JP2009031713A - Dipyrromethene-based boron complex compound and its tautomer, colored photosensitive curing composition, color filter, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored photosensitive curing composition useful for color filters in primary colors, including blue, green and red, having a high molar absorption coefficient and allowing a reduction in film thickness and superior color purity and fastness. <P>SOLUTION: The colored photosensitive curing composition comprises, as its colorant, a dipyrromethene-based boron complex compound represented by formula (I), wherein R<SP>1</SP>to R<SP>6</SP>each independently represent a hydrogen atom or a substituent group; R<SP>7</SP>represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group; and X<SP>1</SP>and Y<SP>1</SP>each independently represent a halogen atom, an alkoxy group, an aryloxy group, a hydroxyl group, an alkylthio group, an arylthio group or a heterocyclic thio group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a dipyrromethene-based boron complex compound suitable for forming a color filter used in a liquid crystal display device or a solid-state imaging device, its compatible isomer, a photosensitive colored curable composition, and a color filter using the same. And a manufacturing method thereof.

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

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

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

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

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

  Next, conventional techniques relating to high fastness dyes will be described. In general, colorants used in various applications are required to have the following properties in common. That is, it has favorable absorption characteristics in terms of color reproducibility, fastness under the environmental conditions used, for example, good heat resistance, light resistance, moisture resistance, etc., has a large molar extinction coefficient and can be thinned. That is needed. Furthermore, in a colored curable composition using a dye, the storage stability is important, and when the colored curable composition is stored, it has sufficient solubility in an organic solvent so as not to precipitate crystals. It is necessary to be.

  For example, it is disclosed that a dipyrromethene-based metal complex is used as a functional compound in various applications, and is used as a sensitizer of a radical polymerization initiator in a visible light polymerization composition (for example, a patent Reference 2-8). Also, in liquid crystal displays and electronic displays, it is used not as a pigment for each pixel of red, green, and blue, but as a pigment for a filter for cutting unnecessary light emission such as plasma emission and liquid crystal display. (For example, refer to Patent Documents 9 to 13).

JP-A-6-75375 Japanese Patent No. 3279035 Japanese Patent No. 3324279 Japanese Patent Application Laid-Open No. 11-352685 Japanese Patent Laid-Open No. 11-352686 JP 2000-19729 A JP 2000-19738 A JP 2002-236360 A JP 2003-57436 A JP 2005-77953 A JP 2006-651112 A JP 2006-79011 A JP 2006-79012 A

The present invention is a dipyrromethene-based boron complex compound having excellent color purity, high extinction coefficient, and excellent fastness useful for primary color filters arranged in blue, green, and red, and tautomers thereof, And a boron complex compound thereof and a tautomer thereof, and an object thereof is to provide a photosensitive colored curable composition that can be thinned and to achieve the object.
Another object of the present invention is to provide a blue photosensitive colored curable composition excellent in blue color purity, having a high extinction coefficient capable of being thinned, and excellent in fastness. The challenge is to achieve.
Furthermore, it aims at providing the color filter which is excellent in color purity using the photosensitive coloring curable composition, can be thinned, and is excellent in fastness, and its manufacturing method, and achieves this objective. This is the issue.

  As a result of examining various dyes in detail, the present invention shows that a specific dipyrromethene-based boron complex compound has a good hue and a high extinction coefficient as a dye for pattern coloring, and is good for heat and light. It has been achieved based on the knowledge that it has robustness. Specific means for solving the above-mentioned problems are as follows.

<1> A photosensitive colored curable composition containing a dipyrromethene-based boron complex compound represented by the following general formula (I) as a colorant.

In general formula (I), R ^{1 to} R ⁶ each independently represent a hydrogen atom or a substituent, R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and X ¹ and Y ¹ each independently represent a halogen atom, an alkoxy group, an aryloxy group, a hydroxyl group, an alkylthio group, an arylthio group, or a heterocyclic thio group.

<2> In the general formula (I), at least one of R ¹ and R ⁶ represents an amino group, a carbonamido group, a ureido group, an alkoxycarbonylamino group, or an imide group, and R ² and R ⁵ At least one represents a cyano group or the following structural formula, The photosensitive coloring curable composition as described in <1> characterized by the above-mentioned.

<3> The photosensitive colored curable composition according to <1> or <2>, further comprising a tetraazaporphyrin-based cyan dye represented by the following general formula (A).

In General Formula (A), M ¹ represents a metal or a metal compound, and Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently an atom selected from a carbon atom, a nitrogen atom, and a hydrogen atom. This represents an atomic group necessary for forming a constituted 6-membered ring.

<4> The photosensitive coloring according to <3>, wherein the tetraazaporphyrin-based cyan dye represented by the general formula (A) is a phthalocyanine-based dye represented by the following general formula (B). Curable composition.

In general formula (B), R ^{101 to} R ¹¹⁶ each independently represent a hydrogen atom or a substituent, and M ² represents a metal or a metal compound.

<5> The photosensitive colored curable composition according to any one of <1> to <4>, further comprising a cyan dye represented by the following general formula (C).

In the general formula (C), R ^{50 to} R ⁵⁵ each independently represent a hydrogen atom or a substituent, and R ⁵⁶ and R ⁵⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or hetero Represents a cyclic group, and Za and Zb each independently represent -N = or -C ( ^R58 ) =. R ⁵⁸ represents a hydrogen atom or a substituent. R ⁵² and R ⁵³ , R ⁵³ and R ⁵⁷ , R ⁵⁴ and R ⁵⁵ , R ⁵⁵ and R ⁵⁶ , and / or R ⁵⁶ and R ⁵⁷ are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. May be.

<6> A color filter using the photosensitive colored curable composition according to any one of <1> to <5>.

<7> A color filter having a step of applying the photosensitive colored curable composition according to any one of <1> to <5>, exposing through a mask, and developing to form a pattern image. Manufacturing method.

<8> A dipyrromethene-based boron complex compound represented by the following general formula (I) and its compatible isomers.

In general formula (I), R ¹ , R ² , R ⁵ and R ⁶ each independently represent a hydrogen atom or a substituent, and at least one of R ¹ and R ⁶ is an amino group, a carbonamido group, or a ureido A group, an alkoxycarbonylamino group, or an imide group, and at least one of R ² and R ⁵ represents a cyano group or the structural formula. R ³ and R ⁴ each independently represents a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. X ¹ and Y ¹ each independently represent a halogen atom, an alkoxy group, an aryloxy group, a hydroxyl group, an alkylthio group, an arylthio group, or a heterocyclic thio group.

According to the present invention, a dipyrromethene-based boron complex compound that is useful for primary color filters arranged in blue, green, and red, has excellent color purity, has a high extinction coefficient, and is excellent in fastness, and tautomerism thereof. And a photosensitive colored curable composition containing the boron complex compound and its tautomer and capable of being thinned.
In addition, according to the present invention, it is possible to provide a blue photosensitive colored curable composition that is excellent in blue color purity, has a high extinction coefficient capable of being thinned, and is excellent in fastness.
Furthermore, it is possible to provide a color filter using a photosensitive colored curable composition that is excellent in color purity, can be thinned, and is excellent in fastness, and a method for producing the same.

Below, the photosensitive coloring curable composition of this invention, the dipyrromethene type | system | group boron complex compound which can be used in the composition, its tautomer, a color filter, and the manufacturing method of a color filter are explained in full detail.
<< Photosensitive colored curable composition >>
The photosensitive colored curable composition of the present invention contains at least one dipyrromethene-based boron complex compound (hereinafter, appropriately referred to as “specific boron complex compound”) represented by the following general formula (I) as a colorant. It is characterized by doing. Among the “photosensitivity”, “ultraviolet sensitive” is preferable.

In general formula (I), R ^{1 to} R ⁶ each independently represent a hydrogen atom or a substituent, R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and X ¹ and Y ¹ each independently represent a halogen atom, an alkoxy group, an aryloxy group, a hydroxyl group, an alkylthio group, an arylthio group, or a heterocyclic thio group.

In general formula (I), the substituents in R ^{1 to} R ⁶ are, for example, a halogen atom (for example, fluorine, chlorine, bromine), an alkyl group (preferably having 1 to 48 carbon atoms, and more preferably having 1 to 48 carbon atoms). 24 linear, branched or cyclic alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl , Cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), an alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, such as vinyl, allyl, 3-butene-1- Yl), an aryl group (preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, , Phenyl, naphthyl), a heterocyclic group (preferably a C1-C32, more preferably a C1-C18 heterocyclic group such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), a silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, Trimethylsilyl, triethylsilyl, tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), hydroxyl group, cyano group, nitro group, alkoxy group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms). Alkoxy groups such as methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, A butoxy, dodecyloxy, cycloalkyloxy group, for example, cyclopentyloxy, cyclohexyloxy), an aryloxy group (preferably an aryloxy group having 6-48 carbon atoms, more preferably 6-24 carbon atoms, for example, phenoxy 1-naphthoxy), a heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 1-phenyltetrazol-5-oxy and 2-tetrahydropyranyl Oxy), a silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), an acyloxy group (preferably 2 to 48 carbon atoms, more preferably 2 to 2 carbon atoms 24 acyloxy groups such as acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), alkoxycarbonyloxy groups (preferably having 2 to 48 carbon atoms, more preferably having 2 to 24 carbon atoms, Ethoxycarbonyloxy, t-butoxycarbonyloxy, cycloalkyloxycarbonyloxy group, for example, cyclohexyloxycarbonyloxy), aryloxycarbonyloxy group (preferably having 7 to 32 carbon atoms, more preferably aryl having 7 to 24 carbon atoms) An oxycarbonyloxy group such as phenoxycarbonyloxy), a carbamoyloxy group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dimethyl). Carbamoyloxy, N- butylcarbamoyl-oxy, N- phenylcarbamoyloxy, N- ethyl -N- phenylcarbamoyloxy),
Sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy) An alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, such as methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy),

  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 phenylsulfonyloxy), an acyl group (preferably having 1 to 48 carbon atoms, more preferably carbon An acyl group having 1 to 24, for example, formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl), an alkoxycarbonyl group (preferably having 2 to 48 carbon atoms, more preferably an alkoxy having 2 to 24 carbon atoms) A carbonyl group, for example, methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl, a group represented by the following structural formula),

  An aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably an aryloxycarbonyl group having 7 to 24 carbon atoms, such as phenoxycarbonyl), a carbamoyl group (preferably having 1 to 48 carbon atoms, more preferably a carbon number). 1 to 24 carbamoyl groups such as carbamoyl, N, N-diethylcarbamoyl, N-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methyl-N- Phenylcarbamoyl, N, N-dicyclohexylcarbamoyl), amino group (preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as amino, methylamino, N, N-dibutylamino, tetra Decylamino, 2-ethylhexylamino, Rohexylamino), anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as anilino, N-methylanilino), a heterocyclic amino group (preferably having 1 to 32 carbon atoms, and more). Preferably it is a 1-18 heterocyclic amino group, for example, 4-pyridylamino), a carbonamido group (preferably a C2-48, more preferably 2-24 carbonamide group, for example, acetamide, benzamide, tetradecane. Amide, pivaloylamide, cyclohexaneamide), ureido group (preferably a ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as ureido, N, N-dimethylureido, N-phenylureido), imide Group (preferably an imide group having 36 or less carbon atoms, more preferably 24 or less carbon atoms) , For example, N-succinimide, N-phthalimide), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonylamino), aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, for example, phenoxy Carbonylamino), sulfonamide group (preferably a sulfonamide group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methanesulfonamide, butanesulfonamide, benzenesulfonamide , Hexadecanesulfonamide, cyclohexanesulfonamide), a sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dipropylsulfamoyl group). Amino, N-ethyl-N-dodecylsulfamoylamino), an azo group (preferably an azo group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, phenylazo, 3-pyrazolylazo),

  An alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably an alkylthio group having 1 to 24 carbon atoms, for example, methylthio, ethylthio, octylthio, cyclohexylthio), an arylthio group (preferably having 6 to 48 carbon atoms, more preferably An arylthio group having 6 to 24 carbon atoms, such as phenylthio, and a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic thio group having 1 to 18 carbon atoms, such as 2-benzothiazoli Ruthio, 2-pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably an alkylsulfinyl group having 1 to 24 carbon atoms, for example, dodecanesulfinyl group), an arylsulfinyl group ( Preferably it has 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms. An arylsulfonyl group (for example, phenylsulfinyl), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, Isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as phenylsulfonyl, 1-naphthylsulfonyl), a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as sulfamoyl, N, N-dipropylsulfa , N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl), sulfo group, phosphonyl group (preferably having 1 to 32 carbon atoms, more preferably carbon A phosphonyl group having 1 to 24 carbon atoms, for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), phosphinoylamino group (preferably having 1 to 32 carbon atoms, more preferably phosphino having 1 to 24 carbon atoms) Ilylamino group includes, for example, diethoxyphosphinoylamino, dioctyloxyphosphinoylamino).

When the substituents of R ^{1 to} R ⁶ are further substitutable groups, they may have the substituents described in R ^{1 to} R ⁶ , and have two or more substituents. These substituents may be the same or different.

R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and / or R ⁵ and R ⁶ are each independently bonded to each other to form a 5-membered, 6-membered, or 7-membered saturated ring, or A saturated ring may be formed. When the 5-membered, 6-membered, and 7-membered rings formed are further substitutable groups, they may be substituted with the substituents described for R ^{1 to} R ⁶ above. When substituted with a substituent, these substituents may be the same or different.

R ⁷ in the general formula (I) represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and the halogen atom, alkyl group, or aryl group described above for the substituents of R ^{1 to} R ^6. And the same group as the heterocyclic group, and the preferred range thereof is also the same.
When the alkyl group, aryl group, and heterocyclic group of R ⁷ are further substitutable groups, they may be substituted with the substituents described for the substituents of R ^{1 to} R ^6. When substituted with the above substituents, these substituents may be the same or different.

X ¹ and Y ¹ in the general formula (I) each independently represent a halogen atom, an alkoxy group, an aryloxy group, a hydroxyl group, an alkylthio group, an arylthio group, or a heterocyclic thio group. Preferred ranges of these halogen atoms, alkoxy groups, aryloxy groups, hydroxyl groups, alkylthio groups, arylthio groups, and heterocyclic thio groups are the same as those described for R ^{1 to} R ⁶ above.

In the case where X ¹ and Y ¹ in the general formula (I) are substitutable groups, they may be substituted with the groups described for the substituents of R ^{1 to} R ⁶ , and two or more substituents In the case where the substituent is substituted, the substituents may be the same or different.

Next, the preferable range of the compound represented by the general formula (I) will be described.
In general formula (I), R ¹ and R ⁶ are preferably each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, alkoxy group, aryloxy Group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfone Represents an amide group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group, and R ² and R ⁵ each independently represent a hydrogen atom, a halogen atom, Alkyl group, alkenyl group, aryl group, heterocyclic group, hydroxyl Group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkoxycarbonylamino group, sulfonamide group, azo group, An alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, or a group represented by the following structural formula; R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom; , Alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, anilino group, carbonamide Group, ureido group, imide group, alkoxy It represents Ruboniruamino group, a sulfonamido group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, or a phosphinoylamino group, R ⁷ is a hydrogen atom, a halogen It represents atom, an alkyl group, an aryl group, or a heterocyclic group, X ^1, and Y ¹ represents a fluorine atom, an alkoxy group, an aryloxy group.

More preferably, in the general formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, Amino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, azo group, alkylsulfonyl group, arylsulfonyl group, or phosphinoylamino group R ² and R ⁵ are each independently an alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, nitro group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, Alkylsulfonyl group, arylsulfonyl group, or sulfamoy R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, or an alkoxycarbonyl group. Carbamoyl group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, sulfonamido group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl group, R ⁷ Represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and X ¹ and Y ¹ represent a fluorine atom, an alkoxy group, or an aryloxy group.

Particularly preferably, in general formula (I), at least one of R ¹ and R ⁶ represents an amino group, a carbonamido group, a ureido group, an alkoxycarbonylamino group, or an imide group, and other than R ¹ and R ⁶ One of them is a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, heterocyclic amino group, carbonamido group, ureido group, imide Group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido group, an azo group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group, and at least one of R ² and R ⁵ is a cyano group , or a group represented by the following structural formula, another of R ² and R ⁵ are alkyl groups, alkenyl , Aryl group, heterocyclic group, cyano group, nitro group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl group, or the following structural formula R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and X ¹ and Y ¹ represent a fluorine atom, an alkoxy group, or an aryloxy group.

Most preferably, in the general formula (I), at least one of R ¹ and R ⁶ represents an amino group, another of R ¹ and R ⁶ are a hydrogen atom, an alkyl group, an alkenyl group, an aryl group , Heterocyclic group, cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group , an azo group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group, at least one of R ² and R ⁵ is represented by a group represented by the cyano group, or the formula, R ² , and another one of R ⁵ is an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acyl group, an alkoxycarbonyl Boniru group, an aryloxycarbonyl group, a carbamoyl group, an imido group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, or a group represented by the following structural formula, R ⁷ represents a methyl group or a hydrogen atom, X ¹ and Y ¹ represent a fluorine atom.

In general formula (I), R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and / or R ⁵ and R ⁶ are independently bonded to each other and have no substituent. In the case of forming a 5-membered, 6-membered, or 7-membered saturated ring or an unsaturated ring, examples of the 5-membered, 6-membered, or 7-membered saturated or unsaturated ring having no substituent include pyrrole Ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexene ring, benzene ring, pyridine ring, pyrazine ring, pyridazine ring, and the like. Preferably, a benzene ring and a pyridine ring are mentioned.
Also, if having a substituent, examples of the substituent, for example, the include substituents described in R ¹ to R ^6, the same preferred substituents also R ¹ to R ^6.
In addition, the compound represented by general formula (I) may be a tautomer.

The molar extinction coefficient of the specific boron complex compound in the present invention is preferably as high as possible from the viewpoint of film thickness. The maximum absorption wavelength λmax is preferably 520 nm to 570 nm, more preferably 530 nm to 570 nm, from the viewpoint of improving color purity. The maximum absorption wavelength and molar extinction coefficient are measured with a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation).
The melting point of the specific boron complex compound in the present invention is preferably not too high from the viewpoint of solubility.

  Next, specific boron complex compounds in the present invention (Exemplary compounds Ia-1 to Ia-19, Ib-1 to Ib-13, Ic-1 to Ic-17, II-1 to II-17, III-1 to III Specific examples of (-15, IIIa-1 to IIIa-47, IV-1 to IV-20) are shown below, but the present invention is not limited thereto.

The boron complex compounds represented by the above general formula (I) are disclosed in U.S. Pat. Nos. 4,774,339, 5,433,896, JP-A Nos. 2001-240761, 2002-155052, and JP 3614586. No., Aust. J. et al. Chem, 1965, 11, 1835-1845, J. Am. H. Boger et al, Heteroatom Chemistry, Vol. 1, No. 1 5,389 (1990) and the like.
Below, the synthesis example of exemplary compound (Ia-1, Ib-1, Ic-6, III-4) mentioned above is explained in full detail.

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

(Synthesis of Intermediate 1)
N-methylpyrrolidone (NMP) was added to 96.2 g (1.04 mol) of 300 ml of chloroacetone and stirred at 15 to 20 ° C. To this solution, 175 g (0.945 mol) of phthalimide potassium was added in several portions so that the temperature of the reaction solution was kept at 30 ° C. or lower. After completion of the addition, the reaction was completed by stirring at room temperature for 2 hours. After completion of the reaction, the reaction solution was poured into 3000 ml of water with stirring to precipitate crystals. The crystals were filtered, washed with water and dried. 163 g (yield: 84.9%) of intermediate 1 was obtained.

(Synthesis of Intermediate 2)
400 ml of toluene was added to 56.2 g (0.66 mol) of cyanoacetic acid and 136 g (0.6 mol) of 2,6-di-tert-butyl-4-methylcyclohexanol, followed by stirring at room temperature. To this solution, 53.5 ml of pyridine was added dropwise. Subsequently, 125 ml (0.132 mol) of acetic anhydride was added dropwise so as to keep the temperature of the reaction solution at 30 ° C. or lower. After completion of the dropwise addition, the reaction was completed by stirring at room temperature for 4 hours. This reaction solution was slowly added to an aqueous solution consisting of 110 g of sodium bicarbonate and 2000 ml of water. Subsequently, 1200 ml of ethyl acetate was added and extracted. The ethyl acetate solution was washed with water and then dried over anhydrous magnesium sulfate. The ethyl acetate solution was concentrated under reduced pressure, 400 ml of methanol was added to the residue, and the mixture was stirred to precipitate crystals. Further, 100 ml of water was added dropwise and stirred at room temperature for 1 hour. The crystals were filtered, washed with a mixed solution of methanol / water = 4/1, and dried. 137 g (yield: 77.8%) of intermediate 2 was obtained.

(Synthesis of Intermediate 3)
To 102 g (0.5 mol) of Intermediate 1 and 147 g (0.5 mol) of Intermediate 2 obtained by the above method, 500 ml of ethanol was added and cooled to 5 ° C. to 10 ° C. and stirred. To this dispersion, 201 ml of SM-28 (sodium methoxide 28% methanol solution) was added dropwise. The temperature of the reaction solution was kept at 10 ° C. or lower. After completion of the dropwise addition, the mixture was returned to room temperature and stirred for 30 minutes, and then 20 ml of water was added and stirred for 4 hours while heating under reflux. After completion of the reaction, the reaction solution was cooled to room temperature, and 750 ml of water was added dropwise to precipitate crystals. The crystals were filtered, washed with water and dried. The crystals were dispersed in 1000 ml of n-hexane, washed by stirring, filtered and dried. 143 g (yield: 82.2%) of intermediate 3 was obtained.

(Synthesis of Intermediate 4)
50 ml of acetic acid was added to 14.0 g (0.04 mol) of Intermediate 3 obtained by the above method and stirred at room temperature. To this solution, 3.3 g (0.022 mol) of triethyl orthoformate was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 12 hours. The precipitated crystals were filtered, washed with acetonitrile and dried. 9.5 g (yield: 67.2%) of intermediate 4 was obtained.
The molar absorption coefficient (ε) was 65400 at the maximum absorption wavelength (λmax = 531.7 nm) in an ethyl acetate solution. The melting point was 236-238 ° C.

(Synthesis of Exemplified Compound Ia-1)
To 7.07 g (0.01 mlo) of intermediate 4 obtained by the above method, 100 ml of dehydrated tetrahydrofuran was added and stirred at room temperature. To this solution, 1.8 g of 1,8-diazabicyclo [5.4.0] undecene (DBU) was added and stirred at room temperature, and then 32 ml of a trifluoroborane diethyl ether solution having a concentration of 46 to 49 wt% was added dropwise. The reaction solution was stirred at room temperature for 1 hour, and then heated to reflux and stirred for 5 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and slowly poured into 1500 ml of 3% sodium bicarbonate water while stirring. Subsequently, 500 ml of ethyl acetate was added and extracted. The ethyl acetate solution was washed with saturated brine and then dried over anhydrous magnesium sulfate. The ethyl acetate solution was concentrated under reduced pressure. The residue was separated and purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 2/1), crystals were precipitated from acetonitrile, filtered and dried. 4.2 g (yield: 55.6%) of Exemplary Compound Ia-1 was obtained. The maximum absorption wavelength of the visible part in ethyl acetate was 561.4 nm, and the extinction coefficient was 163300.

The ¹ H-NMR data of the obtained exemplary compound (Ia-1) is shown below.
¹ HNMR (CDCl ₃ )
6.94 (s, 1H), 6.80 to 6.45 (br, 4H), 6.00 (s, 2H), 2.48 (s, 6H), 1.75 to 1.63 (br, 4H), 1.60 to 1.45 (br, 4H), 1.35 to 1.15 (m, 6H), 1.02 (d, 6H), 0.88 (s, 36H)

-Synthesis Example 2-
(Synthesis of Exemplified Compound Ib-1)
Synthesis was performed according to the same method as in Synthesis Example 1.
In an ethyl acetate solution of Exemplified Compound Ib-1, λamx = 583.5 nm, and the extinction coefficient was 169500.

-Synthesis Example 3-
(Synthesis of Exemplified Compound 1c-6)
Synthesis was performed according to the same method as in Synthesis Example 1.
In an ethyl acetate solution of Exemplified Compound Ic-6, λamx = 588.1 nm, and the extinction coefficient was 163000.

(Synthesis of Exemplified Compound III-4)
Synthesized according to Reaction Scheme B below.

(Synthesis of Intermediate 7)
100 ml of dehydrated dimethylformamide (DMF) was cooled to 5 ° C. and stirred. To this solution, 14.0 ml of phosphorus oxychloride was added dropwise. After completion of dropping, the mixture was stirred at 5 ° C to 10 ° C for 30 minutes. To this solution, 32.2 g (0.1 mol) of Intermediate 6 synthesized according to the method described in JP-A-2000-63353 was added in several portions. The reaction temperature was kept at 5-10 ° C. After completion of the addition, the mixture was returned to room temperature and stirred for 1 hour. After completion of the reaction, the reaction solution was poured into 1000 ml of water with stirring, and then adjusted to a pH of 7 to 8 using a 2N aqueous sodium hydroxide solution. After stirring this solution at room temperature for 1 hour, the precipitated crystals were filtered, washed with water, and dried. 30.7 g (yield: 87.6%) of Intermediate 7 was obtained.

(Synthesis of Intermediate 9)
30 ml of acetic acid was added to 7.0 g (0.02 mol) of Intermediate 7 obtained by the above method and 8.2 g (0.02 mol) of Intermediate 8 synthesized according to the same method as in Synthesis Example 1, and stirred at room temperature. Next, 2 ml of trifluoroacetic acid was added to this solution and stirred at room temperature for 5 hours. After completion of the reaction, 20 ml of acetonitrile was added to the reaction solution and stirred. The precipitated crystals were filtered, washed with acetonitrile and dried. 12.3 g (yield: 82.7%) of intermediate 9 was obtained.

(Synthesis of Exemplified Compound III-4)
To 7.43 g (0.01 mol) of intermediate 9 obtained by the above method was added 60 ml of dehydrated tetrahydrofuran, and the mixture was stirred at room temperature. To this solution was added 2.3 g of DBU. Next, 15 ml of a 46% -49 wt% trifluoroborane diethyl ether solution was added dropwise. After completion of the dropwise addition, the mixture was heated and refluxed for 3 hours. After completion of the reaction, it was poured into 600 ml of water with stirring. Next, the mixture was neutralized with sodium bicarbonate and extracted by adding 500 ml of ethyl acetate. The ethyl acetate solution was washed with water and then dried over anhydrous magnesium sulfate. The ethyl acetate solution was concentrated under reduced pressure, and the residue was separated and purified by column chromatography (eluent: n-hexane / ethyl acetate = 2/1). 2-Propanol was added to precipitate crystals, and then filtered and dried. 5.32 g (yield: 67.3%) of Exemplary Compound III-4 was obtained. Λmax = 525.6 nm in ethyl acetate solution and ε = 79700.

The ¹ H-NMR data of the obtained exemplary compound (III-4) is shown below.
¹ HNMR (CDCl ₃ )
8.15 to 8.00 (br, 1H), 7.6 to 7.2 (m, 9H), 6.62 (s, 1H), 6.45 to 6.30 (br, 1H), 5. 90 (s, 1H), 4.05 (t, 2H), 3.07 (s, 3H), 2.36 (s, 3H), 1.35 to 1.13 (m, 6H), 1.07 ˜0.96 (m, 2H), 0.82 (s, 18H), 0.73 (d, 3H), 0.50 to 0.30 (m, 2H).

  In addition, it can synthesize | combine by the method similar to the above also about other exemplary compounds other than the exemplary compound Ia-1, Ib-1, Ic-6, and III-4 mentioned above.

  In the photosensitive colored curable composition of the present invention, each of the specific boron complex compounds may be used alone or in combination of two or more.

  The content of the specific boron complex compound in the present invention in the ultraviolet-sensitive colored curable composition varies depending on the molecular weight and the molar absorption coefficient, but is 0.5% relative to the total solid content component of the ultraviolet-sensitive colored curable composition. -80 mass% is preferable, 0.5-60 mass% is more preferable, 0.5-50 mass% is the most preferable.

<Tetraazaporphyrin-based cyan dye represented by formula (A)>
In addition to the specific boron complex compound, the photosensitive colored curable composition of the present invention includes a tetraazaporphyrin-based cyan dye represented by the following general formula (A) (hereinafter referred to as “specific dye-A” as appropriate). By using together, it is possible to produce a color filter having excellent color purity and fastness and using the photosensitive colored curable composition. In particular, it can be suitably used for CCDs and CMOSs.

In General Formula (A), M ¹ represents a metal or a metal compound, and Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently an atom selected from a carbon atom, a nitrogen atom, and a hydrogen atom. This represents an atomic group forming a configured 6-membered ring.
The metal or metal compound may be any metal or metal compound capable of forming a complex, and may be any divalent metal atom, divalent metal oxide, divalent metal hydroxide, or 2 Valent metal chlorides are included.

M ¹ in the general formula (A) is, for example, Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, etc., and AlCl, InCl, FeCl , TiCl ₂ , SnCl ₂ , SiCl ₂ , GeCl ₂ and other metal chlorides, TiO, VO and other metal oxides, and Si (OH) _{2 and} other metal hydroxides.
Z ¹ , Z ² , Z ³ , and Z ⁴ in the general formula (A) are each independently formed to form a 6-membered ring composed of atoms selected from a carbon atom, a nitrogen atom, and a hydrogen atom. Represents the necessary atomic group. The 6-membered ring may be a saturated ring or an unsaturated ring, and may be unsubstituted or have a substituent. Furthermore, other 5-membered or 6-membered rings may be condensed. The 6-membered ring includes a benzene ring, a cyclohexane ring, a pyridine ring, a pyrimidine ring, a pyrazine ring and the like.

  In the present invention, the maximum absorption wavelength λmax of the specific dye-A is preferably 580 nm to 700 nm, and more preferably 600 nm to 680 nm, from the viewpoint of improving color purity. In addition, the maximum absorption wavelength was measured similarly to the specific boron complex compound.

<Phthalocyanine dye represented by the following general formula (B)>
Of the tetraazaporphyrin dyes represented by the general formula (A), a phthalocyanine dye represented by the following general formula (B) (hereinafter, “specific dye-B” as appropriate) is particularly preferable.

In general formula (B), R ^{101 to} R ¹¹⁶ each independently represent a hydrogen atom or a substituent, and M ² represents a metal or a metal compound.

In the general formula (B), M ² is the same as the examples of M ¹ in the compound represented by Formula (A), is the same a preferred embodiment thereof.
In General Formula (B), R ^{101 to} R ¹¹⁶ each independently represents a hydrogen atom or a substituent, and the substituent represented by R ^{101 to} R ¹¹⁶ is R ¹ in General Formula (I) described above. to R ⁶ have the same meanings as illustrative of substituents represented by the same also its preferred embodiments. When the substituents R ^{101 to} R ¹¹⁶ of the compound represented by the general formula (B) are further substitutable groups, they may be substituted with the substituents described in the above R ^{1 to} R ⁶ , When substituted with two or more substituents, these substituents may be the same or different.

Hereinafter, examples (T-1 to T141) of the substituents R ^{101 to} R ¹¹⁶ of the specific dye-B are shown. However, the present invention is not limited to these.

Next, a preferable range of the phthalocyanine dye represented by the general formula (B) will be described.
The phthalocyanine dye represented by the general formula (B) has (R ¹⁰¹ and R ¹⁰⁴ ), (R ¹⁰⁵ and R ¹⁰⁸ ), and (R ¹⁰⁹ and R ¹¹² ) as α-substituents (α-substituents). , And (R ¹¹³ and R ¹¹⁶ ) have a substituent in at least one pair, or as β-substituents (β-substituents) (R ¹⁰² and R ¹⁰³ ), (R ¹⁰⁶ and R ¹⁰⁷ ) , (R ¹¹⁰ and R ¹¹¹ ), and (R ¹¹⁴ and R ¹¹⁵ ) have a substituent in at least one pair, or as substituents at the α-position and β-position, (R ¹⁰¹ and R ¹⁰³ And / or R ¹⁰² and R ¹⁰⁴ ), (R ¹⁰⁵ and R ¹⁰⁷ and / or R ¹⁰⁶ and R ¹⁰⁸ ), (R ¹⁰⁹ and R ¹¹¹ and / or R ¹¹⁰ and R ¹¹² ), and (R ¹¹³ and R ¹¹⁵ and / or R Among the combinations of ¹⁴ and R ^116), preferably it has at least one pair substituent.
Here, examples of the substituent represented by R ^{101 to} R ¹¹⁶ include a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, and an alkoxy group. Group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acyl group , Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, anilino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, sulfamoy Examples include amino group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, phosphonyl group, and phosphinoylamino group. . Examples of M ² include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, TiO, and VO.

As a preferable range of the phthalocyanine dye represented by the general formula (B), (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ) as an α-substituted product (mono-substituted product). , And (R ¹¹³ or R ¹¹⁶ ) have a substituent, or β-substitution (mono-substitution) (R ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ¹¹¹ ), and (R ¹¹⁴ or R ¹¹⁵ ).
Here, examples of the substituent represented by R ^{101 to} R ¹¹⁶ include a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, and an alkoxy group. Group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, anilino group, carbonamido group, ureido group, imide group, alkoxy Carbonylamino group, aryloxycarbonylamino group, sulfonamido group, sulfamoylamino group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, Rufamoiru group, a sulfo group, and a phosphinoylamino group. Examples of M ² include Zn, Pd, Cu, Ni, Co, TiO, and VO.

As a more preferable range of the phthalocyanine dye represented by the general formula (B), (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ) having a substituent in at least three of them, or (R ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ¹¹¹ ), and ( R ¹¹⁴ or R ¹¹⁵ ) is a compound having a substituent in at least three of them.
Here, examples of the substituent represented by R ^{101 to} R ¹¹⁶ include a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, and an aryl group. Oxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, anilino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, sulfo group Examples include a famoylamino group, an azo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, and a sulfo group. Examples of M ¹ include Zn, Pd, Cu, Ni, Co, and VO.

As a further preferable range of the phthalocyanine dye represented by the general formula (B), (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ) having the same substituent in at least three of them, or (R ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ¹¹¹ ) as β-substituents, And (R ¹¹⁴ or R ¹¹⁵ ) at least three of them have the same substituent.
Here, examples of the substituent represented by R ^{101 to} R ¹¹⁶ include a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a carboxyl group, a cyano group, an alkoxy group, an aryloxy group, and a heterocyclic oxy group. Groups, acyl groups, alkoxycarbonyl groups, carbamoyl groups, carbonamido groups, ureido groups, imide groups, sulfonamido groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, sulfamoyl groups, sulfo groups. . Examples of M ² include Zn, Pd, Cu, Ni, Co, and VO.

As a particularly preferable range of the phthalocyanine dye represented by the general formula (B), (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ) having substituents on at least three of them, or (R ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ¹¹¹ ), and (R ¹¹⁴ or R ¹¹⁵ ) has a substituent in at least three, and the substituents are all the same compound.
Here, examples of the substituent represented by R ^{101 to} R ¹¹⁶ include a halogen atom, an alkyl group, a heterocyclic group, a carboxyl group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkoxycarbonyl group, A carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, or a sulfo group can be mentioned. Examples of M ² include Zn, Pd, Cu, Ni, Co, and VO.

As the most preferable range of the phthalocyanine dye represented by the general formula (B), (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ) having substituents on at least three of them, or (R ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ¹¹¹ ), and (R ¹¹⁴ or R) as β-substituents ¹¹⁵ ) have a substituent, and all of the substituents are the same compound, and the substituents represented by R ^{101 to} R ¹¹⁶ include a halogen atom, an alkyl group, and a heterocyclic ring. Group, carboxyl group, alkoxy group, aryloxy group, heterocyclic oxy group, alkoxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group Group, a sulfamoyl group, or a sulfo group. Examples of M ² include Zn, Cu, Co, and VO.

  Specific examples (example compounds CA-1 to CA-46, CB-1) of tetraazaporphyrin dyes represented by the general formula (A) (including phthalocyanine dyes represented by the general formula (B)) are shown below. CB-46, CC-1 to CC-10, CK-1 to CK-19, CE-1 to CE-46, CF-1 to CF-46, CG-1 to CG-46, CI-1 to CI -46, and CH-1 to CH-46). However, the present invention is not limited to these.

-Synthesis example-
Next, a synthesis example of the dye represented by the general formula (A) or (B) will be described in detail with reference to the following scheme D by taking the synthesis of the exemplified compound CI-29 as an example.

(Synthesis of Intermediate A)
3-nitrophthalonitrile (25 g, 0.144 mol), DMSO (200 ml),
Sodium carbonate (16.5 g, 0.156 mol) was added to a mixture of 3-mercaptopropanesulfonic acid sodium salt (32 g, 0.18 mol), heated to 60 ° C. and stirred for 3 hours. The reaction mixture was poured into 10% brine (300 g), and the precipitated solid was collected by filtration and washed with an isopropanol / water (3/1) mixture. Water (200 ml), acetic acid (3 ml) and Na2WO4 (2 g) were added to the obtained solid, and 31% hydrogen peroxide (50 ml) was added, followed by heating and stirring at 60 ° C. After stirring for 4 hours, the reaction mixture was poured into isopropanol (500 ml), and the precipitated solid was collected by filtration and washed with an isopropanol / water (3/1) mixture. The solid obtained here was dried to obtain 24 g of intermediate A (yield from 3-nitrophthalonitrile 49%).

(Synthesis of Intermediate B)
200 ml of acetonitrile was added to 67.3 g (0.2 mol) of Intermediate A, and the mixture was heated to 70 ° C. to 75 ° C. and stirred. To this dispersion, 37 ml of phosphorus oxychloride was added dropwise. After completion of the dropwise addition, the reaction was completed by stirring at 70 to 75 ° C. for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature and poured into 2000 ml of water with stirring to precipitate crystals. The crystals were filtered and washed with water, and then dispersed in 300 ml of 2-propanol. The dispersion was stirred for 1 hour, then filtered and dried. 63.0 g (yield: 94,5%) of intermediate B was obtained.

(Synthesis of Intermediate C)
250 ml of acetonitrile was added to 50.0 g (0.15 mol) of the intermediate B obtained by the above method, and the mixture was cooled to 5 ° C. and stirred. To this solution, 31.0 g of 3-ethoxypropylamine was added dropwise. After completion of the dropwise addition, the mixture was returned to room temperature and stirred for 2 hours to complete the reaction. The reaction solution was poured into 1500 ml of water while stirring to precipitate crystals. The crystals were filtered and washed with water, and then dispersed in 500 ml of 2-propanol. The mixture was stirred at room temperature for 2 hours, filtered and dried. 52.6 g of intermediate C was obtained (yield: 87.7%).

(Synthesis of CI-29)
Intermediate C 799 g (0.02 mol), o-phthalonitrile 1.28 g (0.01 mol) obtained by the above-mentioned method, intermediate A 3.36 g (0.01 mol), diethylene glycol 30 ml, 2-methoxypropanol 100 ml was added and heated to 100 ° C. and stirred. To this solution was added 3.87 g ammonium benzoate and 1.26 g copper acetate. After completion of the addition, the mixture was stirred at 95 ° C to 100 ° C for 6 hours to complete the reaction. The reaction solution was cooled to room temperature, 60 ml of methanol was added, and 75 ml of hydrochloric acid was poured into an aqueous solution diluted with 800 ml of water while stirring. The precipitated crystals were filtered, washed with water and dried. The crystals were dissolved in 250 ml of methanol by heating and filtered to remove insoluble matters. The filtrate was concentrated under reduced pressure, and 250 ml of ethyl acetate was added to the residue and stirred. The dispersed crystals were filtered and dried. 24.7g (yield: 92.9%) of exemplary compound CI-29 was obtained. The maximum absorption wavelength and molar extinction coefficient of CI-29 in chloroform were λmax = 665.6 nm and ε = 84600, respectively.

  When the maximum absorption wavelength (λmax) and molar extinction coefficient (ε) of the obtained dye were measured with a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation), the maximum absorption wavelength λmax, molar extinction coefficient (Ε) were 623.4 nm and 47000, respectively.

  In addition, it can synthesize | combine by the method similar to the above about other exemplary compounds other than the pigment | dye CI-29 mentioned above.

  In the present invention, the maximum absorption wavelength λmax of the specific dye-B is preferably 580 nm to 700 nm, and more preferably 600 nm to 680 nm, from the viewpoint of improving color purity. The maximum absorption wavelength was measured with a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation).

<Pyrroazole azomethine dye represented by formula (C)>
In the present invention, in addition to the specific dye-A and the specific dye-B, a pyrroloazole azomethine dye represented by the following general formula (C) (hereinafter referred to as “specific dye-C” as appropriate) is preferable. It is possible to obtain a photosensitive colored curable composition having excellent color purity, particularly having a high transmittance of 450 nm or less, and a color filter using the composition. The color filter can be suitably used for a CCD, a CMOS, and the like.

In formula (C), R ^{50 to} R ⁵⁵ each independently represent a hydrogen atom or a substituent, and R ⁵⁶ and R ⁵⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or hetero Represents a cyclic group, and Za and Zb each independently represent -N = or -C ( ^R58 ) =. R ⁵⁸ represents a hydrogen atom or a substituent. R ⁵² and R ⁵³ , R ⁵³ and R ⁵⁷ , R ⁵⁴ and R ⁵⁵ , R ⁵⁵ and R ⁵⁶ , and / or R ⁵⁶ and R ⁵⁷ are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. It may be formed.

The substituents of R ^{50 to} R ^{55 in} the general formula (C) are synonymous with the groups described for the substituents of R ^{1 to} R ^{6 in} the general formula (I), and their preferred ranges are also the same.
When the substituents of R ^{50 to} R ^{55 in} the general formula (C) are further substitutable groups, they may be substituted with the groups described for the substituents of R ^{1 to} R ^6. When substituted with the above substituents, these substituents may be the same or different.
R ⁵⁶ and R ^{57 in} formula (C) each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. Alkyl group, an alkenyl group, an aryl group, and preferred ranges of the heterocyclic group, the alkyl group described for R ¹ to R ⁶ in the general formula (I), an alkenyl group, an aryl group, and synonymous with a heterocyclic group is there.
The alkyl group, alkenyl group, aryl group, and heterocyclic group of R ⁵⁶ and R ^{57 in} the general formula (C) may be further substituted with the substituents described in the above R ^{1 to} R ^6. When it is substituted with more than one substituent, these substituents may be the same or different.

Za and Zb in the general formula (C) each independently represent -N = or -C ( ^R58 ) =. R ⁵⁸ represents a hydrogen atom or a substituent. Substituents R ⁵⁸ are the same as the substituents described in Formula (I), and also the same preferred ranges thereof. When the substituent of R ⁵⁸ is a further substitutable group, it may have the substituent described in the general formula (I), and may be substituted with two or more substituents. These substituents may be the same or different.

The dyes represented by the general formula (C) are bonded to each other and R ⁵² and R ⁵³ , R ⁵³ and R ⁵⁷ , R ⁵⁴ and R ⁵⁵ , R ⁵⁵ and R ⁵⁶ , and / or R ⁵⁶ and R ⁵⁷ are bonded to each other. , 6 or 7 membered rings may be formed.

The specific dye-C is preferably such that R ⁵⁰ and R ⁵¹ are selected from the substituents described in the above R ^{1 to} R ⁶ , and the Hammett substituent constant σp value of the substituent represented by R ⁵⁰ and R ⁵¹ is This represents a substituent having a total sum of 0.7 or more, and R ⁵⁹ is represented by a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

  Hammett's law was established in 1935 by L. P. This is an empirical rule proposed by Hammett and is described in a general book. For example, J. et al. A. Dean, “Lange's and book of Chemistry”, 12th edition, 1979 (McGrew-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo). However, in the present invention, even if each substituent is limited or specified by Hammett's substituent constant σp value, it is not limited to only a substituent having a known document value that can be found in the above-mentioned booklet. Substituents whose values fall within the range when measured based on As for the “Hammett substituent constant σp value” in the present invention, the σp value is used as a scale indicating the electronic effect of a substituent even for a substituent that is not a benzene derivative, regardless of the substitution position.

  Examples of the electron-withdrawing group having a Hammett substituent constant σp value of 0.3 or more include an acyl group (preferably an acyl group having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms such as acetyl, pivaloyl, 2 -Ethylhexyl, benzoyl, cyclohexanoyl), acyloxy group (preferably an acyloxy group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, for example, acetoxy, pivaloyloxy), carbamoyl group (preferably having 1 to 24 carbon atoms, More preferably, it is a carbamoyl group of 1 to 18, for example, carbamoyl, N-methylcarbamoyl, N-ethylcarbamoyl, Nt-butylcarbamoyl, N-cyclohexylcarbamoyl, N-phenylcarbamoyl, N, N-diethylcarbamoyl, N , N-diisopropylcarbamoyl, N-ethyl- -Phenylcarbamoyl), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, cyclohexylcarbonyl), aryloxycarbonyl group ( Preferably an aryloxycarbonyl group having 7 to 24 carbon atoms, more preferably 7 to 18 carbon atoms, such as phenoxycarbonyl, cyano group, nitro group, alkylsulfinyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 1 carbon atoms). 18 alkylsulfinyl groups, for example, methylsulfinyl, ethylsulfinyl, butylsulfinyl, 2-ethylhexylsulfinyl, cyclopentylsulfinyl), arylsulfinyl groups (preferably having 6 to 6 carbon atoms) 24, more preferably an arylsulfinyl group having 6-18, for example, phenylsulfinyl, p-toluenesulfinyl), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1-24 carbon atoms, more preferably 1-18, , Methylsulfonyl, ethylsulfonyl, isopropylsulfonyl, cyclohexylsulfonyl), arylsulfonyl groups (preferably arylsulfonyl groups having 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, such as phenylsulfonyl, naphthylsulfonyl), sulfamoyl groups ( A sulfamoyl group having preferably 24 or less carbon atoms, more preferably 18 or less carbon atoms, such as N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-phenylsulfoyl. Moyl, N-cyclohexylsulfamoyl), halogenated alkyl group (preferably a halogenated alkyl group having 1 to 24 carbon atoms, more preferably 1 to 12, for example, trifluoromethyl, pentafluoropropyl), halogenated alkoxy A group (preferably a halogenated alkoxy group having 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms such as trifluoromethoxy), a halogenated aryloxy group (preferably having 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms). A halogenated aryloxy group, for example, pentafluorophenyloxy), a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1-12, such as 2-benzoxazoyl, 2-benzothiazolyl 1-phenyl-2-benzimidazolyl, 5-chloro-1-tetrazolyl, 1 It is possible to increase the pyrrolyl), and the like.

  Specific examples (CD-1 to CD-46) of the compound represented by the general formula (C) are shown below, but the present invention is not limited thereto.

  Synthesis of the compound represented by the general formula (C) is described in paragraphs [0070] to [0072] of JP-A-5-177959, paragraphs [0041] to [0054] of JP-A-2003-96326, It can be synthesized by the method described in paragraph numbers [0043] to [0056] of 2003-96327.

  In the present invention, the maximum absorption wavelength λmax of the specific dye-C is preferably 580 nm to 700 nm, more preferably 600 nm to 680 nm, from the viewpoint of improving color purity. The maximum absorption wavelength and molar extinction coefficient were measured with a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation).

The content in the case of containing the specific dye-A, specific dye-B, or specific dye-C varies depending on the molar extinction coefficient, required spectral characteristics, film thickness, etc., but the photosensitive coloring in the present invention. The content is preferably 1% by mass to 80% by mass and more preferably 10% by mass to 70% by mass with respect to the total solid content of the curable composition.
These colorants may be contained alone in the photosensitive colored curable composition of the present invention, or two or more kinds may be used in combination.

  The photosensitive colored curable composition of the present invention and the color filter using the photosensitive colored curable composition are triarylmethane-based having an absorption maximum at 550 nm to 650 nm in addition to the dye in the present invention. Coloring agents, for example, C.I. Acid Blue 7 (C.I. Acid Blue 7), C.I. Acid Blue 83, C.I. Acid Blue 90 (C.I. Acid Blue 90) ), CI Solvent Blue 38 (CI Solvent Blue 38), CI Acid Violet 17 (CI Acid Violet 17), CI Acid Violet 49 (CI Acid Violet 49). Violet 49), CI Acid Green 3 (CI Aci) d Green3) or the like can be used.

  Furthermore, a xanthene dye having an absorption maximum at 500 nm to 600 nm, such as C.I. Acid Red 289, can be used.

  Content of the said triarylmethane type | system | group coloring agent can be used in the range which does not impair the effect of this invention, and is 0.5 mass%-50% with respect to the total solid of the photosensitive coloring curable composition of this invention. It is preferable that it is mass%.

In order to produce a blue filter array, it is preferable to use a mixture of the specific boron complex compound and at least one of the specific dye-A, the specific dye-B, and the specific dye-C.
At this time, each mixing ratio varies depending on each molar extinction coefficient, required spectral characteristics, film thickness, etc., but in general, the content ratio (total content of the specific boron complex compound): The total content of the specific dye-A, the specific dye-B, and the specific dye-C) = 20: 1 to 1:20. Preferably it is used in the range of 10: 1 to 1:10.

<Binder>
The photosensitive colored curable composition of the present invention preferably contains at least one binder. The binder according to the present invention is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoint 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, JP-B 54-. No. 25957, JP-A-59-53836, JP-A-59-71048, etc., and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. There are polymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like, and acidic cellulose derivatives having a carboxylic acid in the side chain are particularly useful. In addition to this, an acid anhydride added to a polymer having a hydroxyl group, polyhydroxystyrene resin, polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. Is also useful.

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

  Other monomers having a hydrophilic group include tetrahydrofurfuryl group, phosphoric acid moiety, phosphate ester moiety, quaternary ammonium salt moiety, ethyleneoxy chain, propyleneoxy chain, sulfonic acid and its salt moiety, morpholinoethyl group, etc. Monomers are also useful.

In order to improve the crosslinking efficiency, a polymerizable group may be included in the side chain, and a polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is also useful.
Examples of the polymer having these polymerizable groups include KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.), and the like.
In order to increase the strength of the cured coating, alcohol-soluble nylon, polyether of 2,2-bis (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful.

  Among the various binders, the binder in the present invention is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance. From the viewpoint of control of developability, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable. Examples of the acrylic resin include a copolymer composed of monomers selected from benzyl (meth) acrylate, (meth) acryl, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and KS-resist-106 (Osaka Organic Chemical). Kogyo Co., Ltd.), Cyclomer P-series and the like are preferable.

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

  Specific examples of the novolak resin include, for example, a condensation product of metacresol, paracresol or a mixture thereof and formalin.

  The novolak resin may be adjusted in molecular weight distribution by means of fractionation or the like. Moreover, you may mix the low molecular weight component which has phenolic hydroxyl groups, such as bisphenol C and bisphenol A, with the said novolak resin.

The binder preferably has a mass average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 × 10 ⁵ , more preferably 2000 to 1 × 10 ⁵ , and 5000 to ⁵ × 10 ^4. The polymer is particularly preferred.
The amount of the binder used in the photosensitive colored curable composition of the present invention is preferably 10% by mass to 90% by mass, and 20% by mass with respect to the total solid content of the photosensitive colored curable composition of the present invention. -80 mass% is still more preferable, and 30 mass%-70 mass% is especially preferable.

<Crosslinking agent>
The photosensitive colored curable composition of the present invention contains the above-described specific boron complex compound as a colorant, has excellent color purity in comparison with the prior art, and has a high extinction coefficient that can be thinned, and Although it is the gist of the invention excellent in fastness, it is also possible to constitute such that a more highly cured film can be obtained by additionally using a crosslinking agent.

  The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, at least one selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. A melamine compound substituted with one group, a guanamine compound, a glycoluril compound, or a urea compound, (c) a phenol compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, naphthol A compound, or a hydroxyanthracene compound. Of these, polyfunctional epoxy resins are particularly preferred.

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

  The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in the crosslinking agent (b) is 2 to 6 in the case of melamine compounds, in the case of glycoluril compounds, guanamine compounds, and urea compounds. Although it is 2-4, Preferably it is 5-6 in the case of a melamine compound, and 3-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound.

  Hereinafter, the melamine compound, guanamine compound, glycoluril compound and urea compound of (b) are collectively referred to as a compound (methylol group-containing compound, alkoxymethyl group-containing compound, or acyloxymethyl group-containing compound) according to (b). There is.

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

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

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

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

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

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

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

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

  Examples of the skeletal compound in the crosslinking agent (c) include a phenol compound, a naphthol compound, a hydroxyanthracene compound, etc., in which the ortho-position or para-position of the phenolic OH group is unsubstituted. For example, phenol, cresol isomers, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol A, 4,4′-bishydroxybiphenyl, TrisP-PA (Honshu Chemical) Kogyo Co., Ltd.), naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, and the like are used.

  Specific examples of the crosslinking agent (c) include trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, trimethylol-3-cresol, tri ( Methoxymethyl) -3-cresol, a compound obtained by methoxymethylating one or two methylol groups of trimethylol-3-cresol, dimethylolcresol such as 2,6-dimethylol-4-cresol, tetramethylolbisphenol A, tetra Methoxymethyl bisphenol A, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethoxymethyl-4,4′-bishydroxybiphenyl, Tr Hexamethylol of sP-PA, hexamethoxymethyl of Tris P-PA, compounds in which 1 to 5 methylol groups have been methoxymethylated hexamethylol of Tris P-PA, Bis-hydroxymethyl naphthalene diol.

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

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

  When the crosslinking agent is contained, the content of the crosslinking agent (a) to (c) in the colorant-containing curable composition varies depending on the material, but with respect to the total solid content (mass) of the composition, 1-70 mass% is preferable, 5-50 mass% is more preferable, and 7-30 mass% is especially preferable. When the content is within the above range, a sufficient degree of curing and elution of the unexposed area can be maintained, and the degree of cure of the exposed area is not insufficient and the elution of the unexposed area is not significantly reduced. .

<Polymerizable monomer>
The photosensitive colored curable composition of the present invention can be suitably constituted by containing at least one polymerizable monomer. A polymerizable monomer is mainly contained when a photosensitive coloring curable composition is comprised in a negative type.
In addition, it can contain in the positive type | system | group containing the below-mentioned naphthoquinone diazide compound with the below-mentioned photoinitiator, and in this case, the hardening degree of the pattern formed can be promoted more. Hereinafter, the polymerizable monomer will be described.

  The polymerizable monomer is preferably a compound having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as anurate, glycerin and trimethylolethane, JP-B-48-41708, JP-B-50-6034, JP-A-51- Urethane acrylates as described in JP-B-37193, polyester acrylates and epoxy resins described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490 Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with (meth) acrylic acid, and mixtures thereof.

  Furthermore, the Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.

  The content of the polymerizable monomer in the photosensitive colored curable composition is preferably 0.1% by mass to 90% by mass, and 1.0% by mass with respect to the solid content in the photosensitive colored curable composition. -80% by mass is more preferable, and 2.0% by mass to 70% by mass is particularly preferable.

<Radiation sensitive compounds>
The photosensitive coloring curable composition of this invention can be comprised suitably by containing at least 1 type of a radiation sensitive compound. The radiation-sensitive compound according to the present invention is a compound capable of causing a chemical reaction such as radical generation, acid generation, and base generation with respect to UV light of 400 nm or less. It is used for the purpose of insolubilizing the coating film in an alkali developer by insolubilization by a reaction such as polymerization of a polymerizable monomer or oligomer present in the coating film or crosslinking of a crosslinking agent.

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

<Photopolymerization initiator>
Next, the photopolymerization initiator contained when the photosensitive colored curable composition of the present invention is a negative composition will be described.
The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable monomer, but is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.
In addition, you may further contain in the positive type | system | group containing said naphthoquinone diazide compound, In this case, the pattern hardening degree formed can be promoted more.
Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyloxadiazole compound, a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, an acetophenone compound, and Examples thereof include cyclopentadiene-benzene-iron complexes and salts thereof, and oxime compounds.

  Examples of active halogen compounds such as halomethyloxadiazole include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds described in JP-B-57-6096, 2-trichloromethyl-5, and the like. -Styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole and the like.

  Examples of the halomethyl-s-triazine compound include vinyl-halomethyl-s-triazine compounds described in JP-B-59-1281 and 2- (naphth-1-yl)-described in JP-A-53-133428. Examples include 4,6-bis-halomethyl-s-triazine compounds and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compounds.

  Other examples include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,6-bis (trichloromethyl) -4- (3,4-methylenedioxyphenyl)- 1,3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (1- p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphth-1-yl) -4,6 -Bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-) ) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2 -Methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis- Trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1- Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- ( 6-methoxy-naphtho- -Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7 -Dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2, 6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4 − [PN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl]- 2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonyl) Methylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophen Le] 2,6-di (trichloromethyl) -s-triazine,

  4- [m-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonyl) Methyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo -PN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbo) Rumethyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) ) -S-triazine, 4- [o-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-p- N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6 -Di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m Chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- ( m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6 -Di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl)- s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethyl) Aminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 -(M-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-chloroethylaminophenyl) -2,6 -Di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 (O-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl) -2,6- And di (trichloromethyl) -s-triazine.

Others, Midori Midori Kagaku TAZ series, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123, T series made by PANCHIM, T- OMS, T-BMP, TR, TB, Ciba Geigy's Irgacure series, Irgacure 369, Irgacure 784, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819, Irgacure 261, Darocur Series, Darocur 11734, 4′-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 2-benzyl-2-dimethylamino-4-morpholinotylophenone, 2,2-dimethoxy-2-phenyl Acetophenone, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4 , 5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- ( 2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diph Niruimidazoriru dimer, benzoin isopropyl ether are used also useful.
Particularly preferably, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- ( And oxime-O-acyl compounds such as 2-methylbenzoyl) -9H-carbazol-3-yl] ethanone.

In addition to the photopolymerization initiator, other known photopolymerization initiators can be used in combination with the photosensitive colored curable composition of the present invention.
Specifically, the vicinal polykettle aldonyl compound disclosed in US Pat. No. 2,367,660, disclosed in US Pat. Nos. 2,367,661 and 2,367,670. Substituted α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, α-hydrocarbons disclosed in US Pat. No. 2,722,512 Aromatic acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, disclosed in US Pat. No. 3,549,367. Triallylimidazole dimer / p-aminophenyl ketone combination, benzothiazole compound disclosed in Japanese Patent Publication No. 51-48516 / Triha And lomethyl-s-triazine compounds.

  The content of the photopolymerization initiator in the photosensitive colored curable composition is preferably 0.01 to 50% by mass, more preferably 1 to 30% by mass, and more preferably 1 to 20% with respect to the polymerizable monomer solid content. Mass% is particularly preferred. When the content is within the above range, the polymerization proceeds well and good film strength can be obtained.

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

  In addition to the above, it is preferable to add a thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4, 4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole and the like are useful.

-Naphthoquinonediazide compound-
Next, the naphthoquinone diazide compound contained when the photosensitive colored curable composition of the present invention is a positive type will be described.
The naphthoquinonediazide compound is a compound having at least one o-quinonediazide group. For example, o-naphthoquinonediazide-5-sulfonic acid ester, o-naphthoquinonediazide-5-sulfonic acid amide, o-naphthoquinonediazide-4- Examples thereof include sulfonic acid esters and o-naphthoquinonediazide-4-sulfonic acid amide. These esters and amide compounds can be produced by a known method using, for example, the phenol compound described in the general formula (I) in JP-A-2-84650 and JP-A-3-49437. .

  When the photosensitive colored curable composition of the present invention is configured as a positive type, the alkali-soluble phenol resin and the crosslinking agent are usually about 2 to 50% by mass and 2 to 30% by mass, respectively, in the organic solvent. It is preferable to dissolve at a certain ratio. The contents of the naphthoquinone diazide compound and the dye are usually added at a ratio of about 2% by mass to 30% by mass and 2% by mass to 50% by mass, respectively, with respect to the solution in which the binder and the crosslinking agent are dissolved. Is preferred.

<Solvent>
In preparing the photosensitive colored curable composition of the present invention, a solvent can generally be contained. The solvent used is not particularly limited as long as it satisfies the solubility of each component of the composition and the applicability of the photosensitive colored curable composition, but in particular, the solubility, applicability, and safety of the binder. Is preferably selected in consideration of
Specific examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, 3-oxypropionic acid 3-oxypropionic acid alkyl esters such as ethyl (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), methyl 2-oxypropionate, -2-oxypropionic acid alkyl esters such as ethyl oxypropionate and propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxypropion) Acid methyl, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methyl Ethyl propionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydro , 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 methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate Propylene glycol propyl ether acetate and the like; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; aromatic hydrocarbons such as toluene and xylene are preferred.

  Among these, 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 acetate Butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate and the like are more preferable.

<Various additives>
In the photosensitive colored curable composition of the present invention, various additives as necessary, for example, fillers, polymer compounds other than those mentioned above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, aggregation prevention An agent or the like can be added.

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

  In the case of promoting the alkali solubility of the area to be developed and removed (for example, the uncured portion in the case of a negative type) and further improving the developability of the photosensitive colored curable composition of the present invention. An organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less can be added to the composition. Specifically, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, glutar Aliphatic dicarboxylic acids such as acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as carbaryl acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acid, merophanic acid, pyromellitic acid; phenylacetic acid, Doroatoropa acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

  The photosensitive colored curable composition of the present invention is used for forming colored pixels such as color filters used in liquid crystal display elements (LCDs) and solid-state imaging elements (for example, CCDs, CMOSs, etc.), printing inks and inkjet inks. And can be suitably used as a production application for paints and the like. In particular, it can be suitably used for forming colored pixels for solid-state imaging devices such as CCDs and CMOSs.

≪Color filter and its manufacturing method≫
The color filter of the present invention will be described in detail through its manufacturing method.
In the method for producing a color filter of the present invention, the above-described photosensitive colored curable composition of the present invention is used. The color filter of the present invention forms a radiation-sensitive composition layer by applying the photosensitive colored curable composition of the present invention onto a support by a coating method such as spin coating, cast coating, roll coating, and the like. A negative or positive colored pattern (resist pattern) can be formed by exposing through the mask pattern and developing with a developer.
The exposure light source that can be applied to the photosensitive colored curable composition for color filters of the present invention is a light source having a wavelength of 400 nm or less, and is not particularly limited. For example, a xenon lamp, a halogen lamp, tungsten Lamp light sources such as lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arcs, fluorescent lamps, Ar ion lasers (364 nm, 351 nm, 10 mW to 1 W), Kr ion lasers (356 nm, 351 nm) 10 mW to 1 W), Nd: YAG (YVO 4) and SHG crystal × 2 combinations (355 nm, 5 mW to 1 W), waveguide wavelength conversion element and AlGaAs, waveguide wavelength conversion element and AlGaInP , Combinations of AlGaAs semiconductors (300 nm to 350 nm, N2 laser (337 nm, pulse 0.1-10 mJ), XeF (351 nm, pulse 10-250 mJ), etc. can be used as other pulse lasers, and optical filters are used when only specific wavelengths are used. You can also
Furthermore, ultraviolet rays such as ArF excimer laser (wavelength 193 nm), KrF excimer laser (wavelength 248 nm), i-line (wavelength 365 nm) can be used. An exposure light source that is particularly preferable from the viewpoints of cost and exposure energy is ultraviolet rays, and i-rays can be mentioned.
Furthermore, the formed pattern can be provided with a curing step for further curing by heating and / or exposure as necessary. As light or radiation used at this time, radiation such as i-line is particularly preferably used.

  In the production of the color filter of the present invention, in the case of the negative type, the image forming step (and the curing step if necessary) is repeated according to the desired number of colors, and in the case of the positive type, the image is obtained. By repeating the forming process and the post-baking process in accordance with the desired number of colors, a color filter configured with a desired number of hues can be created.

  As the above support, for example, 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 thereto, photoelectric conversion element substrates used for imaging elements, etc. A silicon substrate, a complementary metal oxide semiconductor (CMOS), etc. are mentioned. These supports may be formed with black stripes that separate pixels.

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

  The developer used in the method for producing the color filter of the present invention dissolves the region (uncured portion in the case of the negative type) to be developed and removed of the photosensitive colored curable composition of the present invention, while other than that Any material can be used as long as it has a composition that does not dissolve the region (hardened portion in the case of a negative type). Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. Examples of the organic solvent include the aforementioned solvents used in preparing the composition of the present invention.

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

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

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[Example 1]
1) Preparation of resist solution-Propylene glycol monomethyl ether acetate (PGMEA) 19.20 parts-Ethyl lactate 36.67 parts-Resin 30.51 parts [Benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (Molar ratio = 60: 22: 18) 40% PGMEA solution]
・ Dipentaerythritol hexaacrylate (photopolymerizable compound) 12.20 parts ・ Polymerization inhibitor (p-methoxyphenol) 0.0061 parts ・ Fluorine surfactant (F-475, manufactured by Dainippon Ink & Chemicals, Inc.) 0.83 parts, photopolymerization initiator 0.586 parts (TAZ-107 (trihalomethyltriazine-based photopolymerization initiator), manufactured by Midori Chemical Co., Ltd.)
Were mixed and dissolved to prepare a resist solution.

2) Production of glass substrate with undercoat layer A glass substrate (Corning 1737) was ultrasonically washed with 0.5% NaOH water, and then washed with water and dehydrated (200 ° C./20 minutes).
Next, the resist solution of 1) above was applied onto a cleaned glass substrate using a spin coater so as to have a film thickness of 2.0 μm, and dried by heating at 220 ° C. for 1 hour to obtain a cured film (undercoat layer). .

3) Preparation of colored resist solution (photosensitive colored curable composition [negative type]) A compound of the following composition A-1 was mixed and dissolved to prepare a colored resist solution A-1.
<Composition A-1>
・ Cyclohexanone 80.00 parts ・ Exemplary compound Ia-1 1.25 parts (dipyrromethene complex compound represented by formula (I))
-KARAYADA DPHA (Nippon Kayaku Co., Ltd., polymerization compound) 9.91 parts-Photopolymerization initiator (CGI-242 (Ciba Specialty Chemicals) 1.50 parts-Resin 7.32 parts (benzyl methacrylate) / Methacrylic acid copolymer, weight average molecular weight Mw = 28000, number average molecular weight Mn = 11000)

4) Formation of resist film Using the spin coater, the colored resist solution obtained in 3) above is formed on the undercoat layer of the glass substrate with the undercoat layer obtained in 2) so that the film thickness becomes 1.0 μm. This was applied and prebaked at 100 ° C. for 120 seconds to obtain a blue filter.

5) Evaluation The storage stability of the colored resist solution prepared above and the spectral characteristics of the coating film coated on the glass substrate using the colored resist solution were evaluated. The evaluation results are shown in Table 1 below.

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

-Transmittance evaluation-
The transmission spectrum of the color filter (blue filter) obtained as described above was measured, and the transmittance at 450 nm was evaluated. The larger the transmittance, the greater the amount of blue light transmitted, and the better the magenta dye or billet dye that can be used for the blue color filter.
<Criteria>
The transmittance at 450 nm when the transmittance at the maximum absorption wavelength of each dye was corrected (normalized) to 2% was determined.
○: 450 nm transmittance ≧ 90%
Δ: 80 ≦ 450 nm transmittance <90%
×: 450 nm transmittance <80%

[Examples 2-31]
The same procedure as in Example 1 was performed except that Exemplified Compound Ia-1 was replaced with an equimolar amount of the Exemplified Compound in Table 1 below in the preparation of 3) colored resist solution in Example 1. The results are shown in Table 1.

[Comparative Examples 1-3]
The same procedure as in Example 1 was performed except that Example Compound Ia-1 was changed as shown in Table 1 below in the preparation of the 3) colored resist solution of Example 1. The results are shown in Table 1.

  From the results of Table 1, the ultraviolet-sensitive colored curable compositions of the examples were superior in storage stability in the solution state as compared with the comparative examples using the comparative compounds. The image formed using the ultraviolet-sensitive colored curable composition containing the colorant according to the present invention provides a magenta image or violet image having excellent transmittance of 450 nm, and is a magenta for a blue color filter. It was found to be highly useful as a pigment or violet pigment.

[Example 32]
B) Preparation of colored resist solution (photosensitive colored curable composition) A compound of the following composition A-2 was mixed and dissolved to prepare a colored resist solution A-2.
<Composition A-2>
・ Cyclohexanone 80.00 parts ・ Exemplary compound Ia-1 3.84 parts (dipyrromethene complex compound represented by formula (I))
Exemplified compound CI-29 8.16 parts (phthalocyanine dye represented by formula (B))
-KARAYAD DPHA (manufactured by Nippon Kayaku Co., Ltd., polymerizable compound) 4.91 parts-Photopolymerization initiator CGI-242 (manufactured by Ciba Specialty Chemicals) 1.50 parts-Resin 0.98 parts (benzyl methacrylate) / Methacrylic acid copolymer, weight average molecular weight Mw = 28000, number average molecular weight Mn = 11000)
・ Dicyclohexylmethylamine 0.61 part ・ Surfactant (F-781, manufactured by Dainippon Ink & Chemicals, Inc.) 0.02 part

B) Application, exposure and development of colored resist solution The colored resist solution A-2 prepared in the above a) is applied on the undercoat layer of the glass substrate with an undercoat layer obtained in the same manner as 2) of Example 1. The coating film was applied so that the dry film thickness was 1.0 μm to form a photocurable coating film. And it heat-processed for 120 second (prebaking) using the 100 degreeC hotplate, and obtained the blue filter.

Next, using an exposure apparatus, the coating film was irradiated with an exposure dose of 500 mJ / cm ² through a mask having a wavelength of 365 nm and a line width of 20 μm. After the exposure, development was performed using a 60% CD-2000 (manufactured by FUJIFILM Electronics Materials) developer at 25 ° C. for 40 seconds. Then, after rinsing with running water for 30 seconds, spray drying was performed.
As described above, a pattern suitable for a blue color filter was obtained.

C) Evaluation The storage stability of the colored resist solution A-2 prepared above and the heat resistance and light resistance of the coating film applied on the glass substrate were evaluated as follows. The evaluation results are shown in Table 2 below.

<Storage stability>
After the colored resist solution A-2 was stored at room temperature for one month, the degree of visual precipitation of foreign matters was visually evaluated according to the following criteria.
~ Criteria ~
○: No precipitation was observed.
Δ: Slight precipitation was observed.
X: Precipitation was recognized.

<Heat resistance>
The glass substrate coated with the colored resist solution A-2 was heated at 200 ° C. for 1 hour with a hot plate, and then the ΔEab value of the color difference before and after the heat resistance test was measured with a chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics). The evaluation was made according to the following criteria. A smaller ΔEab value indicates better heat resistance.
~ Criteria ~
○: ΔEab value <5 or less Δ: 5 ≦ ΔEab value ≦ 10
×: 10 <ΔEab value

<Light resistance>
The glass substrate coated with the colored resist solution A-2 was irradiated with a xenon lamp at 50,000 lux for 20 hours (equivalent to 1 million lux · h), and then the ΔEab value of the color difference before and after the light resistance test was measured. The smaller the ΔEab value, the better the light resistance.
~ Criteria ~
○: ΔEab value <5
Δ: 5 ≦ ΔEab value ≦ 10
×: 10 <ΔEab value

[Examples 33 to 59]
For the preparation of the colored resist solution A-2 of Example 32, Exemplified Compound Ia-1 which is a dipyrromethene-based boron complex compound and Exemplified Compound CI-29 which is a phthalocyanine-based dye are each equimolar to the compounds in Table 2 below. All operations were performed in the same manner as in Example 32 except that However, in Examples 52 to 59, the contents of Exemplified Compound Ia-1 and Ib-1 were each changed to ½ molar amount of Ia-1 in Example 32. The results are shown in Table 2.

  From the results of Table 2, the UV-sensitive colored curable composition using the colorant according to the present invention has excellent storage stability in the resist solution, and the blue spectral characteristics ( A film suitable for a color filter excellent in color separation can be obtained. Furthermore, it was found that the film was excellent in heat resistance and light resistance and excellent in image forming properties.

[Examples 60 to 85]
-Application, exposure and development of resist solution (image formation)-
A) Preparation of resist solution A resist solution was prepared in the same manner as in Example 1).
B) Production of silicon wafer substrate with undercoat layer A 6-inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, on this silicon wafer, the resist solution prepared in 1) of Example 1 was applied using a spin coater so as to have a film thickness of 1.0 μm, and further heated and dried in an oven at 220 ° C. for 1 hour. An undercoat layer was formed to obtain a silicon wafer substrate with an undercoat layer.

The colored resist solution used in Examples 32 to 59 is applied on the undercoat layer of the silicon wafer substrate with the undercoat layer obtained in (b) so as to have a dry film thickness of 1.0 μm, and is photocurable. The coating film was formed. And the heat processing (prebaking) were performed for 120 second using a 100 degreeC hotplate so that the dry film thickness of this coating film might be set to 0.6 micrometer. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Co., Ltd.), an exposure dose of 100 mJ / cm in the range of 100 to 2500 mJ / cm ² through an island pattern mask having a pattern of 1.2 μm square at a wavelength of 365 nm. Irradiation was carried out while changing by ² cm ² . Thereafter, the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type; manufactured by Chemitronics Co., Ltd.), and CD-2000 (FUJIFILM Corporation). Using paddle development for 60 seconds at 23 ° C. using Electronics Materials Co., Ltd., a blue colored pattern was formed on the silicon wafer substrate.

  The silicon wafer substrate on which the blue colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and pure water is ejected from above the rotation center while rotating the silicon wafer substrate at a rotation speed of 50 rpm by a rotating device. A rinsing process was carried out by supplying from a nozzle in the form of a shower, followed by spray drying to obtain a blue filter.

  The formed blue pattern image showed a favorable profile in which a square section having a film thickness of 0.6 μm, which is suitable for an image sensor, was rectangular.

[Example 86]
1) Preparation of a colored resist solution (UV-sensitive colored curable composition [positive type]) 30 parts of ethyl lactate (EL) 3.0 parts of the following resin P-1 1.8 naphthoquinone diazide compound N-1 1.8 Part / Crosslinking agent: Hexamethoxymethylolated melamine 0.6 part / Photoacid generator: TAZ-107 (manufactured by Midori Chemical) 1.2 parts / Fluorine-based surfactant (F-475, Dainippon Ink and Chemicals) 0 .0005 part / dye: 0.3 part of exemplary compound Ia-1 (dipyrromethene-based boron complex compound represented by general formula (I))
Dye: Exemplified compound CI-29 0.8 part (phthalocyanine dye represented by formula (B))
The above were mixed and dissolved to obtain a positive colored resist solution.

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

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

3) Synthesis of naphthoquinone diazide compound (N-1) Trispamine PA (Honshu Chemical Co., Ltd.) 42.45 g, o-naphthoquinone diazide-5-sulfonyl chloride 61.80 g, and acetone 300 ml were charged into a three-necked flask and triethylamine at room temperature. 44 g was added dropwise over 1 hour. After completion of dropping, the mixture was further stirred for 2 hours, and then the reaction solution was poured into a large amount of water while stirring. Precipitated naphthoquinone diazide sulfonate was collected by suction filtration and dried in vacuo at 40 ° C. for 24 hours to obtain photosensitive compound N-1.

  When the storage stability of the photosensitive colored curable composition using the colorant in the present invention, the heat resistance of the coated composition, and the light resistance were evaluated in the same manner as in Example 32, the storage stability was excellent, the heat resistance, It was found that the light resistance was good.

Claims (8)

A photosensitive colored curable composition containing a dipyrromethene-based boron complex compound represented by the following general formula (I) as a colorant.

[In General Formula (I), R ^{1 to} R ⁶ each independently represent a hydrogen atom or a substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, X ¹ and Y ¹ each independently represent a halogen atom, an alkoxy group, an aryloxy group, a hydroxyl group, an alkylthio group, an arylthio group, or a heterocyclic thio group. ] In the general formula (I), at least one of R ¹ and R ⁶ represents an amino group, a carbonamido group, a ureido group, an alkoxycarbonylamino group, or an imide group, and at least one of R ² and R ⁵ represents The photosensitive colored curable composition according to claim 1, which represents a cyano group or a structural formula shown below.

The photosensitive colored curable composition according to claim 1 or 2, further comprising a tetraazaporphyrin-based cyan dye represented by the following general formula (A).

[In General Formula (A), M ¹ represents a metal or a metal compound, and Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently an atom selected from a carbon atom, a nitrogen atom, and a hydrogen atom. Represents an atomic group necessary for forming a 6-membered ring composed of ] 4. The photosensitive colored curable composition according to claim 3, wherein the tetraazaporphyrin-based cyan dye represented by the general formula (A) is a phthalocyanine-based dye represented by the following general formula (B). object.

[In General Formula (B), R ^{101 to} R ¹¹⁶ each independently represent a hydrogen atom or a substituent, and M ² represents a metal or a metal compound. ] The photosensitive coloring curable composition according to any one of claims 1 to 4, further comprising a cyan dye represented by the following general formula (C).

[In General Formula (C), R ^{50 to} R ⁵⁵ each independently represent a hydrogen atom or a substituent, and R ⁵⁶ and R ⁵⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or Represents a heterocyclic group, and Za and Zb each independently represent —N═ or —C (R ⁵⁸ ) ═. R ⁵⁸ represents a hydrogen atom or a substituent. R ⁵² and R ⁵³ , R ⁵³ and R ⁵⁷ , R ⁵⁴ and R ⁵⁵ , R ⁵⁵ and R ⁵⁶ , and / or R ⁵⁶ and R ⁵⁷ are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. May be. ]   The color filter which uses the photosensitive coloring curable composition of any one of Claims 1-5.   A method for producing a color filter, comprising: applying a photosensitive colored curable composition according to any one of claims 1 to 5, exposing through a mask, and developing to form a pattern image. . A dipyrromethene-based boron complex compound represented by the following general formula (I) and its compatible isomers.

[In General Formula (I), R ¹ , R ² , R ⁵ and R ⁶ each independently represents a hydrogen atom or a substituent, and at least one of R ¹ and R ⁶ is an amino group, a carbonamido group, It represents a ureido group, an alkoxycarbonylamino group, or an imide group, and at least one of R ² and R ⁵ represents a cyano group or the above structural formula. R ³ and R ⁴ each independently represents a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. X ¹ and Y ¹ each independently represent a halogen atom, an alkoxy group, an aryloxy group, a hydroxyl group, an alkylthio group, an arylthio group, or a heterocyclic thio group. ]