesulfonamido 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-dipropylsulfuryl group). Moylamino group, N-ethyl-N-dodecylsulfamoylamino group), azo group (preferably an azo group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as a phenylazo group, 3 -Pyrazolylazo group),

An alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably an alkylthio group having 1 to 24 carbon atoms, for example, a methylthio group, an ethylthio group, an octylthio group, a cyclohexylthio group), an arylthio group (preferably having a carbon number) 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, and a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic ring having 1 to 18 carbon atoms). Thio group, for example, 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group), alkylsulfinyl group (preferably having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms). Alkylsulfinyl group, for example, dodecanesulfinyl group), arylsulfinyl group (preferably having 6 to 3 carbon atoms) More preferably, it is an arylsulfinyl group having 6 to 24 carbon atoms, such as a phenylsulfinyl group, and an alkylsulfonyl group (preferably having 1 to 48 carbon atoms, more preferably an alkylsulfonyl group having 1 to 24 carbon atoms). For example, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropylsulfonyl group, 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, octylsulfonyl group, cyclohexylsulfonyl group), arylsulfonyl group (preferably, An arylsulfonyl group having 6 to 48 carbon atoms, more preferably an arylsulfonyl group having 6 to 24 carbon atoms, such as a phenylsulfonyl group or a 1-naphthylsulfonyl group, and a sulfamoyl group (preferably having 32 or less carbon atoms, more preferably carbon Number 24 or more Sulfamoyl groups such as sulfamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group Group), sulfo group, phosphonyl group (preferably phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as phenoxyphosphonyl group, octyloxyphosphonyl group, phenylphosphonyl group). A phosphinoylamino group (preferably a phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as a diethoxyphosphinoylamino group, a dioctyloxyphosphinoylamino group, ) And the like.

When the monovalent substituent represented by R ^{2 to} R ⁵ in the general formula (I) is a further substitutable group, the monovalent substituent represented by R ^{2 to} R ⁵ is: The monovalent substituent described in R ^{2 to} R ⁵ may further be included. When the monovalent substituent represented by R ^{2 to} R ⁵ has two or more monovalent substituents, these monovalent substituents may be the same or different. Also good.

In the general formula (I), R ² and R ³ or / and R ⁴ and R ⁵ may be independently bonded to each other to form a 5-membered, 6-membered or 7-membered ring. In addition, as a ring formed, there exists a saturated ring or an unsaturated ring. Examples of the 5-membered, 6-membered, or 7-membered saturated ring or unsaturated ring include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, Examples include a piperidine ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, a pyridine ring, a pyrazine ring and a pyridazine ring, and preferably a benzene ring and a pyridine ring.

When the 5-membered, 6-membered and 7-membered rings formed by R ² and R ³ or / and R ⁴ and R ⁵ in the general formula (I) are further substitutable groups, a specific heavy substitution In the case where 5-membered, 6-membered, and 7-membered rings are substituted with two or more substituents R, which may be substituted by R as the monovalent substituent described in the explanation of the group, These substituents R may be the same or different.

In the general formula (I), as R ² and R ⁵ , among the above, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitrile group, an imide group, and a carbamoylsulfonyl group Preferred are alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, nitrile group, imide group, carbamoylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, nitrile group, imide group, carbamoyl. A sulfonyl group is more preferable, and an alkoxycarbonyl group, an aryloxycarbonyl group, and a carbamoyl group are particularly preferable.

In the general formula (I), R ³ and R ⁴ are preferably an alkyl group, an aryl group, or a heterocyclic group, more preferably an alkyl group or an aryl group, among the above.
Each group shown in the preferred embodiment may be unsubstituted or may have the above-described substituent.

In general formula (I), when R ³ and R ⁴ represent an alkyl group, the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and more Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, i-butyl group, t-butyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and Benzyl group, more preferably a branched chain having 1 to 12 carbon atoms or a cyclic alkyl group, and more specifically, for example, isopropyl group, cyclopropyl group, i-butyl group, t- And a butyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group, and more preferably a secondary or tertiary alkyl group having 1 to 12 carbon atoms, and more specifically, In example, an isopropyl group, a cyclopropyl group, i- butyl, t- butyl group, a cyclobutyl group, a cyclohexyl group.
Each group shown in the preferred embodiment may be unsubstituted or may have the above-described substituent.

In general formula (I), when R ³ and R ⁴ represent an aryl group, the aryl group is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
When R ³ and R ⁴ represent a heterocyclic group, the heterocyclic group 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, benzotriazol-1-yl group, and more preferably 2-thienyl group, 4-pyridyl group, 2-furyl group, 2- Examples include a pyrimidinyl group and a 1-pyridyl group.
Each group shown in the preferred embodiment may be unsubstituted or may have the above-described substituent.

In general formula (I), R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group.
When R ⁷ is not a hydrogen atom, that is, when R ⁷ is a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, the halogen atom described for the substituent represented by R ^{2 to} R ⁵ , The same group as an alkyl group, an aryl group, and a heterocyclic group is represented, and its preferable range is also the same.

When the alkyl group, aryl group, and heterocyclic group represented by R ⁷ in general formula (I) are further substitutable groups, the monovalent substituent represented by R ^{2 to} R ⁵ above. And may be substituted with the substituent described above. When the alkyl group, aryl group, and heterocyclic group represented by R ⁷ are substituted with two or more substituents, these substituents may be the same or different.

Ma in the general formula (I) represents a metal or a metal compound. Ma may be any metal atom or metal compound capable of forming a metal complex, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal. Contains chloride.
Examples of the metal include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, and B.
As the metal compound, for _{example, AlCl, InCl, FeCl, TiCl} 2, SnCl 2, SiCl 2, GeCl 2 metal chlorides, such as, TiO, metal oxides such as VO, Si _{(OH) 2} or the like of the metal hydroxide Is mentioned.

  Among these, Ma in the general formula (I) is Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn from the viewpoints of the stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex. Cu, Ni, Co, TiO, B, or VO are preferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO are more preferable, and Fe, Zn, Cu, Co, Most preferred is B or VO (V = O). Among these, Zn is particularly preferable.

In general formula (I), R ⁸ and R ⁹ are each independently an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. Represents a group.
More specifically, it is an alkyl group (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, a propyl group, or an isopropyl group. Group, butyl group, isobutyl group, t-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group), alkenyl group (preferably having 2 to 2 carbon atoms) 24, more preferably an alkenyl group having 2 to 12, for example, a vinyl group, an allyl group, a 3-buten-1-yl group), an aryl group (preferably having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms). An aryl group, for example, a phenyl group, a naphthyl group), a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), alkoxy Group (preferably an alkoxy group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms, such as methoxy group, ethoxy group, propyloxy group, butoxy group, hexyloxy group, 2-ethylhexyloxy group, dodecyloxy group, , A cyclohexyloxy group), an aryloxy group (preferably an aryloxy group having 6 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, such as a phenoxy group or a naphthyloxy group), an alkylamino group (preferably a carbon number). 1 to 36, more preferably 1 to 18 alkylamino groups such as methylamino group, ethyl Mino group, propylamino group, butylamino group, hexylamino group, 2-ethylhexylamino group, isopropylamino group, t-butylamino group, t-octylamino group, cyclohexylamino group, N, N-diethylamino group, N, N-dipropylamino group, N, N-dibutylamino group, N-methyl-N-ethylamino group), arylamino group (preferably an arylamino group having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms) , For example, phenylamino group, naphthylamino group, N, N-diphenylamino group, N-ethyl-N-phenylamino group) or heterocyclic amino group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 heterocyclic amino groups such as 2-aminopyrrole group, 3-aminopyrazole group, 2-aminopyridine group, 3-amino Nopyridine group).

In general formula (I), the alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylamino group, arylamino group, or heterocyclic amino group represented by R ⁸ and R ⁹ is Further, in the case of a group that can be further substituted, it may be substituted by R represented as a monovalent substituent described in the description of the specific heavy substituent. The alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylamino group, arylamino group, or heterocyclic amino group represented by R ⁸ and R ⁹ in the general formula (I) When two or more Rs are substituted, Rs may be the same or different.

In general formula (I), X ³ and X ⁴ each independently represent NRa, a nitrogen atom, an oxygen atom, or a sulfur atom. In NRa, Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group.
More specifically, Ra is a hydrogen atom, an alkyl group (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, and the like. Group, 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), alkenyl group (preferably Is an alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, such as vinyl group, allyl group, 3-buten-1-yl group), aryl group (preferably having 6 to 36 carbon atoms, and more). Preferably it is a 6-18 aryl group, for example, a phenyl group, a naphthyl group), a heterocyclic group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms). A bicyclic group, 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), acyl group (preferably an acyl group having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, for example, acetyl group, pivaloyl group, 2-ethylhexyl group, benzoyl group, cyclohexanoyl group) An alkylsulfonyl group (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, a cyclohexylsulfonyl group), an arylsulfonyl group (preferably Is an arylsulfonyl group having 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, Eg to represent phenylsulfonyl group, a naphthylsulfonyl group). Further, when Ra can be substituted, it may be further substituted with a substituent, and when it is substituted with a plurality of substituents, these substituents may be the same or different.
X ³ and X ⁴ are preferably each independently an oxygen atom or a sulfur atom, and particularly preferably both X ³ and X ⁴ are oxygen atoms.

In general formula (I), Y ¹ and Y ² each independently represent NRb, a nitrogen atom, or a carbon atom, and Rb has the same meaning as Ra in X ³ .
Y ¹ and Y ² are preferably each independently NRb (Rb is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), and Y ¹ and Y ² are particularly preferably both NH.

In general formula (I), R ⁸ and Y ¹ are bonded to each other, and together with R ⁸ , Y ¹ , and carbon atom, a 5-membered ring (for example, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, tetrahydrothiophene, pyrrole, furan) Thiophene, indole, benzofuran, benzothiophene), 6-membered ring (eg, cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane, pentamethylene sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline), or A 7-membered ring (eg, cycloheptane, hexamethyleneimine) may be formed.

In general formula (I), R ⁹ and Y ² may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring together with R ⁹ , Y ² , and the carbon atom. 5-membered to be formed, 6-membered, and 7-membered ring, the ring one bond in the ring formed by said R ⁸ and Y ¹ and the carbon atom is changed to the double bond.

In the general formula (I), when the 5-membered, 6-membered, and 7-membered rings formed by combining R ⁸ and Y ¹ or / and R ⁹ and Y ² are further substitutable rings May be substituted by R represented as a monovalent substituent described in the description of the specific heavy substituent. When the ring is substituted with two or more R, R may be the same or different.

A preferred embodiment of the dipyrromethene-based metal complex compound of the present invention is an embodiment represented by a combination of groups shown as preferred embodiments in the above-described general formulas R ² , R, X ^{5 and the} like.
A more preferred embodiment is as follows.

The more preferable aspect of the compound represented by general formula (I) is shown below.
X ⁵ in the general formula (I) is represented by n is 1 to 20, and L is a single bond or “hydroxyl group, carboxylic acid group, sulfonic acid group, R′-CONHCO-R ′, and R′-CONHSO”. _2- R ′ (R ′ each independently represents an alkyl group, an aryl group, or a heterocyclic group) ”and is represented by a group obtained by removing n hydrogen atoms from a group that can be bonded to Ma. Is represented by a bromine atom, an iodine atom, an alkylthio group having 1 to 30 carbon atoms, an arylthio group having 6 to 30 carbon atoms, an alkylseleno group having 1 to 30 carbon atoms, an arylseleno group having 6 to 30 carbon atoms, and a is 1 and R ² and R ⁵ are each represented by 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. R ³ and R ⁴ are each independently represented by a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R ⁷ is represented by a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma is represented by Zn, Cu, Co, or VO, and X ³ and X ⁴ are each independently represented by an oxygen atom or a sulfur atom. Y ¹ and Y ² are each independently represented by NRb (Rb is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), and R ⁸ and R ⁹ are an alkyl group, an aryl group, a heterocyclic group, It is represented by an alkoxy group or an alkylamino group. In R ⁸ and R ⁹ , R ⁸ and Y ¹ are bonded to each other to form a 5- or 6-membered ring, or R ⁹ and Y ² are bonded to each other to form a 5- or 6-membered ring. May be.
Each group shown in the preferred embodiment may be unsubstituted or may have the above-described substituent.

Further preferred embodiments of the compound represented by the general formula (I) are shown below.
X ⁵ in the general formula (I), n is represented by 1 to 15, L is a single bond or “hydroxyl group, carboxylic acid group, and R′—CONHCO—R ′ (R ′ is independently An alkyl group, an aryl group, and a heterocyclic group) ”, represented by a group in which n hydrogen atoms are removed from a group that can be bonded to Ma, and D is a bromine atom, an iodine atom, or a carbon number of 1 to 20 It is represented by an alkylthio group, an arylthio group having 6 to 20 carbon atoms, an alkylseleno group having 1 to 20 carbon atoms, or an arylseleno group having 6 to 20 carbon atoms, a is represented by 1, and R ² and R ⁵ are alkoxy a carbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, a nitrile group, an imido group, carbamoyl sulfonyl group, R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, an aryl group, and Represented by heterocyclic group, ^{R 7} is a hydrogen atom, an alkyl group, represented by an aryl group, or a heterocyclic group, Ma is Zn, Cu, represented by Co, or VO. X ³ and X ⁴ are oxygen atoms, Y ¹ and Y ² are NH, and R ⁸ and R ⁹ are an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group. In R ⁸ and R ⁹ , R ⁸ and Y ¹ are bonded to each other to form a 5- or 6-membered ring, or R ⁹ and Y ² are bonded to each other to form a 5- or 6-membered ring. May be.
Each group shown in the preferred embodiment may be unsubstituted or may have the above-described substituent.

Particularly preferred embodiments of the compound represented by formula (I) are shown below.
X ⁵ in the general formula (I), n is represented by 1 to 5, and L is a single bond or “hydroxyl group, carboxylic acid group, and R′—CONHCO—R ′ (R ′ is independently An alkyl group, an aryl group, a heterocyclic group) ”, a group that can be bonded to Ma, and represented by a group in which n hydrogen atoms have been removed; and D is a bromine atom, an iodine atom, or a C 1-15 carbon atom. An alkylthio group, which is represented by an arylthio group having 6 to 15 carbon atoms, a is represented by 1, and R ² and R ⁵ are an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a nitrile group, an imide group, and a carbamoylsulfonyl group. R ³ and R ⁴ are each independently represented by an alkyl group or an aryl group, R ⁷ is represented by a hydrogen atom, and Ma is represented by Zn. X ³ and X ⁴ are oxygen atoms, Y ¹ and Y ² are NH, and R ⁸ and R ⁹ are an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group.
Each group shown in the preferred embodiment may be unsubstituted or may have the above-described substituent.

The compound represented by the general formula (I) may be a tautomer.
The tautomer may be any compound that has a structure that can be formed by movement of one hydrogen atom in the molecule. For example, the structure of the following general formulas (a) to (f) It may be.

The above structure is an example of a tautomer structure, and can take various isomeric structures depending on the structures of R ^{2 to} R ⁵ , R ^{7 to} R ⁹ , Y ¹ , Y ² , and X ^{3 to} X ^5. . For example, when the “group capable of binding to Ma” in X ⁵ is a monovalent group derived from succinimide, two more types of isomeric structures can be considered.

In the general formula (g) and the general formula (h), the monovalent group derived from succinimide is represented by “n + 1 valent group capable of binding to Ma” represented by L in the general formula (I). "Is a structural formula that does not contain a specific heavy substituent.
In the tautomer of the dipyrromethene-based metal complex compound of the present invention, the monovalent group derived from the succinimide in the general formula (g) and the general formula (h) is used as the substituent. A structure having a group.

The molar extinction coefficient of the dipyrromethene metal complex compound 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, exemplary compounds A-1 to A-30 and exemplary compounds B-1 to B-6, which are specific examples of the dipyrromethene-based metal complex compound in the present invention, are shown below. However, the present invention is not limited to these.
In the specific examples shown in the exemplary compounds A-1 to A-30, R ⁸ and R ⁹ in the general formula (I) are the same group (R ⁸ = R ⁹ ).

  The dipyrromethene metal complex compound or the tautomer thereof in the present invention described above is disclosed in U.S. Pat. No., Aust. J. Chem, 1965, 11, 1835-1845, JH Boger et al, Heteroatom Chemistry, Vol. 1, No. 5, 389 (1990) and the like.

<Coloring composition>
The colored composition of the present invention is composed of one or more selected from the above-described dipyrromethene-based metal complex compound of the present invention and tautomeric compounds thereof, and preferably, And an anthraquinone compound.
Moreover, you may comprise a polymeric compound and a photoinitiator, and you may comprise as a photosensitive curable composition. In this case, the colored composition of the present invention is preferably configured to contain an alkali-soluble binder and an organic solvent, and can be further configured using various additives as necessary.
In the coloring composition of the present invention, the dipyrromethene-based metal complex compound of the present invention or a tautomer thereof may be contained singly or in combination of two or more.
In the present specification, “to” represents a range from the lower limit value to the upper limit value.

  The content of the dipyrromethene-based metal complex compound of the present invention or the tautomer thereof in the colored composition varies depending on the molecular weight and the extinction coefficient, but is 1 to 70 mass based on the total solid content of the colored composition. % Is preferable, and 10% by mass to 50% by mass is more preferable. When the dye content is 10% by mass or more, a good color density (for example, a color density suitable for liquid crystal display) can be obtained, and when it is 50% by mass or less, pixel patterning becomes good. Is advantageous.

Furthermore, the coloring composition of the present invention may contain a dye or pigment having a different structure from the structure of the dipyrromethene-based metal complex compound of the present invention or a tautomer thereof, and a dispersion thereof.
-Other dyes-
There is no restriction | limiting in particular as dye, 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.

-Pigment-
In the coloring composition of the present invention, a pigment can be used in combination with the above dye or together with the above dye.
As the pigment, a pigment having an average primary particle diameter of 10 nm to 30 nm is preferable. In the above aspect, a colored composition having excellent hue and contrast can be obtained.

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 composition of the present invention is preferably 1% by mass to 55% by mass and more preferably 5% by mass to 45% by mass with respect to 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.

[Anthraquinone compound]
The colored composition of the present invention preferably contains at least one anthraquinone compound.
Although the reason is not clear due to the inclusion of the anthraquinone compound, the contrast can be effectively enhanced when the colored composition of the present invention is applied to a color filter, an image display device, a solid-state imaging device or the like.

  The anthraquinone compound in the present invention is a compound having an absorption maximum at 400 nm to 700 nm. In the present invention, the anthraquinone compound preferably has an absorption maximum at 500 nm to 700 nm, and particularly preferably has 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, an aminoanthraquinone compound represented by the following general formula (IX) is preferable.
Among these aminoanthraquinone 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, compounds represented by the following general formula (XII) or the following general formula (XIII) are particularly preferred.

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 represent a hydrogen atom at the same time. Absent. 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.

The alkyl group represented by 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, Examples include iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like.

The aryl group represented by 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- Examples thereof include methylphenyl, p-methylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenylbiphenyl, 2,6-dibromophenyl, naphthyl, anthranyl, phenanthryl and the like.

The heterocyclic group represented by 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 sulfur. Contains atoms. Examples of the heterocyclic group include imidazolyl, pyridyl, quinolyl, furyl, thienyl, benzoxazolyl, benzimidazolyl, benzthiazolyl, naphthothiazolyl, benzoxazolyl, carbazolyl group, azepinyl group, and the like.

Moreover, the alkyl group, aryl group, and heterocyclic group represented by 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, and particularly preferably 0 to 10 carbon atoms). Group, arylamino group, or heterocyclic amino group, and specific examples include amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino, etc.), alkoxy group ( Preferably 1-30 carbon atoms, more preferably 1-20 carbon atoms, particularly preferably A C1-C10 alkoxy group such as methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc.), an aryloxy group (preferably having 6-30 carbon atoms, more preferably 6-20 carbon atoms). Particularly preferably an aryloxy group having 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyloxy, 2-naphthyloxy, etc.), an aromatic heterocyclic oxy group (preferably having 1 to 1 carbon atoms). 30 and more preferably an aromatic heterocyclic oxy group having 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include 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 having 7 to 30 carbon atoms, more preferably having 7 to 20 carbon atoms, particularly preferably An aryloxycarbonylamino group having 7 to 12 carbon atoms, such as And sulfonylamino group (preferably a sulfonylamino group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms. For example, methane Sulfonylamino, benzenesulfonylamino and the like), a sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, and particularly preferably 0 to 12 carbon atoms. , Methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, etc.), a carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms). For example, 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, and particularly preferably 1 to 12 carbon atoms, such as methylthio and ethylthio), an arylthio 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 phenylphosphoric acid amide.), Hydroxy group, mercapto group, halogen atom (For example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having 1 to 1 carbon atoms) 30, more preferably a heterocyclic group having 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. Specific examples include imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, azepinyl group, and the like. Group (preferably a silyl group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyl and triphenylsilyl). . 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. n ¹¹ is preferably an integer of 2 to 3, and n ¹¹ is more preferably 2.

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 represented by 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, Examples include iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like.

The aryl group represented by R ^21a and R ^22a 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- Examples thereof include methylphenyl, p-methylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenylbiphenyl, 2,6-dibromophenyl, naphthyl, anthranyl, phenanthryl and the like.

In addition, the alkyl group and aryl group represented by R ^21a and R ^22a may further have a substituent. Examples of the substituent include R ^11a and R ^12a in the general formula (IX). Examples described above as substituents of the alkyl group, aryl group, and heterocyclic group represented can be given. 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 represented by R ^31a , R ^32a , R ^33a , and R ^34a 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. Examples include methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like.

Examples of the halogen atom represented by R ^31a , R ^32a , R ^33a , and R ^34a include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and 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.

The alkyl group represented by R ^35a and R ^36a has the same meaning as the alkyl group represented by R ^31a , R ^32a , R ^33a and R ^34a , and the preferred embodiment is also the same.

The alkoxy group represented by R ^35a and R ^36a is preferably an alkoxy group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms. , Butoxy, 2-ethylhexyloxy and the like.

The aryloxy group represented by 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. Examples include oxy, 1-naphthyloxy, 2-naphthyloxy and the like.

The sulfo group represented by R ^35a and R ^36a and a salt thereof are preferably a sulfonic acid group and a group derived from a sulfonic acid salt. The sulfonate is preferably a quaternary ammonium salt or an amine salt, and particularly preferably a sulfonate having 4 to 30 carbon atoms (preferably 10 to 30, more preferably 15 to 30).

The aminosulfonyl group represented by R ^35a and R ^36a is preferably an aminosulfonyl group having 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 15 carbon atoms. Ethylaminosulfonyl group, propylaminosulfonyl group, isopropylaminosulfonyl group, butylaminosulfonyl group, isobutylaminosulfonyl group, sec-butylaminosulfonyl group, pentylaminosulfonyl group, isopentylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylamino Examples include a sulfonyl group, 2-ethylhexylaminosulfonyl group, decylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group and the like. Phonyl group, diethylaminosulfonyl group, dipropylaminosulfonyl group, diisopropylaminosulfonyl group, dibutylaminosulfonyl group, disec-butylaminosulfonyl group, disec-propylaminosulfonyl group, dihexylaminosulfonyl group, methylethylaminosulfonyl group, Examples thereof include a methylbutylaminosulfonyl group, an ethylbutylaminosulfonyl group, and a phenylmethylaminosulfonyl group. Among these, a dialkylaminosulfonyl group having 4 to 15 carbon atoms in the alkyl moiety is particularly preferable.

The alkoxysulfonyl group represented by R ^35a and R ^36a is preferably an alkoxysulfonyl group having 1 to 30 carbon atoms, more preferably 2 to 20, still more preferably 2 to 15 and particularly preferably 4 to 15 carbon atoms. Examples include butylsulfonyl group, hexanesulfonyl group, decylsulfonyl group, dodecylsulfonyl group and the like.

The phenoxysulfonyl group represented by 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 include a phenoxysulfonyl group, And a tolylsulfonyl group.

R ^35a and R ^36a may further have a substituent. Examples of the substituent include an alkyl group, an aryl group, and a heterocyclic ring represented by R ^11a and R ^12a in the general formula (IX). Examples described above as the substituent of the group are given.

In the general formula (XI), n ³¹ and n ³² represent an integer of 0 to 2, and when n = 2, a plurality of R ^35a and R ^36a may be the same or different.

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

[Diaminoanthraquinone compound represented by the general formula (XII)]

In the general formula (XII), R ^41a , R ^42a , R ^43a , and R ^44a each independently represent an alkyl group or a halogen atom, and R ^31a , R ^32a , R in the general formula (XI) It is synonymous with the alkyl group and halogen atom in ^33a , ^R34a , and its preferable aspect is also the same.

R ^45a , R ^46a , R ^47a and R ^48a in the general formula (XII) each independently represents 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. R ^45a , R ^46a , R ^47a , and R ^48a have the same ^meanings as the alkyl group, sulfo group or salt thereof, and aminosulfonyl group represented by R ^35a and R ^36a in the general formula (XI). Is the same.

[Diaminoanthraquinone compound represented by the general formula (XIII)]

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 R ^31a , R ^32a , R ^{33a in the} general formula (XI) , R ^{34a have} the same meaning as the alkyl group and halogen atom, and the preferred embodiments are also the same.

In the general formula (XIII), R ^55a and R ^56a each independently represent a hydrogen atom or an alkyl group, and the alkyl group represents R ^31a , R ^32a , R ^33a , R ^{34a in the} general formula (XI). And the 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, when the compound represented by the general formula (I) is used in combination with a metal atom or a dipyrromethene-based metal complex compound coordinated to the metal compound, the effect of the present invention is further improved. It is preferable in that it is effectively played.

  Hereinafter, the specific example of the anthraquinone compound in this invention is shown. However, the present invention is not limited to these.

  The ratio of the anthraquinone compound to the total mass of the dipyrromethene-based metal complex compound of the present invention and its tautomer is preferably 100% by mass or less, more preferably in the range of 4% by mass to 100% by mass. More preferably, the content is in the range of 20% by mass to 100% by mass. When the ratio of the anthraquinone compound is 100% 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 composition of the present invention preferably contains at least one polymerizable compound.
Examples of the polymerizable compound include a polymerizable compound having at least one ethylenically unsaturated double bond. Such a polymerizable compound can be selected from components constituting a known composition and used, for example, the components described in paragraphs [0010] to [0020] of JP-A-2006-23696, The components described in JP-A 2006-64921, paragraphs [0027] to [0053] can be mentioned.

In addition, as the polymerizable compound, a urethane addition polymerizable compound produced by using an addition reaction between isocyanate and a hydroxyl group is also suitable, and Japanese Patent Application Laid-Open No. 51-37193 and Japanese Patent Publication No. 2-32293 are also preferable. Urethane acrylates as described in JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, JP-B-62-39418 Urethane compounds having an ethylene oxide skeleton described in the publication 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 include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate. And pentaerythritol tetra (meth) acrylate EO modified product, dipentaerythritol hexa (meth) acrylate EO modified product, and the like. Moreover, you may use a commercial item, and as a commercial item, NK ester A-TMMT, NK ester A-TMM-3, NK oligo UA-32P, NK oligo UA-7200 (above, Shin-Nakamura Chemical Co., Ltd. product) ), Aronix M-305, Aronix M-306, Aronix M-309, Aronix M-450, Aronix M-402, TO-1382 (above, manufactured by Toagosei Co., Ltd.), V # 802 (Osaka Organic Chemical Industry ( Can be mentioned as a preferred example.
These polymerizable compounds may be used alone or in combination of two or more.

  The content of the polymerizable compound in the total solid content of the coloring composition (total content in the case of two or more) is preferably 10% by mass to 80% by mass, more preferably 15% by mass to 75% by mass, 20 mass%-60 mass% is especially preferable.

[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.

Alkali-soluble binder, developability, from the viewpoint of liquid viscosity, weight average molecular weight (measured in terms of polystyrene by GPC method) is preferably a polymer of 1,000 to 2 × 10 ^5, the weight of the 2000-1 × 10 ⁵ A coalescence is more preferable, and a polymer of 5000 to 5 × 10 ⁴ is particularly preferable.
These alkali-soluble binders may be used alone or in combination of two or more.

[Photopolymerization initiator]
The colored 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 the following general formula (i) is also suitable as an oxime type compound from a viewpoint of sensitivity, time stability, and coloring at the time of post-heating.

  In the general formula (i), 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, and Japanese Examined 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 particularly, 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% by mass to 30% by mass and more preferably 2% by mass to 20% by mass with respect to the total solid content in the colored 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.

[Photosensitizer]
At least one photosensitizer can also be added to the colored composition of the present invention.
Typical sensitizers used in the present invention include those disclosed in Crivello [JV Crivello, Adv. In Polymer Sci, 62, 1 (1984)]. Specific examples include pyrene, perylene, Acridine, thioxanthone, 2-chlorothioxanthone, benzoflavin, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, benzophenone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives and the like can be mentioned. The photosensitizer is preferably added in a proportion of 50% by mass to 200% by mass with respect to the photopolymerization initiator.

[Chain transfer agent]
At least one chain transfer agent may be added to the coloring composition 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% by mass to 15% by mass with respect to the total solid content of the coloring composition of the present invention, from the viewpoint of reducing the sensitivity variation. 1 mass%-10 mass% are more preferable, and 0.5 mass%-5 mass% are especially preferable.

[Polymerization inhibitor]
The coloring composition of the present invention may contain at least one polymerization inhibitor.
A polymerization inhibitor means hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation (or electron donation) to polymerization initiation species such as radicals generated in the colored composition by light or heat. A substance that plays a role of suppressing the initiation of polymerization unintentionally by deactivating the polymerization initiating 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 composition of the present invention is preferably 0.0001% by mass to 5% by mass and more preferably 0.001% by mass to 5% by mass with respect to the total weight of the ethylenically unsaturated compound. Preferably, 0.001 mass%-1 mass% are especially preferable.

[Organic solvent]
The coloring composition of the present invention can contain at least one organic solvent.
The organic solvent is basically not particularly limited as long as it can satisfy the solubility of each coexisting component and the coating property when it is a colored composition, and in particular, the solubility, coating property, and safety of the binder. Is preferably selected in consideration of

  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 (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate and the like (specifically, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Methyl ethoxypropionate, 3-ethoxy Ethyl propionate, etc.)), 2-oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (specifically, 2 -Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.)), 2-oxy-2-methylpropionic acid Methyl, ethyl 2-oxy-2-methylpropionate (specifically, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, 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 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 coloring composition of the present invention may contain at least one 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 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 number. 1 represents an alkyl group having 4 or less, 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% by mass to 80% by mass. Q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and n represents an integer of 1 to 10.

The L is preferably a branched alkylene group represented by the following formula (2). R ⁵ in the formula (2) 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. More preferred is an alkyl group of 3. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.

The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
These surfactants can be used individually by 1 type or in mixture of 2 or more types. 0.01 mass%-2.0 mass% are preferable in solid content, and, as for the addition amount of surfactant in the coloring composition of this invention, 0.02 mass%-1.0 mass% are especially preferable. Within this range, the coatability and the uniformity of the cured film are good.

[Adhesion improver]
The coloring composition of the present invention may contain at least one 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 composition of the present invention is preferably 0.1% by mass to 20% by mass and more preferably 0.2% by mass to 5% by mass with respect to the total solid content.

[Crosslinking agent]
The coloring composition of the present invention may contain at least one crosslinking agent.
A supplementary crosslinking agent may be used in the colored composition of the present invention to further increase the hardness of the colored cured film obtained by curing the colored 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]
In order to promote alkali solubility in the non-exposed region and further improve the developability of the coloring composition, at least one kind of development accelerator can be added.
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.

[Various additives]
In addition to the above-mentioned components, the coloring composition of the present invention is within the range not impairing the effects of the present invention, and further various additives such as fillers, polymer compounds other than those described above, ultraviolet absorbers, and antioxidants. An agent, an anti-aggregation agent and the like can be blended. Examples of these additives include those described in paragraphs [0155] to [0156] of JP-A No. 2004-295116.
In the coloring composition of this invention, the light stabilizer as described in Paragraph [0078] of Unexamined-Japanese-Patent No. 2004-295116 and the thermal-polymerization inhibitor as described in Paragraph [0081] of the same gazette can be contained.

Further, when promoting the alkali solubility in the non-exposed area and further improving the developability of the colored composition, an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less is added to the composition. Is preferably performed.
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, other carboxylic acids such as umbellic acid.

[Preparation Method of Colored Composition]
The coloring composition of the present invention is prepared by mixing the above-described components and optional components as necessary.
In preparing the colored composition, the components constituting the colored composition may be mixed together, 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 composition prepared as described above can preferably be used after being filtered using a filter having a pore size of about 0.01 μm to 3.0 μm.

  Since the colored composition of the present invention can form a colored cured film excellent in hue and contrast, such as a color filter used in a liquid crystal display (LCD) or a solid-state imaging device (for example, CCD, CMOS, etc.) It can be suitably used for forming colored pixels and for producing printing inks, inkjet inks, paints, and the like. In particular, it is suitable for use in forming colored pixels for liquid crystal display devices.

<Color filter and manufacturing method thereof>
The color filter of the present invention is formed using the colored composition of the present invention containing the dipyrromethene-based metal complex compound of the present invention and / or a tautomer thereof.
More specifically, the color filter of the present invention is configured by providing a substrate and a colored region containing the above-described dipyrromethene metal complex compound and / or a tautomer thereof on the substrate. It is. 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. Since the color filter of the present invention is formed by including a dipyrromethene-based metal complex compound having a predetermined structure, it is vivid and has high contrast when displaying an image, and is particularly suitable for a liquid crystal display device.

  The color filter of the present invention may be formed by any method as long as it can form a colored region (colored pattern) cured by containing a dipyrromethene metal complex compound. Preferably, it is produced using the coloring composition of the present invention.

The method for producing a color filter of the present invention comprises the steps of coating the above-described colored composition of the present invention on a support to form a colored layer, and exposing the developed colored layer in a pattern and developing it. And forming a colored region.
More specifically, the method for producing a color filter of the present invention includes a step (A) of applying the above-described colored composition on a support to form a colored layer (also referred to as a colored composition layer); The colored composition layer formed in the step (A) is exposed in a pattern (preferably through a mask), and the uncured portion of the coating film is developed and removed with a developer to form a colored region (colored pattern). Step (B) is provided. By passing through these steps, a colored pattern composed of pixels of each color (3 colors or 4 colors) is formed, and a color filter can be obtained. 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.
By such a method, a color filter used for a liquid crystal display element or a solid-state imaging element can be manufactured with low process difficulty, high quality, and low cost.
Hereinafter, the manufacturing method of the color filter of this invention is demonstrated in detail.

-Process (A)-
In the method for producing a color filter of the present invention, first, the above-described colored composition of the present invention is applied onto a support by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, and inkjet. Then, a colored composition layer is formed, and then the colored 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 liquid crystal 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.
Moreover, the thickness of the colored composition layer formed of the colored composition is appropriately selected according to the purpose. In the color filter for liquid crystal 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 coloring 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 coloring 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, development is performed with a developer on the colored composition layer after exposure. Thereby, a colored pattern can be formed. As long as the developing solution dissolves the uncured portion of the colored 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, 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, post-exposure by ultraviolet irradiation can be performed on a colored pattern (pixel) formed using a colored 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 the monochromatic coloring composition layer are completed (for each color), or the desired number of colors After all the colored composition layers have been formed, exposed and developed, the step (C) and / or the step (D) may be performed collectively.

  Since the color filter obtained by the method for producing a color filter of the present invention (the color filter of the present invention) uses the coloring composition of the present invention, it is excellent in hue and contrast. When used in a liquid crystal display device, an image having excellent spectral characteristics and contrast can be displayed while achieving a good hue.

[Image display device, solid-state image sensor]
The image display device and the solid-state imaging device of the present invention include the color filter of the present invention described above or the color filter created by the method of manufacturing the color filter of the present invention described above. More specifically, for example, an alignment film is formed on the inner surface side of the color filter, is opposed to the electrode substrate, and a gap portion is filled with liquid crystal and sealed to obtain a panel that is a liquid crystal display element. For example, the solid-state image sensor of this invention is obtained by forming a color filter on a light receiving element.
Examples of the image display device include a plasma display device, an EL display device, a CRT display device, and a liquid crystal display device.

For the definition of the image display device and details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Device (Junaki Ibuki, Sangyo Tosho) Issued in 1989). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”.
The image display device to which the color filter of the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next-generation liquid crystal display technology”.

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

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

  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 dipyrromethene-based metal complex compound According to the following reaction scheme A, the exemplified compounds A-11 and A-15 described above of the dipyrromethene-based metal complex compound of the present invention were synthesized.

-Synthesis of Intermediate 1-
Intermediate 1 was synthesized by the method described in US Patent Application Publication No. 2008/0076044.
Intermediate 2 to Intermediate 6, Exemplified Compounds A-11 and A-15 were synthesized as shown below.

-Synthesis of Intermediate 2-
600 ml of acetonitrile was added to 205.3 g (0.5 mol) of Intermediate 1 obtained by the method described in US Patent Application Publication No. 2008/0076044, and the mixture was stirred under ice cooling. To this solution, 66.3 g (0.55 mol) of pivaloyl chloride was added dropwise. Thereafter, 47.5 g (0.6 mol) of pyridine was added dropwise, and the mixture was stirred for 1 hour under ice cooling and 2 hours at room temperature. After completion of the reaction, the precipitated solid was filtered, and the filtrate was washed with acetonitrile and dried. In this way, 238.5 g of intermediate 2 was obtained (yield: 96%).
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 11.02 (s, 1H), 10.81 (s, 1H), 7.37-7.26 (m, 5H), 6.28. (D, 1H), 5.87 (s, 1H), 1.36 (s, 9H), 1.26 to 1.15 (m, 3H), 1.04 to 0.97 (m, 2H) 0 .83 (s, 18H), 0.70 (d, 3H), 0.63 to I0.46 (m, 2H).

-Synthesis of Intermediate 3-
In 625 ml of acetonitrile, 123.7 g (0.25 mol) of Intermediate 2 and 74.1 g (0.5 mol) of triethyl orthoformate were added and stirred at room temperature. To this solution, 85.5 g (0.75 mol) of trifluoroacetic acid was added dropwise and stirred at room temperature for 2 hours. After completion of the reaction, the reaction solution was poured into 5000 ml of water, then 107.5 g of sodium bicarbonate was added, and the mixture was stirred at room temperature for 5 hours. Thereafter, the precipitated solid was filtered, the filtrate was washed with water, acetonitrile, and ethyl acetate, and the obtained solid was dried. In this way, 100 g (80%) of Intermediate 3 was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 10.99 (s, 2H), 7.29 to 7.12 (m, 10H), 6.06 (d, 1H), 5.87. (S, 2H), 1.42 (s, 18H), 1.22-1.12 (m, 6H), 1.00 to 0.95 (m, 4H) 0.80 (s, 36H), 0 .64 (d, 6H), 0.44 to I0.31 (m, 4H).

-Synthesis of Intermediate 4-
To 50 ml of water and 40 ml of methanol, 14.9 g (0.066 mol) of 4-bromophthalimide and 4.56 g (0.033 mol) of potassium carbonate were added and stirred at room temperature. A solution prepared by dissolving 4.0 g (0.014 mol) of zinc sulfate heptahydrate in 20 ml of water was added to this solution, and the mixture was stirred at room temperature for 6 hours. After completion of the stirring, the obtained precipitate was filtered, and the residue was washed with water and methanol and dried. In this way, 10.1 g (95%) of intermediate 6 was obtained.
The details of 1H-NMR (CDCl3) were δ: 8.01 (m, 2H), 7.92-7.89 (m, 2H), 7.76-7.29 (m, 2H). It was.

-Synthesis of Intermediate 5-
In 40 ml of dimethyl sulfoxide, 9.6 g (0.05 mol) of nitrophthalimide and 8.3 g (0.06 mol) of potassium carbonate were added and stirred at room temperature. To this solution, 11.1 g (0.055 mol) of n-dodecyl mercaptan was added and stirred at room temperature for 4 hours. After completion of the stirring, the reaction solution was poured into 600 ml of water. The resulting precipitate was filtered, and the filtrate was washed with acetonitrile and dried. In this way, 11.6 g (67%) of Intermediate 5 was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 8.50 (s, 1H), 7.72 to 7.65 (m, 2H), 7.55 to 7.52 (m, 1H) 3.06 to 3.01 (t, 3H), 1.74 to 1.61 (m, 2H), 1.49 to 1.41 (m, 2H), 1.27 (m, 16H), 0 90-0.86 (t, 3H).

-Synthesis of Intermediate 6-
10.7 g (0.03 mol) of Intermediate 5 and 2.1 g (0.015 mol) of potassium carbonate were added to 30 ml of water and 30 ml of methanol, and the mixture was stirred at room temperature. A solution prepared by dissolving 4.0 g (0.014 mol) of zinc sulfate heptahydrate in 20 ml of water was added to this solution, and the mixture was stirred at room temperature for 6 hours. After completion of the stirring, the obtained precipitate was filtered, and the residue was washed with water and methanol and dried. In this way, 10.1 g (95%) of intermediate 6 was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 7.74 to 7.67 (m, 4H), 7.57 to 7.53 (m, 2H), 3.07 to 3.03 ( t, 6H), 1.76 to 1.56 (m, 4H), 1.52 to 1.41 (m, 4H), 1.27 (m, 32H), 0.91 to 0.87 (t, 6H).

(Synthesis of Exemplary Compound A-11)
5 g (0.05 mol) of Intermediate 3 and 3.1 g (0.06 mol) of Intermediate 4 were added to 50 ml of tetrahydrofuran, and the mixture was stirred at 50 ° C. for 48 hours. After completion of the reaction, the precipitated solid was filtered, and the filtrate was concentrated under reduced pressure. 200 ml of methanol was added to the obtained solid, and the mixture was stirred at 60 ° C. for 1 hour, filtered, and washed again with methanol. In this way, 5.7 g (88%) of Exemplary Compound A-11 was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 11.52 (s, 2H), 7.76-7.75 (m, 1H), 7.63-7.60 (m, 1H) 7.49-7.47 (m, 1H), 7.28-7.11 (m, 10H), 6.30 (s, 1H), 5.87 (s, 2H), 1.41 (s) 9H), 1.25 to 0.78 (m, 10H), 0.88 (s, 18H), 0.72 (s, 18H), 0.63 to 0.61 (d, 6H),. It was 54-0.41 (m, 2H), 0.29-0.17 (m, 2H).

Moreover, about the obtained compound, the molar absorption coefficient ((epsilon)) in an ethyl acetate solution was measured using spectrophotometer UV-1800PC (made by Shimadzu Corporation), and also the light absorbency in the maximum absorption wavelength ((lambda) max). Absorbance at 450 nm was evaluated by normalizing (Abs) to 1.0. Illustrative compound A-11 had a maximum absorption wavelength λmax of 550 nm and a molar extinction coefficient (ε) of 126,000.
The results of absorbance (Abs value), maximum absorption wavelength λmax, and molar extinction coefficient (ε) are shown in Table 1 below.

(Synthesis of Exemplary Compound A-15)
5 g (0.05 mol) of Intermediate 3 and 4.6 g (0.06 mol) of Intermediate 6 were added to 50 ml of tetrahydrofuran, and the mixture was stirred at 50 ° C. for 48 hours. After completion of the reaction, the precipitated solid was filtered, and the filtrate was concentrated under reduced pressure. 200 ml of methanol was added to the obtained solid, and the mixture was stirred at 60 ° C. for 1 hour, filtered, and washed again with methanol. In this way, 5.2 g (74%) of Exemplary Compound A-15 was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 11.51 (s, 2H), 7.56 to 7.48 (m, 3H), 7.36 to 7.10 (m, 10H) 6.30 (s, 1H), 5.87 (s, 2H), 2.98 to 2.93 (t, 2H), 1.41 (s, 9H), 1.75 to 0.78 (m) 14H), 1.26 to 1.25 (m, 16H), 0.87 (s, 18H), 0.71 (s, 18H), 0.63 to 0.61 (d, 6H), 0. 54 to 0.42 (m, 2H), 0.28 to 0.16 (m, 2H).

Further, when the maximum absorption wavelength λmax and the molar absorption coefficient (ε) were measured in the same manner as described above, the maximum absorption wavelength λmax of Exemplified Compound A-15 was 549 nm, and the molar absorption coefficient (ε) was 123,000. It was.
The results of absorbance (Abs value), maximum absorption wavelength λmax, and molar extinction coefficient (ε) are shown in Table 1 below.

[Example 2]
In addition to synthesizing exemplary compounds (dipyrromethene-based metal complex compounds or tautomers thereof) shown in Table 1 below by a method similar to the reaction scheme in Example 1, they were identified by the same method as in Example 1, and The maximum absorption wavelength λmax and the molar extinction coefficient (ε) were measured. The measurement results are shown in Table 1 below.

  As shown in Table 1, the compound of the present invention has a high molar extinction coefficient (ε), a low absorbance (Abs value) at 450 nm, excellent color separation, and is suitable for color filters. It was.

Hereinafter, specific examples of producing a colored composition and a color filter are shown.
Example 3
First, each component used for preparation of a coloring 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) photopolymerizable compound: Kayalad DPHA (manufactured by Nippon Kayaku Co., Ltd .; mixture of dipentaerythritol pentaacrylate and 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) photopolymerization initiation assistant: 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 (large (Made by Nippon Ink Chemical Co., Ltd.)

-B1. Preparation of coloring composition (coating solution)
The component in the following composition was mixed and the coloring composition 1 was prepared.
<Composition>
-Exemplified Compound A-1 6.9 parts (dipyrromethene metal complex compound)
· (S-1) · · · 43.0 parts · (T-1) · · · 103.4 parts · (U-1) · · · 212.2 parts (solid content converted value: 84) .9)
· (V-1) · · · 21.2 parts · (W-1) · · · 3.5 parts · · (X-1) · · · 71.9 parts · (X -2) ... 3.6 parts · (Y-1) ··· 0.06 parts

-B2. Preparation and evaluation of color filter by coloring composition
B1. The colored composition (color resist solution) obtained in (1) was applied onto a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) so that the x value serving as an index of color density was 0.650. It was dried in an oven at 60 ° 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- The sample was covered with a 1% aqueous solution of No. 1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) and allowed to stand for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been exposed and developed as described above is heated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored pattern (colored resin film) for the color filter on the glass substrate, 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. Light resistance>
The color filter 1 was irradiated with a xenon lamp at 50,000 lux for 20 hours (equivalent to 1 million lux · h), and then the ΔEab value of the color difference before and after the light resistance test was measured. A smaller ΔEab value indicates better light resistance.
-Criteria-
5: ΔEab value <3
4: 3 ≦ ΔEab value <5
3: 5 ≦ ΔEab value <10
2: 10 ≦ ΔEab value <20
1: 20 ≦ ΔEab value

<2. Luminance (Y value)>
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.

<3. 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

[Examples 4 to 17]
In the preparation of the colored composition 1 of Example 3, Exemplified Compound A-1 was replaced with the aforementioned Exemplified Compound (dipyrromethene metal complex compound) shown in Table 2, respectively, and the Exemplified Compound and S-1 so that the colors matched. Coloring compositions 2 to 15 were prepared in the same manner as in Example 3 except that the ratio was adjusted, and then color filters 2 to 15 were prepared.

Example 18
A color filter was prepared in the same manner as in Example 3 except that the colored composition 16 was prepared by mixing the components in the following composition in Example 3, and the colored composition 16 was used instead of the colored composition 1. 16 was obtained.
-Composition-
-Exemplified Compound A-1 ... 6.9 parts-(S-1) ... 43.0 parts-(T-1) ... 103.4 parts-(U- 1) ... 212.2 parts (solid content conversion value: 84.9 parts)
· (V-2) · · · 21.2 parts · (W-1) · · · 3.5 parts · · (X-1) · · · 71.9 parts · (X -2) ... 3.6 parts · (Y-1) ··· 0.06 parts

[Examples 19 to 21]
In the preparation of the coloring composition 16 of Example 18, Exemplified Compound A-1 was replaced with the aforementioned Exemplified Compound (dipyrromethene-based metal complex compound) shown in Table 2, and the Exemplified Compound and S-1 Coloring compositions 17 to 19 were prepared in the same manner as in Example 18 except that the ratio was replaced, and then color filters 17 to 19 were obtained.

[Example 22]
A color filter was prepared in the same manner as in Example 3 except that the colored composition 20 was prepared by mixing the components in the following composition in Example 3, and the colored composition 20 was used instead of the colored composition 1. 20 was obtained.
-Composition-
-Exemplified Compound A-1-4.7 parts-(S-1)-... 42.1 parts-Compound (5) below-2.3 parts-(T -1) ... 103.4 parts · (U-1) ... 212.2 parts (solid content conversion value: 84.9 parts)
· (V-2) · · · 21.2 parts · (W-1) · · · 3.5 parts · · (X-1) · · · 71.9 parts · (X -2) ... 3.6 parts · (Y-1) ··· 0.06 parts

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

Example 23
In the preparation of the coloring composition 20 of Example 22, the coloring composition 21 was prepared by replacing the exemplary compound A-1 with A-11, and the coloring composition 21 was used instead of the coloring composition 20, except that the coloring composition 21 was used. In the same manner as in Example 22, a color filter 21 was obtained.

[Comparative Examples 1 to 4]
In the preparation of the colored composition 1 of Example 3, Exemplified Compound A-1 was replaced with Comparative Compounds 1 to 4 shown in Table 2, respectively, and the ratio of the Comparative Compound and S-1 was changed so that the colors matched. Similarly, colored compositions 101 to 104 were prepared. Furthermore, it replaced with the coloring composition 1 and obtained the color filters 101-104 like Example 3 except having used the coloring compositions 101-104.
The details of comparative compounds 1 to 4 are as follows.

Comparative Compound 1 ... C. I. Acid Violet 17
Comparative Compound 2 ... C. I. Acid Violet 49

  As shown in Table 2, the color filters 1 to 21 prepared using the exemplified compounds have very high light resistance and luminance as compared with the comparative examples (Comparative Examples 1 and 2) using conventionally known compounds. (Y value) and a contrast. Furthermore, even when compared with conventionally known dipyrromethene-based metal complex compounds (Comparative Examples 3 to 4), the color filters 1 to 21 produced using the exemplified compounds are highly evaluated, and particularly excellent in contrast. I found out.

Claims (9)

A dipyrromethene metal complex compound represented by the following general formula (I) or a tautomer thereof.

[In General Formula (I), R ² , R ³ , R ⁴ and 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. Ma represents a metal or a metal compound, and X ³ and X ⁴ each independently represent NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group) A nitrogen atom, an oxygen atom, or a sulfur atom. Y ¹ and Y ² each independently represent NRb (Rb represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, or Represents a carbon atom. R ⁸ and R ⁹ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. R ⁸ and Y ¹ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. A ring may be formed. X ⁵ represents -L- (D) n, L represents a single bond or an n + 1 valent group that can be bonded to Ma, and D represents a bromine atom, an iodine atom, -S-R or -Se- R (wherein R represents a hydrogen atom or a monovalent substituent). n is 1-20. When n is 2 or more, D may be the same or different. a represents 1 or 2. When a is 2, X ⁵ may be the same or different. ] The coloring composition containing the dipyrromethene type metal complex compound or its tautomer represented by the following general formula (I).

[In General Formula (I), R ² , R ³ , R ⁴ and 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. Ma represents a metal or a metal compound, and X ³ and X ⁴ each independently represent NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group) A nitrogen atom, an oxygen atom, or a sulfur atom. Y ¹ and Y ² each independently represent NRb (Rb represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, or Represents a carbon atom. R ⁸ and R ⁹ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. R ⁸ and Y ¹ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. A ring may be formed. X ⁵ represents -L- (D) n, L represents a single bond or an n + 1 valent group that can be bonded to Ma, and D represents a bromine atom, an iodine atom, -S-R or -Se- R (wherein R represents a hydrogen atom or a monovalent substituent). n is 1-20. When n is 2 or more, D may be the same or different. a represents 1 or 2. When a is 2, X ⁵ may be the same or different. ]   Furthermore, the coloring composition of Claim 2 containing a polymeric compound and a photoinitiator.   Furthermore, the coloring composition of Claim 2 or Claim 3 containing an anthraquinone compound. The colored composition according to claim 4, wherein the anthraquinone compound is a diaminoanthraquinone compound represented by the following general formula (X).

[In the general formula (X), R ^21a and R ^22a each independently represents an alkyl group or an aryl group. ]   The color filter formed using the coloring composition of any one of Claims 3-5. Applying the colored composition according to any one of claims 3 to 5 on a support to form a colored layer;
Exposing the formed colored layer in a pattern and developing to form a colored region; and
The manufacturing method of the color filter which has this.   An image display device comprising the color filter according to claim 6 or a color filter produced by the method for producing a color filter according to claim 7.   A solid-state imaging device comprising a color filter according to claim 6 or a color filter produced by the method for producing a color filter according to claim 7.