JP5827842B2 - Curable coloring composition and color filter - Google Patents

Description

  The present invention relates to a curable coloring composition and a color filter using the curable coloring composition. The present invention also relates to a method for manufacturing a color filter. Furthermore, the present invention relates to a liquid crystal display device using a color filter and a solid-state imaging device. Furthermore, it is related with the novel compound effective for a color filter.

  Conventionally, a color filter has a curable coloring composition by containing 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 as necessary. It is manufactured by forming a colored pattern by using a photolithography method, an ink jet 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 image sensors (solid-state imaging devices) are required to further improve color characteristics such as reduction of color unevenness and improvement of color resolution.

  However, in the conventional pigment dispersion system, problems such as the occurrence of scattering due to coarse particles of the pigment and the increase in viscosity due to poor dispersion stability are likely to occur, and it is often difficult to further improve the contrast and brightness.

  Therefore, conventionally, as a coloring material, use of not only a pigment but also a dye has been studied (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.

  As examples of dyes, compounds having a wide variety of dye bases such as arylmethane dyes, dipyrromethene dyes, pyrimidineazo dyes, pyrazole azo dyes, xanthene dyes are known (for example, Patent Documents 2 to 2). 4). As for dipyrromethene dyes, it is known that heat resistance and light resistance are improved by forming a metal complex, and an application example to a blue color filter using this technology is known (for example, patents). References 5-8).

JP-A-6-75375 JP 2008-292970 A JP 2007-039478 A Japanese Patent No. 3387541 JP 2008-292970 A JP 2009-31713 A JP 2010-13639 A JP 2010-18788 A

However, the conventionally provided dipyrromethene metal complex dye has absorption in the violet region, and when it is assumed to be used as a green color filter, it has a short wavelength as a cyan dye, and its utilization is greatly limited. There was a problem.
The present invention has been made in view of such problems of the prior art, and is capable of transmitting light in the magenta region and absorbing light in the cyan region, a color filter, and a method for producing the same. Another object of the present invention is to provide a liquid crystal display device and a solid-state imaging device in which the color of a display image is vivid and exhibits high contrast.

As a result of intensive studies, the present inventors have determined that if a metal complex having a skeleton shown below is used, a curable coloring composition having a preferable absorption wavelength characteristic of transmitting light in the magenta region and absorbing light in the cyan region. Has been found to provide the present invention. The metal complex having the skeleton shown below is preferable because the conventionally known pyromethene dye has a tetracoordinate structure of nitrogen 2-coordinate and oxygen 2-coordinate, whereas in the present invention, a central metal such as zinc is used rather than an oxygen atom. High rigidity is expressed by taking a nitrogen four-coordinate structure with high affinity for and forming a ring structure in the A ¹ and A ² parts described later. As a result, this skeleton has a high coordinating power, and gives a dye compound having more excellent hue and heat resistance.

Specifically, the above problem has been solved by the following <1>, preferably by <2> to <20>.
<1> A curable coloring composition comprising a metal complex compound in which a compound represented by the following formula (1) is coordinated to a metal atom or a metal compound.
Formula (1)
(In formula (1), R ¹ , R ² , R ³ , and R ⁴ each represent a hydrogen atom or a substituent. Y ¹ and Y ² are each an oxygen atom, a sulfur atom, or —NH—. A ¹ and A ² each represent a nitrogen-containing ring.)
<2> A curable coloring composition comprising a metal complex compound in which a compound represented by the following formula (2) is coordinated to a metal atom or a metal compound.
Formula (2)
(In Formula (2), R ¹ , R ² , R ³ , and R ⁴ each represent a hydrogen atom or a substituent. X ¹ and X ² represent an oxygen atom, a sulfur atom, or a nitrogen atom, respectively. A ³ and A ⁴ each represent a nitrogen-containing aromatic ring.)
<3> A curable coloring composition containing a metal complex compound represented by the following formula (3).
Formula (3)
(In Formula (3), R ¹ , R ² , R ³ , and R ⁴ each represent a hydrogen atom or a substituent. A ⁵ and A ⁶ each represent a nitrogen-containing aromatic ring. Represents a metal atom or a metal compound, Z ¹ represents a group capable of binding to Ma, and a represents 0, 1 or 2.)
<4> The curable coloring including any one of <1> to <3>, wherein each of A ^{1 to} A ⁶ has a thiadiazole structure, an oxadiazole structure, a triazole structure, or a pyridazine structure. Composition.
<5> Any one of <1> to <4>, wherein R ¹ and R ⁴ are each an aryl group, a heterocyclic group, a cyano group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, or an arylsulfonyl group The curable coloring composition according to item 1.
<6> Any one of <1> to <5>, wherein R ² and R ³ are each an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxycarbonyl group, a carbamoyl group, or a halogen atom. The curable coloring composition according to item.
<7> The curable coloring composition according to any one of <1> to <6>, further comprising a yellow pigment.
<8> The curable coloring composition according to any one of <1> to <7>, further containing a green pigment.
<9> The curable coloring composition according to any one of <1> to <8>, further comprising a monomer and a polymerization initiator.
<10> A color filter having a colored layer using the curable coloring composition according to any one of <1> to <9>.
<11><1> to <9> The curable coloring composition according to any one of <9> is applied on a support to form a colored layer, and the formed colored layer is exposed in a pattern. The manufacturing method of the color filter which has a process to do.
<12> A liquid crystal display device having the color filter according to <10> or the color filter manufactured by the method for manufacturing a color filter according to <11>.
<13> A solid-state imaging device having the color filter according to <10> or the color filter manufactured by the method for manufacturing a color filter according to <11>.
<14> A metal complex compound in which a compound represented by the following formula (1) is coordinated to a metal atom or a metal compound.
Formula (1)
(In formula (1), R ¹ , R ² , R ³ , and R ⁴ each represent a hydrogen atom or a substituent. Y ¹ and Y ² are each an oxygen atom, a sulfur atom, or —NH—. A ¹ and A ² each represent a nitrogen-containing ring.)
<15> A metal complex compound in which a compound represented by the following formula (2) is coordinated to a metal atom or a metal compound.
Formula (2)
(In Formula (2), R ¹ , R ² , R ³ , and R ⁴ each represent a hydrogen atom or a substituent. X ¹ and X ² represent an oxygen atom, a sulfur atom, or a nitrogen atom, respectively. A ³ and A ⁴ each represent a nitrogen-containing aromatic ring.)
<16> A metal complex compound represented by the following formula (3).
Formula (3)
(In Formula (3), R ¹ , R ² , R ³ , and R ⁴ each represent a hydrogen atom or a substituent. A ⁵ and A ⁶ each represent a nitrogen-containing aromatic ring. Represents a metal atom or a metal compound, Z ¹ represents a group capable of binding to Ma, and a represents 0, 1 or 2.)
<17> The metal complex compound according to any one of <14> to <16>, wherein each of A ^{1 to} A ⁶ has a thiadiazole structure, an oxadiazole structure, a triazole structure, or a pyridazine structure.
<18> Any one of <14> to <17>, wherein R ¹ and R ⁴ are each an aryl group, a heterocyclic group, a cyano group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, or an arylsulfonyl group 2. The metal complex compound according to item 1.
<19> Any one of <14> to <18>, wherein R ² and R ³ are each an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxycarbonyl group, a carbamoyl group, or a halogen atom. The metal complex compound according to Item.
<20> R ¹ and R ⁴ are each selected from the following Rx, and the A ^{1 to} A ⁶ are each selected from the following Ry: <14> to <16> and <19> The metal complex compound described in 1.
(Rx)
(In the above, it is connected at the part of *)
(Ry)
(In the above, the nitrogen atom which is connected to the carbon atom constituting the ring of A ^{1 to} A ⁶ at the portion of *, and the nitrogen atom adjacent to * is represented in the ring of A ^{1 to} A ⁶ Corresponding to.)

  The curable coloring composition of the present invention is heat resistant and has preferable absorption characteristics that transmits light in the magenta region and absorbs light in the cyan region. In addition, by adding a yellow pigment compound, a curable coloring composition having a particularly high effect as a green application can be provided. According to the present invention, a curable coloring composition having high color purity, a high absorption coefficient in a thin layer, excellent fastness (especially heat resistance and light resistance) and voltage holding ratio, a color filter, and a production method thereof Can be provided. Further, according to the present invention, it is possible to provide a liquid crystal display device and a solid-state imaging device in which the display image is vividly colored and exhibits high contrast. Furthermore, if the present invention is used, it is possible to provide a liquid crystal display device and a solid-state imaging device in which the display image is vividly colored and exhibits high contrast.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
The coloring compound of the present invention can be used as a coloring component of the curable coloring composition.

Metal Complex Compound of the Present Invention The metal complex compound of the present invention is a metal complex in which a compound represented by the following formula (1) is coordinated to a metal atom or a metal compound. Examples of the metal atom include Zn, Mg, Sc, Fe, Al, Cr, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, or VO, and preferably Zn, Mg , Sc, Fe, Al, Mn, Cu, Ni, Co, TiO, or VO, and more preferably Zn, Cu, or Co. Examples of the metal compound include Zn, Cu, Ni, and Fe, and Zn and Cu are preferable.
Formula (1)
(In formula (1), R ¹ , R ² , R ³ , and R ⁴ each represent a hydrogen atom or a substituent. Y ¹ and Y ² are each an oxygen atom, a sulfur atom, or —NH—. A ¹ and A ² each represent a nitrogen-containing ring.)
In the present invention, by having such a skeleton, a conventionally known pyromethene dye has a tetracoordinate structure of nitrogen 2-coordinate and oxygen 2-coordinate, whereas in the present invention, oxygen atoms are changed to a central metal such as zinc. It becomes a nitrogen four-coordinate structure with a high affinity, and the rigidity is increased by expressing a higher affinity for the central metal. As a result, it is possible to provide an azapyromethene dye having a good sash. Therefore, the effect of the present invention can be achieved regardless of the substituents of R ^{1 to} R ⁴ .

The compound represented by the formula (1) is preferably represented by the following formula (2), more preferably represented by the following formula (3). By adopting the compound represented by the formula (3), the heat resistance tends to be improved.
Formula (2)
(In Formula (2), R ¹ , R ² , R ³ , and R ⁴ each represent a hydrogen atom or a substituent. X ¹ and X ² represent an oxygen atom, a sulfur atom, or a nitrogen atom, respectively. A ³ and A ⁴ each represent a nitrogen-containing aromatic ring.)
By making X ¹ and X ^{2 an} oxygen atom, a sulfur atom, or a nitrogen atom, protons do not exist at such sites, and a complex that is closer to a flat surface is obtained, and the effects of the present invention are more effectively exhibited.

Formula (3)
(In Formula (3), R ¹ , R ² , R ³ , and R ⁴ each represent a hydrogen atom or a substituent. A ⁵ and A ⁶ each represent a nitrogen-containing aromatic ring. Represents a metal atom or a metal compound, Z ¹ represents a group capable of binding to Ma, and a represents 0, 1 or 2.)

The substituents represented by R ^{1 to} R ⁴ in the above formulas (1) to (3) will be described. The substituents represented by R ^{1 to} R ⁴ in the above formulas (1) to (3) have the same meaning, and the preferred range is also the same.
The substituents represented by R ^{1 to} R ⁴ are, for example, a halogen atom (for example, fluorine, chlorine, bromine), an alkyl group (preferably a straight chain having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms). A branched or cyclic alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, A dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group), alkenyl group (preferably having 2 to 48 carbon atoms, more preferably having 2 to 18 carbon atoms) , For example, vinyl group, allyl group, 3-buten-1-yl group), aryl group (preferably having 6 to 48 carbon atoms, more preferably carbon An aryl group of 6 to 24, for example, a phenyl group, a naphthyl group), a heterocyclic group (preferably a heterocyclic group of 1 to 32 carbon atoms, more preferably a heterocyclic group of 1 to 18 carbon atoms, for example, 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 A silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, such as a trimethylsilyl group, a triethylsilyl group, a tributylsilyl group, a tert-butyldimethylsilyl group, a tert-hexyldimethylsilyl group), a hydroxyl group, A cyano group, a nitro group, an alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably an alkoxy group having 1 to 24 carbon atoms). Methoxy group, ethoxy group, 1-butoxy group, 2-butoxy group, isopropoxy group, tert-butoxy group, dodecyloxy group, cycloalkyloxy group, for example, cyclopentyloxy group, cyclohexyloxy group), aryl An oxy group (preferably an aryloxy group having 6 to 48 carbon atoms, more preferably an aryloxy group having 6 to 24 carbon atoms, such as a phenoxy group or 1-naphthoxy group), a heterocyclic oxy group (preferably having 1 to 32 carbon atoms, or more). Preferably it is a C1-C18 heterocyclic oxy group, for example, 1-phenyltetrazol-5-oxy group, 2-tetrahydropyranyloxy group, silyloxy group (preferably C1-C32, more preferably carbon). A silyloxy group having a number of 1 to 18, such as trimethylsilyloxy group, tert-butyldimethyl; Rusilyloxy group, diphenylmethylsilyloxy group), acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a dodecanoyloxy group. ), An alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as ethoxycarbonyloxy group, tert-butoxycarbonyloxy group, cycloalkyloxycarbonyloxy group) And, for example, a cyclohexyloxycarbonyloxy group), an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, for example, phenoxycarboni An oxy group), a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N -Phenylcarbamoyloxy group, N-ethyl-N-phenylcarbamoyloxy group), sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, N, N-diethylsulfamoyloxy group, N-propylsulfamoyloxy group), an alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, , Methylsulfonyloxy group, hexadecylsulfonyloxy group, cyclohexyls Sulfonyloxy group),

An arylsulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, such as a phenylsulfonyloxy group), an acyl group (preferably having 1 to 48 carbon atoms, more preferably C1-C24 acyl group, for example, formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexanoyl group), alkoxycarbonyl group (preferably C2-C48, more preferably An alkoxycarbonyl group having 2 to 24 carbon atoms, for example, a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group), Aryloxycarbonyl group (preferred Or an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as a phenoxycarbonyl group, and a carbamoyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms). Carbamoyl group such as carbamoyl group, N, N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methyl N-phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group), amino group (preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as amino, methylamino group, N, N -Dibutylamino group, tetradecylami group, 2-ethylhexylamino group, cyclohexyl Amino group), anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as an anilino group and an N-methylanilino group), a heterocyclic amino group (preferably having 1 to 32 carbon atoms, More preferably, it is a heterocyclic amino group having 1-18, for example, 4-pyridylamino group), a carbonamido group (preferably a carbonamide group having 2 to 48 carbon atoms, more preferably 2-24, for example, an acetamide group, Benzamide group, tetradecanamide group, pivaloylamide group, cyclohexaneamide group), ureido group (preferably ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, ureido group, N, N-dimethylureido Group, N-phenylureido group), imide group (preferably having 36 or less carbon atoms, more preferably having 24 or less carbon atoms). In the lower imide group, for example, N-succinimide group, N-phthalimide group), alkoxycarbonylamino group (preferably C2-48, more preferably C2-C24 alkoxycarbonylamino group, for example, methoxy Carbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group), aryloxycarbonylamino group (preferably having 7 to 32 carbon atoms, more preferably having 7 to 32 carbon atoms) 24 aryloxycarbonylamino group, for example, phenoxycarbonylamino group), sulfonamido group (preferably 1-48 carbon atoms, more preferably 1-24 carbon sulfonamido group, for example, methanesulfonamido group, butane A sulfonamide group, a benzenesulfonamide group, a hexadecanesulfonamide group, a cyclohexanesulfonamide group), a sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, N, N-dipropylsulfamoylamino group, N-ethyl-N-dodecylsulfamoylamino group), azo group (preferably having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, For example, 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, methylthio group, ethylthio group, octylthio group, cyclohexylthio group), arylthio group (preferably having 6 to 48 carbon atoms). More preferably, it is 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 thio group having 1 to 18 carbon atoms, 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group), alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, Dodecanesulfinyl group), arylsulfinyl group (preferably having 6 to 32 carbon atoms, more preferably An arylsulfinyl group having 6 to 24 prime atoms, such as a phenylsulfinyl group, an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably an alkylsulfonyl group having 1 to 24 carbon atoms, such as a methylsulfonyl group, ethyl Sulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropylsulfonyl group, 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, octylsulfonyl group, cyclohexylsulfonyl group), arylsulfonyl group (preferably having 6 to 48 carbon atoms, more preferably An arylsulfonyl group having 6 to 24 carbon atoms, for example, a phenylsulfonyl group, 1-naphthylsulfonyl v), a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, Rufamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl group), sulfo group, phosphonyl group (Preferably a phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as phenoxyphosphonyl group, octyloxyphosphonyl group, phenylphosphonyl group), phosphinoylamino group (preferably carbon A phosphinoylamino group having 1 to 32, more preferably 1 to 24 carbon atoms, such as a diethoxyphosphinoylamino group or a dioctyloxyphosphinoylamino group).

In the case where the substituents of R ^{1 to} R ⁴ in the formula (1) are further substitutable groups, the substituents described for R ^{1 to} R ⁴ may be included, and two or more substituents In the case of having these, the substituents may be the same or different.

R ¹ and R ⁴ are each preferably an aryl group, a heterocyclic group, a cyano group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, or an arylsulfonyl group, and more preferably a heterocyclic group, a cyano group, An alkoxycarbonyl group and a carbamoyl group.
As the heterocyclic ring, those having a nitrogen atom having an unshared electron pair at the position adjacent to the site bonded to the pyrrole ring are preferred. Specifically, a thiazole structure, an oxazole structure, an imidazole structure, a thiadiazole structure, an oxadiazole structure, Examples thereof include a heterocyclic group having a triazole structure, a pyridine structure, a pyrazine structure, a pyrimidine structure, or a triazine structure.

R ¹ and R ⁴ are more preferably any of the following groups, respectively. Here, it is a site | part which * couple | bonds.
R ¹ and R ⁴ are each particularly preferably any one of the following groups.

R ² and R ³ are each preferably an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxycarbonyl group, a carbamoyl group, or a halogen atom, and more preferably an alkyl group, an aryl group, or a heterocyclic group. is there.
Examples of the heterocyclic ring include heterocyclic groups having a thiazole structure, an oxazole structure, an imidazole structure, a thiadiazole structure, an oxadiazole structure, a triazole structure, a pyridine structure, a pyrazine structure, a pyrimidine structure, and a triazine structure.

In the formulas (1) to (3), R ¹ and R ² , R ³ and R ⁴ are bonded to each other to form a 5-membered, 6-membered, or 7-membered saturated or unsaturated ring. May be. When the 5-membered, 6-membered, or 7-membered ring formed is a group that can be further substituted, it may be substituted with the substituents described in the above R ^{1 to} R ⁴ . When substituted with a substituent, these substituents may be the same or different.

In the formula (3), between the Ma and Z ¹ is preferably at least one is a coordinate bond.
In the formula (3), a is an integer of 2 to 4, and a is preferably 1.
In the formula (3), Ma is preferably Zn, Mg, Sc, Fe, Al, Cr, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, or VO, more preferably Zn, Mg, Sc, Fe, Al, Mn, Cu, Ni, Co, TiO, or VO, particularly preferably Zn, Cu, or Co.

In the formula (3), Z ¹ represents a group capable of ionic bonding or covalent bonding with Ma. Z ¹ includes tetrafluoroboron ion, hexafluorophosphorus ion, hexafluoroantimony ion, tristrifluoromethanesulfonic acid methide ion, perchlorate ion, cyano group, halogen group (chlorine is preferred), alkylcarboxylic acid group (acetate group) , A lactic acid group, a decane carboxylic acid group, etc. The number of carbon atoms is preferably 2 to 20, more preferably 2 to 12, and particularly preferably 2 to 8, and an aryl carboxylic acid (benzoic acid group, anthraquinone carboxylic acid group). , Naphthalenecarboxylic acid group, etc. The number of carbon atoms is preferably 2-20, more preferably 2-11, and particularly preferably 2-7, and alkylsulfonic acid groups (methanesulfonic acid groups, trifluoromethanesulfonic acid groups). 2-20 are preferable, and 2-12 are more preferable. 2-8 are particularly preferred), aryl sulfonic acid groups (benzene sulfonic acid group, p-toluene sulfonic acid group, naphthalene sulfonic acid group are included. Carbon number is preferably 2-20, more preferably 2-11. 2-7 are particularly preferred), hydroxyl groups, imide groups (phthalimide groups, diacetimide groups, bistrifluoromethanesulfonimide groups, etc.) The number of carbon atoms is preferably 2-20, more preferably 2-12, and more preferably 2 To 8 are particularly preferred), aryloxy groups (phenoxy group, etc.). C2-C20 is preferred, 2-12 is more preferred, and 2-8 is particularly preferred.) Alkylthio group (dodecylthio group, etc.). 2-20 are preferable, 2-12 are more preferable, and 2-8 are particularly preferable, and an arylthio group (base). Zenchio group. Preferably 2 to 20 carbon atoms, more preferably 2 to 12, and a 2-8 is particularly preferred.) And the like. Among these, an alkylcarboxylic acid group, an arylcarboxylic acid group, an arylsulfonic acid group, and an imide group are preferable, an alkylcarboxylic acid group and an imide group are more preferable, and an alkylcarboxylic acid group is particularly preferable.

The substituents represented by A ^{1 to} A ⁶ will be described. A ^{1 to} A ⁶ are preferably aromatic rings containing nitrogen atoms, specifically thiazole derivatives, oxazole derivatives, imidazole derivatives, triazole derivatives, thiadiazole derivatives, oxadiazole derivatives, pyridine derivatives, pyrimidine derivatives, pyrazines Derivatives, triazine derivatives and the like may be mentioned, and they may further have an aromatic ring. More preferred are triazole derivatives, thiadiazole derivatives, or oxadiazole derivatives having a structure in which two nitrogen atoms are continuous, and even more preferred are thiadiazole derivatives.
The substituent that the ring represented by A ^{1 to} A ⁶ has is preferably a halogen atom, an alkyl group, or a carbamoyl group (more preferably an alkylcarbamoyl group), and an alkyl group or a carbamoyl group (more preferably an alkylcarbamoyl group). Is more preferable.

In the present invention, A ^{1 to} A ⁶ are more preferably the following ring structures. In the C = N portion constituting the ring of A ^{1 to} A ⁶ , C corresponds to the portion *, and N corresponds to the nitrogen atom adjacent to *.
In the present invention, A ^{1 to} A ⁶ are more preferably the following ring structures.

  Specific examples of the metal complex used in the present invention are shown below, but the present invention is not limited thereto.

In the following, the vertical axis represents Rx, and the part * is bonded to the main skeleton. Further, the horizontal axis represents Ry, and the portion of * is bonded to a connector coming out of the nitrogen atom. For example, the structure of the right half of the following a-22 is as follows.

A compound in which each of the following M is the following metal atom is also preferable.
(D-1): Cu, (d-2): Fe, (d-3), Mg, (d-4): Co, (d-5): Ni

An example of the manufacturing method of the azapyromethene compound contained in the curable coloring composition of this invention is shown. The manufacturing method is not limited to the following method.

Each step will be described. The raw material pyrrole compound can be produced, for example, with reference to Patent Document 5 described above.
(1) Nitrosation The nitrosation can be carried out with reference to the experimental chemistry course (Maruzen Publishing, 5th edition, volume 14, pages 469-473). As a specific example, it can be synthesized by reacting nitrite (which may be generated by reacting nitrite and acid) with pyrrole.
(2) Coupling Obtained by reacting nitrosated pyrrole with pyrrole. It is preferable that a suitable acid coexists as a catalyst. Moreover, it is preferable that a suitable acid anhydride coexists as a dehydrating agent.
(3) Complexation It can be obtained by reacting a dipyrromethene compound with a metal source in an appropriate solvent.

In the curable coloring composition of this invention, the compound represented by Formula (1) may be contained individually by 1 type, and may be used together 2 or more types.
The content of the compound represented by the formula (1) in the curable coloring composition of the present invention varies depending on the molecular weight and the extinction coefficient thereof. 70 mass% is preferable and 10-50 mass% is more preferable. When the content of the compound (dye) represented by the formula (1) is 10% by mass or more, a better color density (for example, a color density suitable for liquid crystal display) is obtained, and 50% by mass or less. This is advantageous in that the patterning of the pixels becomes better.

  Furthermore, the curable coloring composition of the present invention may contain dye compounds and pigment compounds having other structures and dispersions thereof. The dye compound may have any structure as long as it does not affect the hue of the colored image. For example, an anthraquinone type (for example, an anthraquinone compound described in JP-A No. 2001-108815), a phthalocyanine type (E.g., phthalocyanine compounds described in U.S. Patent Application Publication No. 2008/0076044), xanthene series (e.g., CI Acid Red 289), triarylmethane series (e.g., I Acid Blue 7, CI Acid Blue 83, CI Acid Blue 90, CISolvent Blue 38 , CI Acid Violet17, CI Acid Violet 17 Examples include CI 49 (CIAcid Violet49), CI Acid Green3, squarylium, pyrazole azo, methine, pyrazolone azo and barbiturazo. Examples of soluble dyes include CI Solvent Yellow 4, CI Solvent Yellow 88, CI Solvent Yellow 14, CI Solvent Yellow 15, CI Solvent Yellow 24, CI Solvent Yellow 94, CI Solvent Yellow 98, CI Solvent Yellow 162, CI Solvent Yellow 82, and the like.

  Examples of pigment compounds include perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, triarylcarbonium, dioxazine, aminoanthraquinone, diketopyrrolopyrrole, Indigo, thioindigo, isoindoline, isoindolinone, pyranthrone, isoviolanthrone and the like. More specifically, for example, perylene compound pigments such as Pigment Red 190, Pigment Red 224, and Pigment Violet 29, perinone compound pigments such as Pigment Orange 43, and Pigment Red 194, Pigment Violet 19, and Pigment Violet. 42, quinacridone such as Pigment Red 122, Pigment Red 192, Pigment Red 202, Pigment Red 207, or Pigment Red 209, quinacridone compound pigment, Pigment Red 206, Pigment Orange 48, or Pigment Orange 49 Quinone compound pigment, anthraquinone compound pigment such as pigment yellow 147, anthanthrone compound pigment such as pigment red 168, pigment Benzimidazolone compound pigments such as Pigment Brown 25, Pigment Violet 32, Pigment Orange 36, Pigment Yellow 120, Pigment Yellow 180, Pigment Yellow 181, Pigment Orange 62, or Pigment Red 185; Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 166, Pigment Orange 34, Pigment Orange 13, Pigment Orange 31, Pigment Red 144, Pigment Red 166, Pigment Red Red 220, Pigment Red 221, Pigment Red 242, Pigment Red 248, Pigment Red 262, or Pigment Disazo condensation compound pigments such as Brown 23, Pigment Yellow 13, Pigment Yellow 83, or Disazo Compound Pigments such as Pigment Yellow 188, Pigment Red 187, Pigment Red 170, Pigment Yellow 74, Pigment Yellow 150, Pigment Red 48, Pigment Red 53, Pigment Orange 64, Pigment Red 247 and other azo compound pigments, Pigment Blue 60 and other indanthrone compound pigments, Pigment Green 7, Pigment Green 36, Pigment Green 37, phthalocyanine compound pigments such as Pigment Green 58, Pigment Blue 16, Pigment Blue 75, and Pigment Blue 15, Pigment Blue 56 Or triarylcarbonium compound pigments such as Pigment Blue 61, dioxazine compound pigments such as Pigment Violet 23 or Pigment Violet 37, aminoanthraquinone compound pigments such as Pigment Red 177, Pigment Red 254, Pigment Red 255, pigment red 264, pigment red 272, pigment orange 71, or diketopyrrolopyrrole compound pigment such as pigment orange 73, thioindigo compound pigment such as pigment red 88, pigment yellow 139, pigment orange 66 Isoindoline compound pigments such as Pigment Yellow 109, Pigment Orange 61, and Pigment Oren 40, or pyranthrone compound pigments such as Pigment Red 216 or isoviolanthrone compound pigments, such as Pigment Violet 31, and the like.

Content of the said dye and pigment can be used in the range which does not impair the effect of this invention, and is 0.5 mass%-70 mass% with respect to the total solid of the curable coloring composition of this invention. preferable.
When the curable coloring composition of the present invention is prepared by blending the dye or pigment as a dispersion, it can be prepared according to the descriptions in JP-A-9-197118 and JP-A-2000-239544.

In the present invention, a curable green coloring composition can be preferably provided, particularly by adding a yellow pigment compound. The provided curable green coloring composition has high color purity, and when applied to a liquid crystal display device and a solid-state imaging device, the color of the display image can be vivid and exhibit high contrast.
The addition amount of the yellow dye compound is preferably 1% by mass to 70% by mass and more preferably 10% by mass to 50% by mass with respect to the total solid content of the curable coloring composition of the present invention. . Moreover, when the compound represented by Formula (1) of this invention is 100 mass parts, it is preferable that the addition amount of a yellow pigment compound is 10 mass parts-1000 mass parts, and 20 mass parts-500 mass parts. More preferably, it is a part.

[Polymerizable compound]
The colored composition of the present invention preferably contains at least one polymerizable compound. Examples of the polymerizable compound include addition polymerizable compounds having at least one ethylenically unsaturated double bond.

  Specifically, it is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and their (co) polymers.

  Examples of monomers and their (co) polymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, amides, and these (Co) polymers, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and these (co) polymers It is a polymer. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

Specific examples of the ester monomer of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetra Methylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol Diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol tria Relate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanur Examples include acid EO-modified triacrylate.
Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloxy-2-hi Rokishipuropokishi) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane, and the like.

Further, as itaconic acid ester, for example, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol Diitaconate, sorbitol tetritaconate, etc., and crotonic acid esters such as ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate, etc. For example, ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, etc. As, for example, ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetra malate, and the like.
Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. And those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613. Furthermore, the ester monomers described above can also be used as a mixture.

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

Further, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. Vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (B) to a polyisocyanate compound having two or more isocyanate groups Compounds and the like.
CH ₂ = C (R) COOCH ₂ CH (R ′) OH (B)
[In general formula (B), R and R ′ each independently represent H or CH 3. ]

  About these polymeric compounds, the details of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the final performance design of a curable coloring composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Also, from the viewpoint of increasing the strength of the colored cured film, those having three or more functionalities are preferable, and those having different functional numbers and different polymerizable groups (for example, acrylic acid esters, methacrylic acid esters, styrene compounds, vinyl ether compounds). It is also effective to adjust both sensitivity and intensity by using together. In addition, the selection of the polymerizable compound is also possible with respect to the compatibility and dispersibility with other components (for example, photopolymerization initiator, colorant (pigment), binder polymer, etc.) contained in the curable coloring composition. The method of use is an important factor. For example, compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a support.

  The content of the polymerizable compound in the total solid content of the coloring composition (total content in the case of 2 or more types) is not particularly limited, and is 10% by mass from the viewpoint of more effectively obtaining the effects of the present invention. -80% by mass is preferable, 15% by mass to 75% by mass is more preferable, and 20% by mass to 60% by mass is particularly preferable.

[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.

  Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyl oxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, and an acetophenone compound. And derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, oxime compounds, and the like. Specific examples of the photopolymerization initiator include those described in paragraph numbers [0070] to [0077] of JP-A No. 2004-295116. Among these, an oxime compound is preferable from the viewpoint of rapid polymerization reaction.

The oxime-based compound (hereinafter also referred to as “oxime-based photopolymerization initiator”) is not particularly limited. For example, JP-A-2000-80068, WO02 / 100903A1, JP-A-2001-233842, etc. The described oxime compounds are mentioned.
Specific examples include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio). Phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4 -(Phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyloxime)- 1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1, -Butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9- Ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl) Such as 9H- carbazol-3-yl] ethanone and the like. However, it is not limited to these.

  Moreover, in this invention, the compound represented by following General formula (11) is more preferable as an oxime type compound from a viewpoint of a sensitivity, the stability at the time of diameter, and the coloring at the time of post-heating.

  In the general formula (11), 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 in any one of 1-5.

  R is preferably an acyl group from the viewpoint of increasing sensitivity, and specifically, an acetyl group, a propionyl group, a benzoyl group, and a toluyl group are preferable.

  A is an alkylene group substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heat aging, An alkylene group substituted with an alkenyl group (for example, vinyl group, allyl group), an aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) A substituted alkylene group is preferred.

  Ar is preferably a substituted or unsubstituted phenyl group from the viewpoint of increasing sensitivity and suppressing coloring due to heating. In the case of a substituted phenyl group, the substituent is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

X is an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkenyl that may have a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. Group, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthioxy group which may have a substituent, a substituent An arylthioxy group which may have an amino group and an amino group which may have a substituent are preferable.
Further, n in the general formula (11) is preferably 1 or 2.

  In addition to the above photopolymerization initiator, other known photopolymerization initiators described in paragraph [0079] of JP-A No. 2004-295116 are used in the curable coloring composition of the present invention. May be.

A photoinitiator can be contained individually by 1 type or in combination of 2 or more types.
The content (total content in the case of two or more) of the curable coloring composition of the photopolymerization initiator in the total solid content is 3% by mass to 20% by mass from the viewpoint of more effectively obtaining the effects of the present invention. % Is preferable, 4% by mass to 19% by mass is more preferable, and 5% by mass to 18% by mass is particularly preferable.

[Sensitizer (polymerization initiator assistant)]
In the present invention, it is also preferable to add a sensitizer (polymerization initiator assistant).
The inclusion of a sensitizer is effective for improving exposure sensitivity, and is particularly effective when the exposure light source is a g / h line mixed line.
As the sensitizer, anthracene derivatives, acridone derivatives, thioxanthone derivatives, coumarin derivatives, base styryl derivatives, and distyrylbenzene derivatives are preferable.
Anthracene derivatives include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9 , 10-dibromoanthracene, 2-ethylanthracene and 9,10-dimethoxyanthracene are preferred.
As an acridone derivative, acridone, N-butyl-2-chloroacridone, N-methylacridone, 2-methoxyacridone and N-ethyl-2-methoxyacridone are preferable.
As the thioxanthone derivative, thioxanthone, diethylthioxanthone, 1-chloro-4-propoxythioxanthone, and 2-chlorothioxanthone are preferable.
As the coumarin derivative, coumarin-1, coumarin-6H, coumarin-110 and coumarin-102 are preferable.
Examples of the base styryl derivative include 2- (4-dimethylaminostyryl) benzoxazole, 2- (4-dimethylaminostyryl) benzothiazole, and 2- (4-dimethylaminostyryl) naphthothiazole.
Examples of the distyrylbenzene derivative include distyrylbenzene, di (4-methoxystyryl) benzene, and di (3,4,5-trimethoxystyryl) benzene.
Specific examples of the sensitizer include the following. In the following, Me represents a methyl group, Et represents an ethyl group, and Bu represents a butyl group.

  The content of the sensitizer in the present invention is preferably 0.1 to 10 parts by weight, and preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the compound represented by the formula (1). Is more preferable.

[Organic solvent]
The curable 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 used as a curable coloring composition, in particular, the solubility of the binder, the coating property, It is preferable to select in consideration of safety.

  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 of the above-mentioned components when an alkali-soluble binder is included, and improvement of the coating surface condition. 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 curable coloring 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. .

[Other ingredients]
The curable coloring composition of the present invention may further contain other components such as an alkali-soluble binder and a crosslinking agent in addition to the above-described components as long as the effects of the present invention are not impaired.

-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 chain butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like. Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, sulfonic acid group and groups derived from salts thereof, morpholinoethyl group, etc. Monomers comprising it are also useful.

  The alkali-soluble binder may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and includes, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain. Polymers and the like are also useful. Examples of the polymer containing the above-described polymerizable group include commercially available KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.), and the like. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  Among these various alkali-soluble binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.

  Examples of the acrylic resin include a copolymer made of a monomer selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and a commercially available KS resist 106 ( Osaka Organic Chemical Industry Co., Ltd.) and Cyclomer P Series (Daicel Chemical Industries, Ltd.) are preferred.

The alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene conversion value measured by GPC method) of 1000 to 2 × 10 5 from the viewpoint of developability, liquid viscosity, and the like.
A polymer of 00 to 1 × 10 5 is more preferred, and a polymer of 5000 to 5 × 10 4 is particularly preferred.

-Crosslinking agent-
It is also possible to further increase the hardness of the colored cured film formed by curing the curable coloring composition by using a crosslinking agent in addition to the curable coloring composition of the present invention.
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, which is substituted with one substituent; Phenol compounds, naphthol compounds or hydroxyanthracene compounds. Of these, polyfunctional epoxy resins are preferred.
For details such as specific examples of the cross-linking agent, reference can be made to the description of paragraph numbers [0134] to [0147] of JP-A No. 2004-295116.

-Surfactant-
The curable coloring composition of the present invention may contain a surfactant. As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO), MegaFac (manufactured by DIC Corporation), Florard (Sumitomo 3M) (Manufactured by Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and the like.
In addition, the surfactant contains the following structural unit A and structural unit B as repeating units, and has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography of 1,000 to 10,000. A polymer can be mentioned as a preferred example.

(In the structural units (A) and (B), R ¹ and R ³ each independently represents a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴ represents hydrogen. Represents an atom or an alkyl group having 1 to 4 carbon atoms; L represents an alkylene group having 3 to 6 carbon atoms;
(R ⁵ represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 2 or 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. Is preferably a branched alkylene group represented by (preferably), p and q are weight percentages representing a polymerization ratio, p represents a numerical value of 10% to 80% by weight, and q is 20% to 90% by weight. % Represents an integer of 1 to 18, and n represents an integer of 1 to 10. )
As for the weight average molecular weight (Mw) of surfactant which is a copolymer containing the structural unit A and the structural unit B as a repeating unit, 1500-5,000 are more preferable.
These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The addition amount of the surfactant in the curable coloring composition of the present invention is preferably 10 parts by weight or less and preferably 0.01 to 10 parts by weight with respect to 100 parts by weight as the total mass of other components. More preferred is 0.01 to 1 part by weight.

-Other additives-
If necessary, the curable coloring composition of the present invention contains various additives such as fillers, polymer compounds other than those mentioned above, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like. can do. Examples of these additives include those described in paragraphs [0155] to [0156] of JP-A No. 2004-295116.
In the curable coloring composition of the present invention, a sensitizer and a light stabilizer described in paragraph [0078] of JP-A No. 2004-295116, and a thermal polymerization inhibitor described in paragraph [0081] of the same publication. Can be contained.

Further, when the alkali solubility in the non-exposed area is promoted and the developability of the curable coloring composition is further improved, the composition is an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less. Is preferably added.
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.

Manufacturing method of curable coloring composition The curable coloring composition of this invention is prepared by mixing each above-mentioned component and arbitrary components as needed.
In preparing the curable coloring composition, the components constituting the curable coloring composition may be combined at once, or may be combined sequentially 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 curable coloring composition prepared as described above is preferably filtered using a filter having a pore size of 0.01 μm to 3.0 μm, more preferably a pore size of about 0.05 μm to 0.5 μm. Can be used for use.
Since the curable coloring composition of the present invention can form a colored cured film excellent in hue and contrast, 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 such as printing inks, inkjet inks, and paints. 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 configured by providing a colored region on a substrate. The colored region on the substrate is composed of colored films such as red (R), green (G), and blue (B) that form each pixel of the color filter. Since the color filter of the present invention is formed by including a diarylmethane compound having a predetermined structure, the color when displaying an image is bright and the contrast is high, which 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 is a method capable of forming a colored region (colored pattern) cured by containing an arylmethane compound. Preferably, it is produced using the curable coloring composition of the present invention.

The method for producing a color filter of the present invention includes a step (A) of applying the curable coloring composition described above on a support to form a colored layer (also referred to as a colored composition layer), and a step (A). A step of exposing the colored composition layer formed in (1) to a pattern (preferably through a mask) and developing the uncured portion of the coating film with a developer to form a colored region (colored pattern) (B ). 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 the present invention will be described more specifically.

-Process (A)-
In the method for producing a color filter of the present invention, first, the curable coloring composition of the present invention described above is applied directly or via another layer on a support by a desired coating method, and then the curable coloring composition is prepared. A coating film (colored composition layer) made of a product is formed, and then pre-cured (pre-baked) as necessary, and the curable colored composition layer is dried.

As the support, for example, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film to these, solid-state imaging elements, etc. Examples of the photoelectric conversion element substrate include a silicone substrate and a plastic substrate. Further, on these supports, a black matrix for isolating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion. Further, if necessary, an undercoat layer may be provided on the support for improving adhesion to the upper layer, preventing diffusion of substances, or flattening the surface.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

In addition, a driving substrate on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is disposed (hereinafter referred to as “TFT type liquid crystal driving substrate”) is used as a support. A color filter using the curable coloring composition of the present invention can also be formed on the substrate to produce a color filter.
Examples of the substrate in the TFT type liquid crystal driving substrate include glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired. For example, a substrate in which a passivation film such as a silicon nitride film is formed on the surface of the TFT liquid crystal driving substrate can be used.

  The curable coloring composition of the present invention is applied to the substrate directly or via another layer by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, ink jet, or the like, and the curable coloring composition A coating film of an object can be formed.

In the coating step, the method for applying the curable coloring composition of the present invention to the substrate is not particularly limited, but a method using a slit nozzle such as a slit-and-spin method or a spinless coating method (hereinafter, Slit nozzle coating method) is preferable.
In the slit nozzle coating method, the slit-and-spin coating method and the spinless coating method have different conditions depending on the size of the coated substrate. For example, a fifth generation glass substrate (1100 mm × 1250 mm) is coated by the spinless coating method. In this case, the discharge amount of the curable coloring composition from the slit nozzle is usually 500 microliter / second to 2000 microliter / second, preferably 800 microliter / second to 1500 microliter / second. The speed is usually 50 mm / second to 300 mm / second, preferably 100 mm / second to 200 mm / second.
Moreover, as solid content of the curable coloring composition used at an application | coating process, it is 10%-20% normally, Preferably it is 13%-18%.

When forming the coating film by the curable coloring composition of this invention on a board | substrate, as thickness (after a prebaking process) of this coating film, it is generally 0.3 micrometer-5.0 micrometers, Preferably 0.5 micrometer-4 0.0 μm, most desirably 0.5 μm to 3.0 μm.
In the case of a color filter for a solid-state image sensor, the thickness of the coating film (after pre-baking) is preferably in the range of 0.5 μm to 5.0 μm.

In the coating process, usually, a pre-bake treatment is performed after coating. If necessary, vacuum treatment can be performed before pre-baking. The vacuum drying conditions are such that the degree of vacuum is usually about 0.1 to 1.0 torr, preferably about 0.2 to 0.5 torr.
The pre-bake treatment is performed in a temperature range of 50 ° C. to 140 ° C., preferably about 70 ° C. to 110 ° C. using a hot plate, an oven, etc., and can be performed under conditions of 10 seconds to 300 seconds. Note that high-frequency treatment or the like may be used in combination with the pre-bake treatment. The high frequency treatment can be used alone.

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 coloring composition layer formed with a curable coloring composition is suitably selected according to the objective. In the color filter for liquid crystal display devices, the range of 0.2 μm to 5.0 μm is preferable, the range of 1.0 μm to 4.0 μm is more preferable, and the range of 1.5 μm to 3.5 μm is most preferable. Moreover, in the color filter for solid-state image sensors, the range of 0.2 micrometer-5.0 micrometers is preferable, The range of 0.3 micrometer-2.5 micrometers is more preferable, The range of 0.3 micrometer-1.5 micrometers is the most preferable.
In addition, the thickness of a coloring composition layer is a film thickness after prebaking.

-Process (B)-
Subsequently, in the method for producing a color filter of the present invention, the coating film (colored composition layer) made of the colored composition formed on the support as described above is exposed through, for example, a photomask. It is. As light or radiation applicable to exposure, g-line, h-line, i-line, j-line, KrF light and ArF light 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 ^{100mJ / cm 2 ~10000mJ / cm 2} .

  Other exposure rays include ultra high pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser light sources, fluorescent lamps, tungsten lamps, solar Light or the like can also be used.

~ Exposure process using laser light source ~
In an exposure method using a laser light source, an ultraviolet laser is used as the light source.
The irradiation light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm, more preferably an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm matches the photosensitive wavelength of the resist. Is preferable. 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 exposure amount of the exposure object (pattern), in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , the range of 1mJ / cm ² ~50mJ / cm ² is more preferable. An exposure amount within this range is preferable from the viewpoint of pattern formation productivity.

There are no particular restrictions on the exposure apparatus, but those that are commercially available include Callisto.
(Bui Technology Co., Ltd.), EGIS (Bui Technology Co., Ltd.) and DF2200G (Dainippon Screen Co., Ltd.) can be used. Further, devices other than those described above are also preferably used.
When manufacturing a color filter for a liquid crystal display device, exposure using mainly h-line and i-line is preferably used by a proximity exposure machine and a mirror projection exposure machine. Further, when manufacturing a color filter for a solid-state image sensor, it is preferable to mainly use i-line in a stepper exposure machine. When manufacturing a color filter using a TFT type liquid crystal driving substrate, the photomask used has a through hole or a U-shaped depression in addition to a pattern for forming a pixel (colored pattern). The thing in which the pattern for forming is provided is used.

The colored composition layer exposed as described above can be heated.
The exposure can be performed while flowing a nitrogen gas in the chamber in order to suppress oxidation fading of the coloring material in the colored composition layer.

Subsequently, development is performed with a developer on the colored composition layer after exposure. Thereby, a negative type or positive type coloring pattern (resist pattern) can be formed. In the development step, the uncured portion of the coating film after exposure is eluted in the developer, and only the cured portion remains on the substrate.
Any developer can be used as long as it dissolves the coating film (colored composition layer) of the colored composition in the uncured part while not dissolving the cured part. For example, combinations of various organic solvents and alkaline aqueous solutions can be used.
Examples of the organic solvent used for development include the above-described solvents that can be used in preparing the curable coloring composition of the present invention.
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. Concentrations of alkaline compounds such as ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene are 0.001% by mass to 10% by mass, preferably 0.01 The alkaline aqueous solution melt | dissolved so that it may become 1 mass%-1 mass% is mentioned. When the developer is an alkaline aqueous solution, the alkali concentration is preferably adjusted to be pH 11 to 13, more preferably pH 11.5 to 12.5.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.

The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 seconds to 90 seconds.
Development may be any of a dip method, a shower method, a spray method, and the like, and may be combined with a swing method, a spin method, an ultrasonic method, or the like. It is also possible to prevent development unevenness by previously moistening the surface to be developed with water or the like before touching the developer. It is also possible to develop with the substrate tilted.
Further, when manufacturing a color filter for a solid-state image sensor, paddle development is also used.

After the development process, a rinsing process for washing and removing excess developer is performed, followed by drying, followed by heat treatment (post-baking) to complete the curing.
The rinsing process is usually performed with pure water, but in order to save liquid, pure water is used in the final cleaning, and used pure water is used in the initial stage of cleaning, or the substrate is inclined and cleaned. Alternatively, a method of using ultrasonic irradiation together may be used.

  After the rinse treatment, after draining and drying, a heat treatment of about 200 ° C. to 250 ° C. is usually performed. In this heat treatment (post-bake), the coating film after development is continuously or batch-treated using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so as to satisfy the above conditions. It can be done with an expression.

By sequentially repeating the above steps for each color according to the desired number of hues, it is possible to produce a color filter in which a cured film (colored pattern) colored in a plurality of colors is formed.
Since the color filter of the present invention has high contrast, small color density unevenness, and good color characteristics, it can be suitably used for a solid-state imaging device or a liquid crystal display device.

-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 the curable coloring composition of the present invention.

-Process (D)-
It is preferable to further heat-treat the colored pattern that has been post-exposed by ultraviolet irradiation as described above. The colored pattern can be further cured by subjecting the formed colored pattern to heat treatment (so-called post-bake treatment). 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) are 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 is 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.

The color filter obtained by the method for producing a color filter of the present invention (the color filter of the present invention) is excellent in hue and contrast because it uses the curable coloring composition of the present invention.
The color filter of the present invention can be used for a liquid crystal display element or a solid-state image sensor, and is particularly suitable for use in a liquid crystal display device. When used in a liquid crystal display device, it is possible to display an image excellent in spectral characteristics and contrast while achieving a good hue using a dye as a colorant.

As described above, the curable coloring composition of the present invention has been mainly described for the purpose of forming the color pattern of the color filter. However, for the formation of a black matrix that isolates the color pattern (pixels) constituting the color filter. Can also be applied.
The black matrix on the substrate is a curable coloring composition containing a black pigment processed pigment such as carbon black or titanium black, and is subjected to coating, exposure, and development steps. It can be formed by baking.

Liquid crystal display device and solid-state image sensor The liquid crystal display element and the solid-state image sensor of the present invention include the color filter of the present invention. More specifically, for example, by forming an alignment film on the inner surface side of the color filter, facing the electrode substrate, and filling the gap with liquid crystal and sealing, a panel which is the liquid crystal display element of the present invention is obtained. . For example, the solid-state image sensor of this invention is obtained by forming a color filter on a light receiving element.

  For the definition of liquid crystal display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Kogyo Kenkyukai 1990)”, “Display Devices (written by 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 liquid crystal display device to which 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 horizontal electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.
The color filter of the present invention is a bright and high-definition COA (Color-filter On Array).
It is also possible to use the method.

  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.

When described in color order, the blue light emitting diode includes a material mainly composed of gallium nitride (GaN), and specifically, a sapphire substrate / n-GaN / n-Al0.15Ga0.85N / MQW or SQW layer. Some have a layer structure of /p-Al0.15Ga0.85N/p-GaN/electrode. Here, the MQW or SQW layer is a multi-quantum well structure (MQW
) Or single quantum well structure (SQW). As a material constituting these quantum well structures, InxGaN1-xN can be exemplified, and blue color is generated when x = 0.2, and green color is generated when x = 0.4. With this material, when the In (indium) composition is increased, green light emission can be obtained. However, as the In composition increases, the crystallinity deteriorates, so that the light emission efficiency decreases.

  As another material for ensuring sufficient light emission luminance, a GaInN green LED or a combination of GaInN blue LED + green phosphor can be used. By doing so, the peak wavelength can be brought to an appropriate wavelength in the range of 520 to 570 nm.

  Examples of the green phosphor that can be used include oxides, nitrides, and oxynitrides activated with cerium and / or europium.

  As the red LED, satisfactory light emission characteristics can be obtained by using an AlInGaP-based LED. As another red LED, there is a GaAlAs red LED. The structure has a layer structure of GaAs substrate / n-GaAs / n-InGaAlP / undoped InGaAlP / p-InGaAlP / p-GaAs / electrode. Among the three elements of In, Ga, and Al, the emission wavelength can be changed by changing the ratio of Ga and Al by combining the lattice constant of GaAs with an In atomic ratio of 0.5. Increasing the proportion of Al shifts the emission to a short wavelength. When the atomic ratio of Ga is 0.25 and the atomic ratio of Al is about 0.25, red light emission with a wavelength of about 600 nm can be obtained.

  The LEDs listed above can be made by chemical vapor deposition using organic metal (MOCVD), so the composition can be controlled relatively easily by controlling the proportion of the organic metal raw material introduced into the reaction chamber. can do. Accordingly, it is relatively easy to bring the peak wavelength of light emission of the blue LED into the range of 430 to 480 nm, or to bring the peak wavelength of light emission of the red LED into the range of 600 to 660 nm.

  In addition to these LEDs, it is also possible to use a phosphor material that emits light of each color.

  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” is based on mass.

<Synthesis Example of Compound b-4>

Compound b-4 was synthesized according to the above scheme.
Compound 1 as a raw material was synthesized by mixing and reacting one equivalent each of malononitrile and 2-aminobenzenethiol in acetic acid at room temperature.

To a mixture of Compound 1 (12.06 g), Compound 1-2 (20.3 g) and 1-butanol (50 mL) was added 50% aqueous sodium hydroxide solution (12 mL) under a nitrogen stream, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was further stirred at 90 ° C. for 3 hours. Water (100 mL) was added to the reaction mixture, and the resulting precipitate was filtered, washed with water and dried to obtain compound 2 (13.7 g, yield 62%).
Next, the obtained compound 2 was dissolved in toluene (100 ml), cooled to 5 ° C. or lower, and 8% aqueous sodium hydroxide solution (100 mL) was added. Here, 3-chloro-6-methylpyridazine (7.2 g, manufactured by Aldrich) was added in portions while maintaining the temperature at 5 ° C. or lower, and further stirred at room temperature for 1 hour.
The aqueous phase was removed from the reaction mixture by a liquid separation operation, and the remaining ethyl acetate phase was washed with aqueous sodium bicarbonate and brine, dried over magnesium sulfate, and then the solvent was distilled off. The obtained oil was dissolved in heated methanol and then cooled to obtain crystals, which were collected by filtration to obtain Compound 3 (8.3 g, yield 47%).
Compound 3 (8.3 g) was mixed with acetic acid (80 mL), and a solution of sodium nitrite (1.6 g) dissolved in 5 mL of water was added dropwise while maintaining 5 to 10 ° C. The mixture was stirred at room temperature for 1 hour and then 320 mL of water was added. The produced solid was collected by filtration to obtain Compound 4 (7.3 g, yield 83%).
Next, acetic acid (20 mL) was added to compound 4 (4.4 g) and compound 2 (3.2 g), and the mixture was stirred for 1 hour. The reaction solution was poured into methanol (100 mL), and the resulting precipitate was filtered and washed with methanol to obtain Compound 5 (6.15 g, yield 83%).

The obtained compound 5 (3.7 g) was dissolved in toluene (100 mL), cooled to 5 ° C. or lower, and 8% aqueous sodium hydroxide solution (100 mL) was added. Here, 3-chloro-6-methylpyridazine (4.0 g, manufactured by Aldrich) was added in portions while maintaining at 5 ° C. or lower, and the mixture was further stirred at room temperature for 1 hour.
The aqueous phase was removed from the reaction mixture by a liquid separation operation, and the remaining ethyl acetate phase was washed with aqueous sodium bicarbonate and brine, dried over magnesium sulfate, and then the solvent was distilled off. The obtained oil was dissolved in heated methanol and then cooled to obtain crystals, which were collected by filtration to obtain Compound 6 (5.9 g, yield 67%).

Compound 6 (1.1 g) and tetrahydrofuran (3 mL) were added to a 100 mL round bottom flask, and a solution of zinc acetate dihydrate (0.3 g) in methanol (3 mL) was added thereto. After stirring at room temperature for 1 hour, the resulting crystals were filtered off. The crystals were stirred and washed in 6 mL of methanol and collected by filtration. Compound 7: b-4 (0.9 g) was obtained by drying at room temperature.
This compound showed an absorption maximum at 696 nm in ethyl acetate, and the molar extinction coefficient was 245,000. Further, this compound was analyzed by MS and confirmed to be a compound having the notation structure.

<Synthesis Example of Compound a-20>
Synthesized according to the above scheme.
The synthesis was possible in the same manner except that 3-chloro-6-methylpyridazine (7.2 g, manufactured by Aldrich) in the b-4 synthesis example was changed to 2-chlorobenzoxazole (manufactured by TCI). It was.
This compound a-20 showed an absorption maximum at 708 nm in ethyl acetate, and the molar extinction coefficient was 221,000. Further, this compound was analyzed by MS and confirmed to be a compound having the notation structure.

  Other compounds were synthesized according to the above synthesis example.

Materials used Each component used for the preparation of the curable coloring composition is shown below.
(YD-1) C.I. I. Pigment Yellow 150 (PY150, 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 (YD-2) obtained as above. I. Solvent Yellow 162 (SY162, 10.0 parts) dissolved in propylene glycol monomethyl ether acetate (90.0 parts) (GD-1) C.I. I. Pigment Green 58 (PG58, 10.0 parts) and acrylic pigment dispersant (5.0 parts) are mixed with propylene glycol monomethyl ether acetate (80.0 parts), and the pigment is sufficiently dispersed using a bead mill. Pigment dispersion (GD-2) obtained as above. I. Pigment Green 7 (PG7, 10.0 parts) and acrylic pigment dispersant (10.0 parts) are mixed with propylene glycol monomethyl ether acetate (80.0 parts), and the pigment is sufficiently dispersed using a bead mill. Pigment dispersion (cyan dye solution b-4) obtained by mixing the compound b-4 (10.0 parts) and propylene glycol monomethyl ether acetate (90.0 parts) (T-1) photopolymerizability Compound: Kayalad DPHA (manufactured by Nippon Kayaku Co., Ltd .; mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
(U-1) Binder resin: 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 mass%)
(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) Solvent: Propylene glycol monomethyl ether acetate (X-2) Solvent: Ethyl 3-ethoxypropionate (Y-1) Surfactant: Megafac F781-F (Dainippon Ink (Chemical Industry Co., Ltd.)

Preparation and evaluation of cyan colored film Preparation of curable coloring composition (coating liquid) The components in the following composition were mixed to prepare curable coloring composition 1.
<Composition>
-Cyan dye solution b-4 ... 6.9 parts by mass-(T-1) ... 103.4 parts by mass-(U-1) ... 212.2 parts by mass (in terms of solid content) (Value: 84.9 parts by mass)
-(V-1)-21.2 parts by mass-(W-1)-3.5 parts by mass-(X-1)-71.9 parts by mass- (X-2) ... 3.6 parts by mass, (Y-1) ... 0.06 parts by mass

2. Preparation of colored film by curable coloring composition The above-described curable coloring composition (color resist solution) is 1.5 mm on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) with a maximum absorbance of 1.5. It applied so that rotation number might be adjusted, it applied, and it was made to dry for 180 second in 100 degreeC oven, and the colored film was produced on the board | substrate (Example 1).

  Compound b-4 was changed to the compound shown in the following table, and the other substrates of Examples and Comparative Examples were prepared and evaluated in the same manner as in Example 1.

3. Evaluation of colored film by curable coloring composition The following evaluation was performed about the board | substrate obtained above.
<Evaluation of hue>
About the produced colored film, the absorption maximum position of the dye in methanol and the transmittance | permeability in 550 nm / 580 nm were measured with the ultraviolet visible spectrophotometer (Shimadzu Corporation UV2400-PC). The transmittance is preferably high in the wavelength region of 550 nm, and the transmittance ratio represents a cut edge on the short wave side, so that the transmittance ratio is preferably as small as possible.

<Evaluation of heat resistance>
About the produced colored film, it heated on 200 degreeC / 30 minute conditions, the absorption spectrum change before and behind a heating was measured with the ultraviolet visible spectrophotometer (Shimadzu Corporation UV2400-PC), and an absorption maximum value (at an absorption maximum position) Abs.Change rate) The change rate was evaluated.
It can be evaluated that heat resistance is so high that this change rate value is low.

As is clear from the above table, it can be seen that the compound of the invention is excellent in transmittance in the magenta region and excellent as a cyan dye. In particular, from the comparison with Comparative Examples 1 and 2, the dye compound of the present invention has a hue superiority to the cyan pigment which is considered to be excellent in the prior art, and the heat resistance is as excellent as the pigment. all right. It was shown to be an excellent compound from the viewpoint of the entire cyan dye.
On the other hand, it was found that when a compound corresponding to formula (2) but not corresponding to formula (3) was used (Example 12), the heat resistance tends to be slightly inferior.

Preparation and evaluation of green colored film Preparation of curable coloring composition (coating liquid) The components in the following composition were mixed to prepare a curable coloring composition.
<Composition>
-Cyan dye solution b-4-... 6 parts by mass-Yellow pigment compound (YD-1)-Absorption intensity ratio (absorption at 450 nm / absorption at 650 nm) is in the range of 0.95 to 1.05 The amount of the yellow dye compound was adjusted and added so as to fall within the range.
-(T-1) ... 103.4 parts by mass-(U-1) ... 212.2 parts by mass (solid content conversion value: 84.9 parts by mass)
-(V-1)-21.2 parts by mass-(W-1)-3.5 parts by mass-(X-1)-71.9 parts by mass- (X-2) ... 3.6 parts by mass, (Y-1) ... 0.06 parts by mass

2. Production of colored film by curable coloring composition The curable coloring composition (color resist solution) obtained above has a maximum absorbance at 600 to 700 nm on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning). It apply | coated so that it might become 1.9-2.1, it was made to dry for 180 second in 100 degreeC oven, and the colored film was produced on the board | substrate (Example 101).

  In Example 101, as shown in the following table, the types of the compound and the yellow colorant were changed, and the substrates of the various examples and comparative examples were prepared and evaluated in the same manner.

3. Evaluation of colored film by curable coloring composition The following evaluation was performed about the board | substrate obtained above.
<Evaluation of hue>
About the produced colored film, the absorption maximum position of the dye in ethanol and the transmittance | permeability in 550 nm / 580 nm were measured with the ultraviolet visible spectrophotometer (Shimadzu Corporation UV2400-PC). The transmittance is preferably high in the wavelength region of 550 nm, and the transmittance ratio represents a cut edge on the short wave side, so that the transmittance ratio is preferably as small as possible.

<Evaluation of heat resistance>
About the produced colored film, it heated on 200 degreeC / 30 minute conditions, the absorption spectrum change before and behind a heating was measured with the ultraviolet visible spectrophotometer (Shimadzu Corporation UV2400-PC), and an absorption maximum value (at an absorption maximum position) Abs.Change rate) The change rate was evaluated.
It can be evaluated that heat resistance is so high that this change rate value is low.

From Examples 112 to 124, it was found that the compound of the present invention gave a green colored product having excellent transmittance in the magenta region. It is clear that the achievement level is high compared with Comparative Examples 103 and 1034. Moreover, since the compound of the present invention is a dye and has high heat resistance, it is difficult to cause thermal degradation when a G filter is formed. This is a merit that cannot be achieved with a filter made using a dye such as Comparative Example 104 (SY-162).
Also, increasing the transmittance in the 550 nm region is very important from the viewpoint of improving luminance (energy saving). It was found that the G filter formed with the compound of the present invention has an extremely high partial transmittance and can form a filter with high luminance.
On the other hand, it was found that when a compound corresponding to formula (2) but not corresponding to formula (3) was used (Example 123), the heat resistance tends to be slightly inferior.

Claims (20)

The curable coloring composition in which the compound represented by following formula (1) contains the metal complex compound coordinated to the metal atom or the metal compound.
Formula (1)
(In the formula (1), R ¹ , R ² , R ³ , and R ⁴ each represent a hydrogen atom or a substituent, and R ¹ and R ² , R ³ and R ⁴ are bonded to each other to form a ring. Y ¹ and Y ² each represent an oxygen atom, a sulfur atom, or —NH—, and A ¹ and A ² each represent a nitrogen-containing ring.) The curable coloring composition containing the metal complex compound which the compound represented by following formula (2) coordinated to the metal atom or the metal compound.
Formula (2)
(In the formula (2), R ¹ , R ² , R ³ , and R ⁴ each represent a hydrogen atom or a substituent, and R ¹ and R ² , R ³ and R ⁴ are bonded to each other to form a ring. X ¹ and X ² each represent an oxygen atom, a sulfur atom, or a nitrogen atom, and A ³ and A ⁴ each represent a nitrogen-containing aromatic ring.) The curable coloring composition containing the metal complex compound represented by following formula (3).
Formula (3)
(In the formula (3), R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom or a substituent, and R ¹ and R ² , R ³ and R ⁴ are bonded to each other to form a ring. A ⁵ and A ⁶ each represent a nitrogen-containing aromatic ring, Ma represents a metal atom or a metal compound, Z ¹ represents a group capable of binding to Ma, and a represents 0 Represents 1 or 2.) The curable coloring composition comprising any one of claims 1 to 3, wherein each of the A ^{1 to} A ⁶ has a thiadiazole structure, an oxadiazole structure, a triazole structure, or a pyridazine structure. The R ¹ and R ⁴ are each an aryl group, a heterocyclic group, a cyano group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, or an arylsulfonyl group, according to any one of claims 1 to 4. Curable coloring composition. The curing according to any one of claims 1 to 5, wherein R ² and R ³ are each an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxycarbonyl group, a carbamoyl group, or a halogen atom. Coloring composition.   Furthermore, the curable coloring composition of any one of Claims 1-6 containing a yellow pigment | dye.   Furthermore, the curable coloring composition of any one of Claims 1-7 containing a green pigment | dye.   Furthermore, the curable coloring composition of any one of Claims 1-8 containing a monomer and a polymerization initiator.   The color filter which has a colored layer using the curable coloring composition of any one of Claims 1-9.   The color which has the process of apply | coating the curable coloring composition of any one of Claims 1-9 on a support body, forming a colored layer, and exposing the formed colored layer in pattern form. A method for manufacturing a filter. A liquid crystal display device comprising the color filter according to claim 10. A solid-state imaging device comprising the color filter according to claim 10. A metal complex compound in which a compound represented by the following formula (1) is coordinated to a metal atom or a metal compound.
Formula (1)
(In the formula (1), R ¹ , R ² , R ³ , and R ⁴ each represent a hydrogen atom or a substituent, and R ¹ and R ² , R ³ and R ⁴ are bonded to each other to form a ring. Y ¹ and Y ² each represent an oxygen atom, a sulfur atom, or —NH—, and A ¹ and A ² each represent a nitrogen-containing ring.) A metal complex compound in which a compound represented by the following formula (2) is coordinated to a metal atom or a metal compound.
Formula (2)
(In the formula (2), R ¹ , R ² , R ³ , and R ⁴ each represent a hydrogen atom or a substituent, and R ¹ and R ² , R ³ and R ⁴ are bonded to each other to form a ring. X ¹ and X ² each represent an oxygen atom, a sulfur atom, or a nitrogen atom, and A ³ and A ⁴ each represent a nitrogen-containing aromatic ring.) The metal complex compound represented by following formula (3).
Formula (3)
(In the formula (3), R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom or a substituent, and R ¹ and R ² , R ³ and R ⁴ are bonded to each other to form a ring. A ⁵ and A ⁶ each represent a nitrogen-containing aromatic ring, Ma represents a metal atom or a metal compound, Z ¹ represents a group capable of binding to Ma, and a represents 0 Represents 1 or 2.) The metal complex compound according to any one of claims 14 to 16, wherein each of the A ^{1 to} A ⁶ has a thiadiazole structure, an oxadiazole structure, a triazole structure, or a pyridazine structure. The R ¹ and R ⁴ are each an aryl group, a heterocyclic group, a cyano group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, or an arylsulfonyl group, according to any one of claims 14 to 17. Metal complex compound. The metal according to any one of claims 14 to 18, wherein R ² and R ³ are each an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxycarbonyl group, a carbamoyl group, or a halogen atom. Complex compound. 20. The metal complex compound according to claim 14, wherein R ¹ and R ⁴ are each selected from the following Rx, and the A ^{1 to} A ⁶ are each selected from the following Ry.
(Rx)
(In the above, it is connected at the part of *)
(Ry)
(In the above, the nitrogen atom which is connected to the carbon atom constituting the ring of A ^{1 to} A ⁶ at the portion of *, and the nitrogen atom adjacent to * is represented in the ring of A ^{1 to} A ⁶ Corresponding to.)