TW201412711A - Colored curable composition, colored cured film, color filter and production method thereof, display apparatus, solid-state imaging device, and compound - Google Patents

Abstract

A colored curable composition is provided, which has excellent storage stability and can be used to obtain a colored cured film and a color filter having excellent heat resistance, brightness, contrast and pattern shapes. The colored curable composition contains: a polymerizable compound, and at least one selected from groups consisting of a compound represented by the following general formula (I) and a tautomer thereof.

Description

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

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

Conventionally, a color filter is manufactured by using a pigment dispersion composition containing a organic pigment or an inorganic pigment as a colorant, a polymerizable compound, a polymerization initiator, an alkali-soluble resin, and the like. The colored curing composition of the component is formed by a pattern forming method such as photolithography or an inkjet method to form a colored pattern.

In recent years, for display element applications such as liquid crystal display (LCD), color filters have a tendency to be used not only for monitors but also for use in televisions (TVs). With the expansion of this use, for color filters, in terms of chromaticity, contrast, etc. Find the color characteristics of the height. In addition, in color filters used for image sensors (solid-state imaging devices), it is also required to reduce color unevenness and enhance color resolution such as color resolution.

The colored curable composition containing the conventional pigment dispersion composition is liable to cause problems such as generation of scattering by coarse particles of the pigment or increase in viscosity due to poor dispersion stability, and it is difficult to further improve the contrast and brightness.

Therefore, the use of a dye in place of a pigment as a coloring agent has been studied (for example, refer to Japanese Laid-Open Patent Publication No. Hei 6-75375). When a dye is used, it is advantageous from the viewpoint that the color purity of the dye itself or the vividness of the color tone thereof can improve the hue or brightness of the display image when the image is displayed, and the coarse particles disappear. Increase the contrast.

Dyes which are expected to be used for the above purposes have the following properties. In other words, it has a good color tone in terms of color reproduction, excellent in spectral absorption, heat resistance, light resistance, and the like, and is excellent in solubility in a solvent.

For example, Japanese Patent Publication No. 2008-292970 discloses a dipyrromethene dye which is useful for a colored curable composition for a color filter and has a color. It is excellent in purity, has a high molar absorption coefficient, and is excellent in firmness. Further, Japanese Patent Publication No. 2010-85454 discloses a dipyrromethene dye which is useful for a colored curable composition for a color filter and has a high molar. A color hardening composition excellent in developability can be obtained by the light absorption coefficient.

However, as a color filter for making display elements or solid-state elements A pigment which is contained in the colored curable composition of the light sheet is desirably desired to have a dye having a high molar absorption coefficient and further improved solubility and heat resistance.

Further, it is highly desirable that the color stability of the color-curable composition containing the above-mentioned known dye is excellent, and the heat stability (heat resistance) and brightness of the color filter produced using the color filter are excellent. A color hardening composition excellent in contrast and pattern shape.

According to one aspect of the present invention, an object of the present invention is to provide a coloring curable composition which is excellent in storage stability and which has heat resistance, brightness, contrast, and A colored cured film excellent in pattern shape.

According to another aspect of the present invention, an object of the invention is to provide a colored cured film using the colored curable composition, a color filter including the colored cured film, a method for producing the same, a display device using the color filter, and Solid photographic element.

According to still another aspect of the present invention, an object of the invention is to provide a compound which is useful for a colored curable composition for producing a color filter, has a high molar absorption coefficient, and is excellent in solubility and heat resistance.

Examples of the embodiments of the present invention are as follows.

<1> A colored curable composition comprising at least one selected from the group consisting of a polymerizable compound and a compound selected from the group consisting of a compound represented by the following formula (I) and a tautomer thereof.

[In the general formula (I), R ² to R ⁵ each independently represent a hydrogen atom or a monovalent substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. M represents a metal or a metal compound, X ¹ represents a group required for neutralizing the charge of M, and a represents 0, 1, or 2. When a is 2, a plurality of X ¹ may be the same or different. R ⁸ to R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent. Among them, at least two of R ⁸ to R ¹⁰ represent a monovalent substituent. R ¹¹ to R ¹⁴ each independently represent a hydrogen atom or a monovalent substituent. X ² represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group), and oxygen An atom, or a sulfur atom, R ¹⁶ represents a hydrogen atom or a monovalent substituent]

<2> The color hardening composition according to <1>, wherein the coloring composition is selected from the above At least one of the group consisting of the compound represented by the formula (I) and a tautomer thereof is selected from the group consisting of a compound represented by the following formula (II) and a tautomer thereof. At least one of them.

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

<3> The colored curable composition according to <1> or <2>, which further comprises a photopolymerization initiator.

The colored curable composition according to any one of <1> to <3>, further comprising at least one selected from the group consisting of a pigment and a cerium compound.

<5> The colored curable composition according to <4>, wherein the hydrazine compound is a compound represented by the following formula (IX).

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

The colored curable composition according to any one of <1> to <5>, wherein the compound represented by the above formula (I) and the mutual mutation thereof are selected from the total solid content of the composition. The content of at least one of the groups consisting of the structures is in the range of 0.1% by mass or more and 30% by mass or less.

<7> A color-hardening film which is obtained by hardening the color hardening composition as described in any one of <1> to <6>.

<8> A color filter comprising the colored hardening film according to <7>.

<9> A method of manufacturing a color filter, comprising: as <1> to < (6) The step of forming a color-curable composition layer on a support by applying the color-curable composition according to any one of the above aspects, and exposing the colored curable composition layer to a pattern and developing the color-curable composition layer A step of forming a colored pattern.

<10> A display device comprising the color filter according to <8> or a color filter produced by the method of manufacturing the color filter according to <9>.

<11> A solid-state imaging element comprising the color filter according to <8> or a color filter produced by the method of producing a color filter according to <9>.

<12> A compound selected from the group consisting of a compound represented by the following formula (I) and a tautomer thereof.

[In the general formula (I), R ² to R ⁵ each independently represent a hydrogen atom or a monovalent substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. M represents a metal or a metal compound, X ¹ represents a group required for neutralizing the charge of M, and a represents 0, 1, or 2. When a is 2, a plurality of X ¹ may be the same or different. R ⁸ to R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent. Among them, at least two of R ⁸ to R ¹⁰ represent a monovalent substituent. R ¹¹ to R ¹⁴ each independently represent a hydrogen atom or a monovalent substituent. X ² represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or a sulfur An atom, R ¹⁶ represents a hydrogen atom or a monovalent substituent]

<12> A compound selected from the group consisting of a compound represented by the following formula (II) and a tautomer thereof.

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

According to the present invention, there is provided a color-curable composition which is excellent in storage stability of the colored curable composition and which forms a colored cured film excellent in heat resistance, brightness, contrast, and pattern shape.

Further, according to the present invention, there is provided a colored cured film using the colored curable composition, a color filter including the colored cured film, a method for producing the same, and a display device and a solid-state imaging device using the color filter. .

Further, according to the present invention, there is provided a coloring matter which is useful for a coloring curable composition for producing a color filter, has a high molar absorption coefficient, and is excellent in solubility and heat resistance.

Hereinafter, the colored curable composition, colored cured film, and color of the present invention The color filter, the method of producing the color filter, the liquid crystal display device, the solid-state imaging device, and the dye are described in detail. The description of the constituent elements described below is based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

In addition, the numerical range represented by "~" in this specification is the range which contains the numerical value of the [~~.

In the present specification, the total solid content refers to the total content of all components of the color-curable composition other than the solvent which is a constituent component of the colored curable composition.

In the present specification, for example, "alkyl" means a "linear, branched or cyclic" alkyl group. Further, in the expression of the group (atomic group) in the present specification, the substituted and unsubstituted expressions are not described as including a group having no substituent (atomic group), and also a group having a substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). The same applies to groups other than alkyl groups.

In the present specification, "(meth)acrylate" means either or both of acrylate and methacrylate, and "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid. The "(meth)acrylonitrile group" means either or both of an acryloyl group and a methacryl group.

In addition, in this specification, "single quantity" and "monomer" have the same meaning. The monomer in the present invention is different from the oligomer and the polymer, and means a compound having a weight average molecular weight of 2,000 or less. In the present specification, a polymeric compound, It means a compound having a polymerizable functional group, and may be a single amount, an oligomer, or a polymer. The polymerizable functional group means a group which participates in a polymerization reaction.

In the present specification, the term "step" means not only an independent step, but also cannot be clearly distinguished from other steps, and is included in the term as long as the intended effect of the step is achieved.

In the present invention, the term "radiation" means visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray.

Colored hardening composition

The colored curable composition of the present invention contains at least one selected from the group consisting of a compound represented by the following formula (I) and a tautomer thereof (hereinafter, also referred to as "specific dipyrromethene" The metal complex ") preferably further contains a polymerizable compound and a photopolymerization initiator.

Further, the colored curable composition may be further composed of an alkali-soluble binder and an organic solvent, and may be formed using various additives.

Further, the colored curable composition may further contain at least one coloring agent selected from the group consisting of dyes having other structures different from the specific dipyrromethene metal complex and pigments.

a compound represented by the formula (I) and a tautomer thereof

The specific dipyrromethene metal complex of the present invention is at least one compound selected from the group consisting of a compound represented by the following formula (I) and a tautomer thereof.

In the formula (I), R ² to R ⁵ each independently represent a hydrogen atom or a monovalent substituent; R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group; and M represents a metal or a metal compound. X ¹ represents a group required for neutralizing the charge of M; a represents 1 or 2; when a is 2, a plurality of X ¹ may be the same or different; and R ⁸ to R ¹⁰ each independently represent a hydrogen atom; Or a monovalent substituent; wherein at least two of R ⁸ to R ¹⁰ represent a monovalent substituent; R ¹¹ to R ¹⁴ each independently represent a hydrogen atom or a monovalent substituent; and X ² represents NR (R) Represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or a sulfur atom; R ¹⁶ represents hydrogen Atom or a monovalent substituent.

The compound represented by the above formula (I) may also be a tautomer.

In the present invention, the tautomer may be any tautomer as long as it is a compound which can be formed by the movement of one hydrogen atom in the molecule. The tautomer of the compound represented by the above formula (I) includes, for example, a compound having the following structures (a) to (f).

In the above formulae (a) to (f), the meanings of R ² to R ⁵ , R ⁷ to R ¹⁴ , R ¹⁶ , X ¹ , X ² , M, and a are respectively in the formula (I) R ² to R ⁵ , R ⁷ to R ¹⁴ , R ¹⁶ , X ¹ , X ² , M and a are the same, and preferred ranges are also the same.

The above structure is an example of a tautomeric structure, and various isomer structures can be obtained by the structures of R ² to R ⁵ , R ⁷ to R ¹⁴ , R ¹⁶ , X ¹ , X ² , and M.

For example, when X ¹ is a monovalent group derived from butylenediamine, two kinds of isomer structures represented by the following general formula (g) and general formula (h) can be further considered.

In the above formula (g) and formula (h), the meanings of R ² to R ⁵ , R ⁷ to R ¹⁴ , R ¹⁶ , X ¹ , X ² and M and R ² ~ in the formula (I) R ⁵ , R ⁷ to R ¹⁴ , R ¹⁶ , X ¹ , X ² and M are the same.

The specific dipyrromethene metal complex of the present invention is chemically characterized by having both of -CR ⁸ R ⁹ R ¹⁰ and -X ² -R ¹⁶ . By having both of the above bases, it has excellent characteristics of high solubility and high heat resistance.

Hereinafter, the specific dipyrromethene metal complex of the present invention will be described below using a compound having a structure represented by the formula (I).

Regarding R ² to R ⁵ in the general formula (I)

The monovalent substituent represented by R ² to R ⁵ in the formula (I) represents a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom) or an alkyl group (preferably, the carbon number is 1~). a linear, branched or cyclic alkyl group of 48, more preferably a linear, branched or cyclic alkyl group having a carbon number of 1 to 24, such as methyl, ethyl, propyl or isopropyl. Base, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecanyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norborn a base, a 1-adamantyl group, or the like, an alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably an alkenyl group having 2 to 18 carbon atoms, such as a vinyl group, an allyl group, or a 3- Buten-1-yl), aryl (preferably an aryl group having a carbon number of 6 to 48, more preferably an aryl group having a carbon number of 6 to 24, such as a phenyl group or a naphthyl group) or a heterocyclic group (more) Preferred is a heterocyclic group having 1 to 32 carbon atoms, more preferably a heterocyclic group having 1 to 18 carbon atoms, such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1- Pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, or benzotriazol-1-yl), decylalkyl (preferably a decyl group having a carbon number of 3 to 38, more preferably for a decyl group having a carbon number of 3 to 18, such as a trimethyl decyl group, a triethyl decyl group, a tributyl decyl group, a tert-butyl dimethyl decyl group, or a third hexyl dimethyl decyl group, a hydroxy group, a cyano group, a nitro group, an alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably an alkoxy group having 1 to 24 carbon atoms), and examples thereof include a methoxy group and an ethoxy group. , 1-butoxy, 2-butoxy, isopropoxy, tert-butoxy, dodecyloxy or cycloalkoxy. Specific examples of the cycloalkoxy group include cyclopentyloxy Or a cyclohexyloxy group, an aryloxy group (preferably an aryloxy group having a carbon number of 6 to 48, more preferably an aryloxy group having a carbon number of 6 to 24, such as a phenoxy group or a 1-naphthyloxy group. a heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 32 carbon atoms, more preferably a heterocyclic oxy group having 1 to 18 carbon atoms, such as 1-phenyltetrazol-5-oxy group or a 2-tetrahydropyranyloxy group or the like, a decyloxy group (preferably a decyloxy group having a carbon number of 1 to 32, more preferably a decyloxy group having a carbon number of 1 to 18, such as a trimethylphosphoniumoxy group. , a tributyl dimethyl methoxy group, or a diphenylmethyl fluorenyloxy group, an alkylcarbonyloxy group (preferably an alkylcarbonyloxy group having a carbon number of 2 to 48, more preferably An alkylcarbonyloxy group having 2 to 24, such as an ethoxycarbonyl group, a trimethylethoxycarbonyl group or a dodecyloxy group, or an arylcarbonyloxy group (preferably having a carbon number of 7 to 32) An arylcarbonyloxy group, more preferably an arylcarbonyloxy group having a carbon number of 7 to 24, such as a benzamidineoxy group or an alkoxycarbonyloxy group (preferably an alkoxy group having a carbon number of 2 to 48) The carbonyloxy group is more preferably an alkoxycarbonyloxy group having 2 to 24 carbon atoms, and examples thereof include an ethoxycarbonyloxy group, a third butoxycarbonyloxy group, or a cycloalkoxycarbonyloxy group. Specific examples of the cycloalkoxycarbonyloxy group include a cyclohexyloxycarbonyloxy group and an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having a carbon number of 7 to 32, more preferably carbon). The number is 7 to 24, an aryloxycarbonyloxy group, for example, a phenoxycarbonyloxy group, an amine methyloxy group (preferably an aminomethyloxy group having a carbon number of 1 to 48, more preferably a carbon number) Aminomethyloxyl group of 1 to 24, such as N,N-dimethylamine methyl methoxy, N-butylamine methyl methoxy, N-phenylamine methyl methoxy, or N-ethyl- N-phenylamine methyl methoxy), amine sulfonyloxy (preferably a sulfonyloxy group having a carbon number of 1 to 32, more preferably an sulfonyloxy group having a carbon number of 1 to 24, for example N,N-diethylamine sulfonate a decyloxy group, or an N-propylamine sulfonyloxy group, an alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having a carbon number of 1 to 38, more preferably a carbon number of 1 to 24) Alkylsulfonyloxy, such as methylsulfonyloxy, hexylsulfonyloxy, or cyclohexylsulfonyloxy), arylsulfonyloxy (preferably having a carbon number of 6 to 32) a sulfonyloxy group, more preferably an arylsulfonyloxy group having a carbon number of 6 to 24, such as a phenylsulfonyloxy group, an alkylcarbonyl group (preferably an alkylcarbonyl group having a carbon number of 2 to 48, More preferably, it is an alkylcarbonyl group having a carbon number of 2 to 24, such as a methyl group, an ethyl fluorenyl group, a trimethylethyl fluorenyl group, a tetradecyl group or a cyclohexyl fluorenyl group, or an arylcarbonyl group (preferably a carbon). The arylcarbonyl group having a number of 7 to 32, more preferably an arylcarbonyl group having a carbon number of 7 to 24, such as a benzamidine group or an alkoxycarbonyl group (preferably an alkoxycarbonyl group having a carbon number of 2 to 48) More preferably, it is an alkoxycarbonyl group having a carbon number of 2 to 24, such as a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, or a 2,6-di-third tributyl group. a 4-methylcyclohexyloxycarbonyl group, an aryloxycarbonyl group (preferably an aryloxycarbonyl group having a carbon number of 7 to 32, more preferably an aryloxy group having a carbon number of 7 to 24) a carbonyl group such as a phenoxycarbonyl group, an amine methyl sulfonyl group (preferably an amine carbaryl group having a carbon number of 1 to 48, more preferably an amine carbaryl group having a carbon number of 1 to 24, such as an amine carbaryl group, N,N-diethylamine, fluorenyl, N-ethyl-N-octylamine, decyl, N,N-dibutylamine, N-phenylamine, N-benzene a base amine methyl sulfhydryl group, an N-methyl-N-phenylamine methyl fluorenyl group, or an N,N-dicyclohexylamine methyl fluorenyl group, an amine group (preferably an amine group having a carbon number of 32 or less, An amine group having a carbon number of 24 or less, such as an amine group, a methylamino group, an N,N-dibutylamino group, a tetradecylamino group, a 2-ethylhexylamino group or a cyclohexylamino group, an aniline a base (preferably an anilino group having a carbon number of 6 to 32, more preferably an anilino group of 6 to 24, such as an anilino group or an N-methylanilino group) or a heterocyclic amino group (preferably having a carbon number of 1) a heterocyclic amino group of ~32, more preferably a heterocyclic amino group having a carbon number of 1 to 18, such as a 4-pyridylamino group, or a carbonamide group (preferably having a carbon number of 2 to 48) The benzylamino group, more preferably a benzylamino group having a carbon number of 2 to 24, such as an acetamino group, a benzamide group, a tetradecyl fluorenyl group, or a trimethyl acetamidine group. Amino group or cyclohexyl Amidino), ureido (preferably a ureido group having a carbon number of 1 to 32, more preferably a ureido group having a carbon number of 1 to 24, such as a urea group, an N,N-dimethylureido group, or a N a -phenylureido group, a quinone imine group (preferably a quinone imine group having a carbon number of 36 or less, more preferably a quinone imine group having a carbon number of 24 or less, such as an N-succinimide group, or N-o-phthalimido), alkoxycarbonylamino (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably an alkoxycarbonyl group having 2 to 24 carbon atoms) Amine group, such as methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, octadecyloxycarbonylamino group or cyclohexyloxycarbonylamino group), aryloxycarbonyl group An amine group (preferably an aryloxycarbonylamino group having a carbon number of 7 to 32, more preferably an aryloxycarbonylamino group having a carbon number of 7 to 24, such as a phenoxycarbonylamino group) or a sulfonylamino group (preferably a sulfonamide group having a carbon number of 1 to 48, more preferably a sulfonamide group having a carbon number of 1 to 24, such as a methanesulfonylamino group, a butanesulfonylamino group or a benzenesulfonylamino group. , hexadecanesulfonylamino, or cyclohexanesulfonylamino), aminesulfonylamino (preferably aminosulfonylamino group having a carbon number of 1 to 48) More preferably, it is an aminesulfonylamino group having a carbon number of 1 to 24, such as N,N-dipropylaminesulfonylamino, or N-ethyl-N-dodecylsulfonylamino) An azo group (preferably an azo group having a carbon number of 1 to 32, more preferably an azo group having a carbon number of 1 to 24, such as a phenylazo group or a 3-pyrazolylazo group) An alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably an alkylthio group having 1 to 24 carbon atoms, such as methylthio, ethylthio, octylthio or cyclohexylsulfide) a thiol group (preferably an arylthio group having a carbon number of 6 to 48, more preferably an arylthio group having a carbon number of 6 to 24, such as a phenylthio group) or a heterocyclic thio group (preferably a carbon) a heterocyclic thio group of 1 to 32, more preferably a heterocyclic thio group having 1 to 18 carbon atoms, such as a 2-benzothiazolylthio group, a 2-pyridylthio group, or a 1-phenyltetrazoliumthio group. An alkylsulfinyl group (preferably an alkylsulfinyl group having a carbon number of 1 to 32, more preferably an alkylsulfinyl group having a carbon number of 1 to 24, such as dodecylsulfinium) An arylsulfinyl group (preferably an arylsulfinyl group having a carbon number of 6 to 32, more preferably an arylsulfinyl group having a carbon number of 6 to 24, such as phenylsulfin Base), alkyl sulfonyl group (preferably having a carbon number of 1 to 4) The alkylsulfonyl group of 8, more preferably an alkylsulfonyl group having a carbon number of 1 to 24, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, or different Propylsulfonyl, 2-ethylhexylsulfonyl, hexadecanosulfonyl, octylsulfonyl, or cyclohexylsulfonyl), arylsulfonyl (preferably having a carbon number of 6~) An arylsulfonyl group of 48, more preferably an arylsulfonyl group having a carbon number of 6 to 24, such as a phenylsulfonyl group or a 1-naphthylsulfonyl group, or an aminesulfonyl group (preferably carbon) The sulfonamide group having a number of 32 or less, more preferably an amine sulfonyl group having a carbon number of 24 or less, such as an amine sulfonyl group, N,N-dipropylamine sulfonyl group, N-ethyl-N-ten Diaminomethanesulfonyl, N-ethyl-N-phenylamine sulfonyl, or N-cyclohexylamine sulfonyl), sulfo, phosphonyl (preferably having a carbon number of 1~) a phosphinium group of 32, more preferably a phosphonium group having a carbon number of 1 to 24, such as a phenoxyphosphonium group, an octyloxyphosphonium group, or a phenylphosphonium group, or a phosphinoyl amine. a group (preferably a phosphinylamino group having a carbon number of 1 to 32, more preferably a phosphinylamino group having a carbon number of 1 to 24, such as a diethoxyphosphinylamino group or a dioctyloxy group; Phosphine Amine).

When the monovalent substituent represented by R ² to R ⁵ in the above formula (I) may be further substituted, it may be further substituted by any of the above groups. Further, when there are two or more further substituents, the substituents may be the same or different.

When the above monovalent substituent further has a substituent, as the further substituent, it is preferably selected from a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a decyl group, a cyano group, a nitro group, an alkoxy group. , aryloxy, heterocyclic oxy, alkylcarbonyloxy, alkoxycarbonyloxy, arylcarbonyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkylcarbonyl, alkoxy a carbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, and an arylsulfonyl group, and furthermore Preferably selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylcarbonyloxy group, an alkoxycarbonyloxy group, an arylcarbonyloxy group, an alkane Sulfosulfonyloxy, arylsulfonyloxy, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylthio, arylthio, heterocyclic thio, alkylsulfonyl, and aryl sulfonate a substituent in the thiol group.

R ³ and R ⁴ in the formula (I) are each independently, preferably an alkyl group, an aryl group or a heterocyclic group, more preferably an alkyl group or an aryl group.

The alkyl group in the above R ³ and R ⁴ is preferably an alkyl group having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a cyclopropyl group, and a n-butyl group. , isobutyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, and benzyl.

In particular, the alkyl group in R ³ and R ⁴ is preferably a branched or cyclic alkyl group having 1 to 12 carbon atoms, and examples thereof include an isopropyl group, a cyclopropyl group, and an isobutyl group. Tributyl, cyclobutyl, cyclopentyl, and cyclohexyl. Further, particularly preferably a secondary or tertiary alkyl group having a carbon number of 1 to 12, and examples thereof include an isopropyl group, a cyclopropyl group, an isobutyl group, a tert-butyl group, a cyclobutyl group, and a cyclohexyl group. .

The aryl group in the above R ³ and R ⁴ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.

The heterocyclic group in the above R ³ and R ⁴ is preferably 2-thienyl, 4-pyridyl, 3-pyridyl, 2-pyridyl, 2-furyl, 2-pyrimidinyl, 2- a benzothiazolyl group, a 1-imidazolyl group, a 1-pyrazolyl group, a benzotriazol-1-yl group, more preferably a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, a 2-pyrimidinyl group, Or 1-pyridyl.

R ² and R ⁵ in the formula (I) are each independently, preferably an alkoxycarbonyl group, an aryloxycarbonyl group, an aminomethyl fluorenyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitrile group, a fluorene group. An amine group or an amine carbaryl sulfonyl group, more preferably an alkoxycarbonyl group, an aryloxycarbonyl group, an amine carbaryl group, an alkyl sulfonyl group, a nitrile group, a quinone imine group, or an amine formazan group. The sulfonyl group, and more preferably an alkoxycarbonyl group, an aryloxycarbonyl group, an amine carbaryl group, a nitrile group, a quinone imine group, or an amine carbaryl sulfonyl group, particularly preferably an alkoxycarbonyl group, a aryl group An oxycarbonyl group, or an amine carbenyl group. Specific examples of such groups are as described above.

Regarding R ⁷ in the general formula (I)

When R ⁷ in the formula (I) is a halogen atom, an alkyl group, an aryl group or a heterocyclic group, examples of such a group include a halogen atom and an alkyl group in the above R ² to R ⁵ . The aryl group or the heterocyclic group is the same, and preferred examples of the groups are also the same.

A preferred example of R ⁷ in the formula (I) is a hydrogen atom, or a halogen atom or an alkyl group, and more preferably a hydrogen atom.

Regarding M in the general formula (I)

M in the formula (I) represents a metal atom or a metal compound. M may be any metal atom or metal compound as long as it is a metal atom or a metal compound capable of forming a complex, including a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, and a divalent metal. Metal chloride. For example, in addition to zinc (Zn), magnesium (Mg), bismuth (Si), tin (Sn), rhodium (Rh), platinum (Pt), palladium (Pd), molybdenum (Mo), manganese (Mn), lead (Pb), copper (Cu), nickel (Ni), cobalt (Co), iron (Fe), boron (B), etc., including AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ , GeCl ₂ Such as metal chlorides, metal oxides such as TiO and VO, and metal hydroxides such as Si(OH) ₂ .

Among these, from the viewpoints of stability, spectral characteristics, heat resistance, light resistance, and manufacturing suitability of the complex, Fe, Zn, Mg, Si, Pt, Pd, Mo, and Mn are preferable. , Cu, Ni, Co, TiO, B, or VO, more preferably Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO, and more preferably Fe, Zn, Cu, Co, B, or VO (V=O), especially, is preferably Zn.

Regarding "(X ¹ ) _a " in the general formula (I)

X ¹ in the formula (I) represents a group required for neutralizing the charge of M, and examples of X ¹ include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxyl group, and an aliphatic group. The quinone imine (for example, succinimide, maleimide, pentaneimine, diethylamine, etc.) is preferable, and preferably, butadiene or succinimide is mentioned. a monovalent group, an aromatic quinone imine group of an amine or a heterocyclic quinone imide (for example, phthalimide, naphthyl imine, 4-bromophthalimide) Amine, 4-methylphthalimide, 4-nitrophthalimide, naphthylcarboxyimine, or tetrabromophthalimide, etc., preferably exemplified a monovalent group of phyphenylimine, 4-bromophthalimide, or 4-methylphthalimide derived from an aromatic carboxylic acid (for example, benzoic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid, 4-methoxybenzoic acid, 4-chlorobenzoic acid, 2-naphthoic acid, salicylic acid, 3,4,5-trimethoxybenzoic acid , 4-heptyloxybenzoic acid, or 4-tert-butylbenzoic acid, etc., preferably exemplified A monovalent group of an acid, 4-methoxybenzoic acid, or salicylic acid, etc. derived from an aliphatic carboxylic acid (for example, formic acid, acetic acid, acrylic acid, methacrylic acid, acetic acid (ethanoic acid) ), propionic acid, lactic acid, trimethylacetic acid, caproic acid, octanoic acid, 2-ethylhexanoic acid, neodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, isostearic acid, 2-hexadecyl octadecanoic acid, 2-hexyl decanoic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, 5-norbornene-2-carboxylic acid, 1-adamantanecarboxylic acid, etc., preferably A monovalent group of acetic acid, methacrylic acid, lactic acid, trimethylacetic acid, 2-ethylhexanoic acid, or stearyl acid, etc. may be mentioned, derived from dithiol formic acid (for example, dimethyl disulfide may be mentioned) A monovalent group of a uric acid, diethyldithiocarbamic acid or dibenzyldithiocarbamic acid derived from a sulfonamide (for example, benzenesulfonamide, 4-chlorobenzenesulfonamide, 4- A valence of methoxybenzenesulfonamide, 4-methylbenzenesulfonamide, 2-methylbenzenesulfonamide, or methanesulfonamide, preferably phenylsulfonamide or methanesulfonamide Base derived from hydroxamic acid (for example, acetamidine) a monovalent group derived from decanoic acid, octyl hydroxamic acid, or benzoxamic acid, and a compound derived from a nitrogen-containing ring (for example, carbendazim, 1-benzyl-5-ethoxy group) Intraurea urea, 1-allyl carbendazim, 5,5-diphenylethylene carbazide, 5,5-dimethyl-2,4-oxazolidinedione, barbituric acid, Imidazole, pyrazole, 4,5-dicyanoimidazole, 4,5-dimethylimidazole, benzimidazole, or diethyl 1H-imidazole-4,5-dicarboxylate, etc., preferably 1 -benzyl-5-ethoxyethyl carbazide, 5,5-dimethyl-2,4-oxazolidinedione, 4,5-dicyanoimidazole, or 1H-imidazole-4,5- A monovalent group of diethyl dicarboxylate.

Among these, from the viewpoint of production, a halogen atom, an aliphatic carboxylic acid group, an aromatic carboxylic acid group, an aliphatic quinone imine group, an aromatic fluorenylene group, a sulfonic acid group, or a source is preferable. The group derived from the nitrogen-containing cyclic compound is more preferably a hydroxyl group, an aliphatic carboxylic acid group, an aromatic quinone imine group, or a group derived from a nitrogen-containing ring compound.

In the formula (I), a represents 0, 1, or 2.

Regarding R ⁸ ~ R ¹⁰ in the general formula (I)

In the formula (I), R ⁸ to R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent. Among them, at least two of R ⁸ to R ¹⁰ represent a monovalent substituent. The monovalent substituent represented by R ⁸ to R ¹⁰ has the same meanings as those described above for the substituent of R ² to R ⁵ , and among them, a halogen atom, an alkyl group, an aryl group or a heterocyclic group is preferred. a decyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, or a heterocyclic thio group, more preferably a halogen atom, an alkyl group, an aryl group, an alkoxy group, or an alkylthio group. base.

When R ⁸ to R ¹⁰ are each independently a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a decyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, or a heterocyclic sulfur Specific examples of the group include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a decyl group, an alkoxy group, and the description of the substituent represented by the above R ² to R ⁵ . The same examples of the aryloxy group, the heterocyclic oxy group, the alkylthio group, the arylthio group or the heterocyclic thio group are the same, and preferred examples of the groups are also the same.

Regarding R ¹¹ to R ¹⁴ in the general formula (I)

Examples of the monovalent substituent of R ¹¹ to R ¹⁴ in the formula (I) include the same groups as those exemplified as the monovalent substituent of the above R ² to R ⁵ .

R ¹¹ to R ¹⁴ are each independently, preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a decyl group, a cyano group, a nitro group, an alkoxy group, an aryloxy group, a heterocyclic oxy group or an alkane group. Carbocarbonyloxy, alkoxycarbonyloxy, arylcarbonyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylthio, An arylthio group, a heterocyclic thio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, or an arylsulfonyl group, more preferably a hydrogen atom, a halogen atom, an alkyl group or an aryl group a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group or a heterocyclic thio group, particularly preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or an alkoxy group. A aryloxy group or a heterocyclic oxy group.

Regarding X ² in the general formula (I)

X ² in the formula (I) represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group or an arylsulfonyl group) , an oxygen atom, or a sulfur atom.

The alkyl group of the above R is preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably a linear, branched or cyclic group having 1 to 12 carbon atoms. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a 2-ethylhexyl group, a dodecyl group, a cyclopropyl group or a cyclopentyl group. Base, cyclohexyl, or 1-adamantyl, and the like.

The alkenyl group of R is preferably an alkenyl group having 2 to 24 carbon atoms, more preferably an alkenyl group having 2 to 12 carbon atoms, and examples thereof include a vinyl group, an allyl group, or a 3-butene group. 1-based and the like.

The aryl group of R is preferably an aryl group having 6 to 36 carbon atoms, more preferably an aryl group having 6 to 18 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

The heterocyclic group of R is preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably a heterocyclic group having 1 to 12 carbon atoms, and preferably containing a nitrogen atom, an oxygen atom, and At least one element of a sulfur atom is a hetero atom.

Specific examples of the heterocyclic group of the above R include a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, a 2-pyrimidinyl group, a 1-pyridyl group, a 2-benzothiazolyl group, and a 1-imidazolyl group. , 1-pyrazolyl, and benzotriazol-1-yl and the like.

The alkylcarbonyl group of the above R is preferably an alkylcarbonyl group having 2 to 24 carbon atoms, more preferably an alkylcarbonyl group having 2 to 18 carbon atoms, and examples thereof include an ethyl fluorenyl group and a trimethyl ethane group. , 2-ethylhexyl, or cyclohexyl group, and the like.

The arylcarbonyl group of the above R is preferably an arylcarbonyl group having 7 to 22 carbon atoms, more preferably an arylcarbonyl group having 7 to 16 carbon atoms, and examples thereof include a benzamidine group.

The alkylsulfonyl group of the above R is preferably an alkylsulfonyl group having 1 to 24 carbon atoms, more preferably an alkylsulfonyl group having 1 to 18 carbon atoms, and examples thereof include methylsulfonium sulfonate. A group, an ethylsulfonyl group, an isopropylsulfonyl group, or a cyclohexylsulfonyl group.

The arylsulfonyl group of the above R is preferably an arylsulfonyl group having 6 to 24 carbon atoms, more preferably an arylsulfonyl group having 6 to 18 carbon atoms, and examples thereof include phenylsulfonyl sulfonate. Or a naphthylsulfonyl group or the like.

Further, the monovalent substituent of R may be further substituted by a substituent, and when substituted by a plurality of further substituents, the substituents may be the same or different.

When the above monovalent substituent further has a substituent, as the further substituent, it is preferably selected from a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group or a heterocyclic oxy group. , alkylcarbonyloxy, arylcarbonyloxy, alkylsulfonyloxy, Arylsulfonyloxy, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylthio, arylthio, heterocyclothio, alkylsulfonyl, and arylsulfonyl, more preferably Selected from a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a decyl group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, And a substituent in the arylsulfonyl group.

X ^{2 is} preferably an oxygen atom or a sulfur atom, and particularly preferably an oxygen atom.

Regarding R ¹⁶ in the general formula (I)

The monovalent substituent of R ¹⁶ in the formula (I) is the same as those exemplified as the monovalent substituent of the above R ² to R ⁵ . Of these, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an amine carbaryl group, a ureido group, an alkylsulfinyl group, an arylsulfinyl group, and an alkyl group are preferred. Sulfonyl, arylsulfonyl, or aminesulfonyl, more preferably alkyl, alkenyl, aryl, heterocyclyl, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, or arylsulfonate The thiol group, and more preferably an alkyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, or an arylcarbonyl group.

The above monovalent substituent may be unsubstituted, and may further have a substituent. When further having a substituent, as the further substituent, it is preferably selected from a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylcarbonyloxy group. , arylcarbonyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylthio, arylthio, heterocyclic thio, alkyl Sulfhydryl group, and arylsulfonyl group, more preferably selected from a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylcarbonyl group, an alkylthio group, a substituent in an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, and an arylsulfonyl group.

Preferred examples of the compound represented by the formula (I) are explained below.

Preferred examples of the specific dipyrromethene metal complex of the present invention are R ² to R ⁵ , R ⁷ to R ¹⁴ , R ¹⁶ , X ¹ , a, X ² and M of the formula (I). The following compounds.

That is, the following forms are mentioned: R ² and R ⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a cyano group, a nitro group, an alkoxy group, or an aryloxy group. a heterocyclic oxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amine carbaryl group, a fluorenylene group, an alkoxycarbonylamino group, a sulfonylamino group, an azo group, An alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or an aminesulfonyl group; and R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, or an alkenyl group; , aryl, heterocyclic, decyl, hydroxy, cyano, alkoxy, aryloxy, heterocyclooxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, amidyl, anilino, Benzylamino, ureido, oximine, alkoxycarbonylamino, sulfonylamino, azo, alkylthio, arylthio, heterocyclic thio, alkylsulfonyl, aryl a sulfonyl group, an amine sulfonyl group, or a phosphinium group; R ⁷ : a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group; and R ⁸ to R ¹⁰ are each independently a hydrogen atom or a halogen atom; , alkyl, aryl a heterocyclic group, a nonyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group or a heterocyclic thio group, and at least two of R ⁸ to R ¹⁰ are a hydrogen atom R ¹¹ to R ¹⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a cyano group, a nitro group, an alkoxy group, an aryloxy group or a heterocyclic oxy group. , mercapto, alkoxycarbonyl, aryloxycarbonyl, amine carbaryl, quinone imine, alkoxycarbonylamino, sulfonylamino, azo, alkylthio, arylthio, heterocycle a thio group, an alkylsulfonyl group, an arylsulfonyl group, or an amine sulfonyl group; X ² is an oxygen atom or a sulfur atom; and R ¹⁶ is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, An alkylcarbonyl group, an arylcarbonyl group, an amine carbenyl group, a ureido group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, or an aminesulfonyl group; Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B, or VO; X ¹ is a halogen atom, an aliphatic carboxylic acid group, an aromatic carboxylic acid group, an aliphatic quinone imine Base, aromatic quinone imine group, sulfonic acid group, or derived from nitrogen-containing ring A base; a is 0, 1, or 2.

More preferred examples of the specific dipyrromethene metal complex of the present invention are R ² to R ⁵ , R ⁷ to R ¹⁴ , R ¹⁶ , X ¹ , a, X ² and M of the formula (I). The following compounds.

That is, the following forms are mentioned: R ² and R ⁵ are each independently an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, An amidyl group, a fluorenylene group, an alkylsulfonyl group, an arylsulfonyl group, or an aminesulfonyl group; and R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic ring; Base, cyano group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, amine carbaryl group, benzammonium group, ureido group, oximine group, alkoxycarbonylamino group, sulfonylamino group, alkane a thio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or an amine sulfonyl group; R ⁷ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group; R ⁸ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, or an alkylthio group, and at least two of R ⁸ to R ¹⁰ are a group other than a hydrogen atom; R ¹¹ ~ R ^{14 is} independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a nitro group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylcarbonyl group, an arylcarbonyl group or an alkoxy group. Carbocarbonyl, aryloxycarbonyl, Mercapto, fluorenylene, alkoxycarbonylamino, sulfonylamino, azo, alkylthio, arylthio, heterocyclothio, alkylsulfonyl, arylsulfonyl, Or a sulfonyl group; X ² is an oxygen atom or a sulfur atom; R ¹⁶ is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an amine carbenyl group, a urea group , alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, or aminesulfonyl; M is Zn, Mg, Si, Pt, Pd, Cu, Ni, Co , B, or VO; X ¹ is a halogen atom, an aliphatic carboxylic acid group, an aromatic carboxylic acid group, an aliphatic quinone imine group, an aromatic fluorenylene group, a sulfonic acid group, or a compound derived from a nitrogen-containing ring compound Base; a is 0, 1, or 2. Further more preferred examples of the specific dipyrromethene metal complex of the present invention are R ² to R ⁵ , R ⁷ to R ¹⁴ , R ¹⁶ , X ¹ , a, X ² and M of the formula (I). A compound that is the following.

That is, the following forms are mentioned: R ² and R ⁵ are each independently an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, An amidyl group, a fluorenylene group, an alkylsulfonyl group, an arylsulfonyl group, or an aminesulfonyl group; and R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic ring; Base, cyano group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, amine carbaryl group, benzammonium group, ureido group, oximine group, alkoxycarbonylamino group, sulfonylamino group, alkane a thio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or an aminesulfonyl group; R ⁷ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group; R ⁸ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, or an alkylthio group, and at least two of R ⁸ to R ¹⁰ are a group other than a hydrogen atom; R ¹¹ ~ R ^{14 is} independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a nitro group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylcarbonyl group, an arylcarbonyl group or an alkoxy group. Carbocarbonyl, aryloxycarbonyl, Mercapto, fluorenylene, alkoxycarbonylamino, sulfonylamino, azo, alkylthio, arylthio, heterocyclothio, alkylsulfonyl, arylsulfonyl, Or sulfonyl; X ² is an oxygen atom or a sulfur atom; R ¹⁶ is an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, or an arylsulfonyl group; M is Zn , Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B, or VO; X ¹ is a halogen atom, an aliphatic carboxylic acid group, an aromatic carboxylic acid group, an aliphatic quinone imine group An aromatic quinone imine group, a sulfonic acid group, or a group derived from a nitrogen-containing cyclic compound; a is 0, 1, or 2.

Stability, spectroscopic properties, heat resistance, light resistance, and stability of the complex From the viewpoint of adaptability and the like, the compound represented by the formula (I) and the tautomer in the present invention are more preferably represented by the following formula (II).

In the formula (II), R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent substituent; X ¹ represents a group required for neutralizing the charge of Zn; and R ⁸ to R ¹⁰ each independently represent hydrogen. An atom or a monovalent substituent; wherein at least two of R ⁸ to R ¹⁰ represent a monovalent substituent; R ¹¹ to R ¹⁴ each independently represent a hydrogen atom or a monovalent substituent; and X ² represents NR ( R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or a sulfur atom; R ¹⁶ represents A hydrogen atom or a monovalent substituent.

The preferred range of each group of the compound represented by the formula (II) is the same as that of the formula (I).

From the viewpoint of film thickness, the molar absorption coefficient of the dipyrromethene metal complex or the tautomer thereof in the present invention is preferably as high as possible. Further, from the viewpoint of improving the color purity, the maximum absorption wavelength λ _{max is} preferably from 520 nm to 580 nm, more preferably from 530 nm to 570 nm. In addition, the maximum absorption wavelength and the molar absorption coefficient were measured by a spectrophotometer UV-1800PC [trade name, manufactured by Shimadzu Corporation (stock)].

Next, specific examples of the specific dipyrromethene metal complex of the present invention are shown below. However, it is not limited to these specific examples.

In the color hardening composition of the present invention, in addition to the specific dipyrromethene metal complex, it may be used in combination insofar as the effects of the present invention are not impaired. Other structures of dyes or pigments.

Dyes with other structures

The dye having another structure is not particularly limited, and a known dye can be used. For example, Japanese Patent Laid-Open No. Sho 64-90403, Japanese Patent Laid-Open No. Hei 64-91102, Japanese Patent Laid-Open No. Hei 1-94301, Japanese Patent Laid-Open No. Hei 6-11614, Japanese Patent Japanese Patent No. 4, 808, 501, U.S. Patent No. 4, 808, 502, U.S. Patent No. 5, 667, 920, U.S. Patent No. 5,059,500, Japanese Patent Laid-Open No. Hei 5-333207, Japanese Patent Laid-Open No. Hei No. Hei 6-35183, Japanese Patent Laid-Open No. Hei 6-- Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Hei. Hei. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The dye described in the Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei.

As a chemical structure of a dye having other structures, pyrazole can be used: Nitrogen, anilino azo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxaphthalocyanine, pyrazolotriazole azo, pyridone azo, flower A dye such as a phthalocyanine, a phenothiazine, a pyrrolopyrazine, a dibenzopyran, a squarylium sulphate, a phthalocyanine, a benzopyran, or an indigo. Among them, from the viewpoint of color tone, a dibenzopyran-based dye or a squaraine ylide-based dye is preferred.

The above dye having another structure may be contained alone or in combination of two or more.

The content of the specific dipyrromethene metal complex in the coloring curable composition in the present invention is preferably from 0.1% by mass to 30% by mass based on the total mass of the coloring-curable composition. Preferably, it is 0.5% by mass to 20% by mass. By setting the content of the dye to the above range, a favorable concentration (for example, a color density suitable for liquid crystal display) can be obtained, and it is advantageous from the viewpoint that the patterning of the pixels is good.

pigment

In the colored curable composition, a pigment may be used in combination with the above dye.

As the pigment, a pigment having an average primary particle diameter of 10 nm to 30 nm is preferred. According to the above aspect, a color hardening composition excellent in color tone and contrast can be obtained.

As the pigment, various conventional inorganic pigments or organic pigments can be used, but from the viewpoint of reliability, it is preferred to use an organic pigment. In the present invention, the organic pigment described in paragraph 0093 of JP-A-2009-256572 is exemplified as the organic pigment.

In addition, in terms of color reproducibility, it is particularly suitable for the following organic Pigment, but the invention is not limited to these organic pigments. These organic pigments may be used singly or in combination for the purpose of improving color purity.

CIPigment Red 177, 224, 242, 254, 255, 264, CIPigment Yellow 138, 139, 150, 180, 185, CIPigment Orange 36, 38, 71, CI Pigment Green 7, 36, 58, CIPigment Blue 15:6, CIPigment Violet 23.

When the pigment is used, the content in the color hardening composition of the present invention is preferably from 0.5% by weight to 50% by weight, more preferably from 1% by weight to 30% by weight based on the total solid content of the composition. When the content of the pigment is within the above range, it is effective for ensuring excellent color characteristics.

Pigment dispersant

When the colored curable composition of the present invention contains the compound represented by the formula (I) or a tautomer thereof and a pigment together, the pigment dispersant may be contained.

Examples of the pigment dispersant include polymer dispersants [for example, polyamidoamine and its salts, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified materials. a poly(meth)acrylate, a (meth)acrylic copolymer, a naphthalenesulfonic acid formaldehyde condensate, and a surfactant such as a polyoxyethylene alkyl phosphate, a polyoxyethylene alkylamine, or an alkanolamine; Pigment derivatives and the like.

The polymer dispersant can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer depending on the structure thereof.

For example, the terminal-modified polymer having a fixed portion on the surface of the pigment has a phosphate group at the terminal as described in JP-A-3-112992, JP-A-2003-533455, and the like. A polymer having a sulfonic acid group at the terminal, as described in JP-A-2002-273191, and a partial skeleton or a heterocyclic ring having an organic dye described in Japanese Laid-Open Patent Publication No. Hei 9-77994. Polymers, etc. In addition, as described in Japanese Laid-Open Patent Publication No. 2007-277514, two or more fixed sites (acid groups, basic groups, partial skeletons of organic dyes, heterocyclic rings, etc.) on the surface of the pigment are introduced into the polymer terminal. The dispersion stability of the molecule is also excellent, and is preferable.

Examples of the graft-type polymer having a fixed portion on the surface of the pigment include a polyester-based dispersant, and the like. Specific examples thereof include Japanese Patent Laid-Open No. 54-37082, and Japanese Patent Laid-Open No. Hei 8- The reaction product of the poly(lower alkylene imine) and the polyester described in JP-A-2009-258668, and the like, and the polyene described in JP-A-9-169821, and the like. Copolymerization of a macromonomer and a monomer containing a nitrogen atom described in JP-A-H05-339949 The graft type of a partial skeleton or a heterocyclic ring having an organic dye described in Japanese Patent Laid-Open Publication No. 2008-281732, and the like. A copolymer of a macromonomer and an acid group-containing monomer described in Japanese Laid-Open Patent Publication No. 2010-106268, and the like. In particular, the dispersibility, dispersion stability, and color hardening property of the pigment dispersion using the pigment dispersion The amphoteric dispersion resin having a basic group and an acidic group described in JP-A-2009-203462 is particularly preferable from the viewpoint of the developability of the composition.

As a macromonomer to be used for the production of a graft polymer having a fixed portion on the surface of a pigment by radical polymerization, a known macromonomer can be used, and examples thereof include: TOAGOSEI Co .,Ltd.) manufactured macromonomer AA-6 (polymethyl methacrylate with terminal group of methacryl fluorenyl), AS-6 (polystyrene with terminal group of methacryl fluorenyl), AN-6S (copolymer of styrene and acrylonitrile with terminal group of methacryl fluorenyl), AB-6 (polybutyl acrylate of methacryl fluorenyl group), Daicel Chemical Industry (shares) PLACEL FM5 (ε-caprolactone 5 molar equivalent adduct of 2-hydroxyethyl methacrylate) manufactured by DAICEL Chemical Industries Ltd., FA10L (ε-caprolactone of 2-hydroxyethyl acrylate 10 mol) The polyester-based macromonomer described in Japanese Laid-Open Patent Publication No. Hei 2-272009, and the like. Among these, in particular, from the viewpoint of dispersibility of the pigment dispersion, dispersion stability, and developability exhibited by the color-curable composition using the pigment dispersion, it is particularly preferable that it is excellent in flexibility and solvophilicity. The polyester-based macromonomer is a polyester-based macromonomer represented by the polyester-based macromonomer described in Japanese Laid-Open Patent Publication No. Hei 2-272009.

The block type polymer described in the above-mentioned Japanese Patent Publication No. 2003-49110, and the like.

The pigment dispersing agent can also be obtained as a commercial product. Specific examples of such a commercial product include "DA-7301" manufactured by Nanben Chemical Co., Ltd., and "Disperbyk-" manufactured by BYK Chemie Co., Ltd. 101 (polyamidoamine phosphate), 107 (carboxylate), 110 (acid group-containing copolymer), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer Copolymer)", "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)", "EFKA4047, 4050, 4010, 4165 (polyurethane), EFKA4330, manufactured by EFKA) ~4340 (block copolymer), 4400~4402 (modified polyacrylate), 5010 (polyester decylamine), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (酞花青) "Derivatives", 6750 (Azo Pigment Derivatives), "AJISPER PB821, PB822, PB880, PB881" manufactured by Ajinomoto Fine-Techno Co., Inc., Kyoritsu Chemical Co., Ltd. ( "FLOWLEN TG-710 (urethane oligomer)", "POLYFLOW No. 50E, No. 300 (acrylic copolymer)" manufactured by Kyoeisha Chemical Co., Ltd., Nanben Chemical "DISPARLON KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725" manufactured by the company, Kao Corporation (Kao) "DEMOL RN, N (naphthalenesulfonic acid formaldehyde polycondensate), MS, C, SN-B (aromatic sulfonic acid formaldehyde polycondensate)", "HOMOGENOL L-18 (polymer polycarboxylic acid) manufactured by Corporation) "EMULGEN 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "ACETAMIN 86 (stearylamine acetate)", manufactured by The Lubrizol Corporation, Japan "SOLSPERSE 5000 (酞 青 衍生物 derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional portion at the end), 24000, 28000, 32000, 38500 (graft-type polymer)", Nikko Chemicals Co., Ltd. ) "NIKKOL T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)", Kawaken Fine Chemicals Co., Ltd. .) manufactured HINOACT T-8000E, etc., organic siloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd., Yusho Co., Ltd. "W001: cationic surfactant", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, Nonionic surfactants such as polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester, and anionic surfactants such as "W004, W005, W017", Morishita Industry (Essence) (EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer100, EFKA Polymer400, EFKA P manufactured by Morishita Sangyo Corporation) Olymer401, EFKA Polymer450", polymer dispersant such as "DISPERSE AID6, DISPERSE AID8, DISPERSE AID15, DISPERSE AID9100" manufactured by San Nopco Ltd., ADEKA Corporation ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123, and Sanyo Chemical (share) "IONET (trade name) S-20" manufactured by Sanyo Chemical Industries Ltd., and the like.

These pigment dispersants may be used singly or in combination of two or more. use. In the present invention, it is particularly preferred to use a pigment derivative in combination with a polymer dispersant. Further, the pigment dispersant of the present invention may be used in combination with the terminal modified polymer having a fixed portion on the surface of the pigment, a graft polymer, a block polymer, and an alkali-soluble resin. Examples of the alkali-soluble resin include a (meth)acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, and the like, and a side chain. An acid cellulose derivative having a carboxylic acid and a resin obtained by modifying an acid anhydride in a polymer having a hydroxyl group are particularly preferably a (meth)acrylic copolymer. In addition, the N-substituted maleimide monomer copolymer described in Japanese Patent Laid-Open Publication No. Hei 10-300922, and the ether dimer copolymer described in JP-A-2004-300204, The alkali-soluble resin containing a polymerizable group described in Japanese Laid-Open Patent Publication No. Hei 7-319161 is also preferable.

The content of the pigment dispersant in the colored curable composition is preferably from 1 part by mass to 80 parts by mass, more preferably from 5 parts by mass to 70 parts by mass, even more preferably from 10 parts by mass to 60 parts by mass per 100 parts by mass of the pigment. Parts by mass.

Specifically, in the case of using a polymer dispersant, the amount thereof is preferably in the range of 5 parts by weight to 100 parts by mass, more preferably in the range of 10 parts to 80 parts, per 100 parts by mass of the pigment.

In addition, when a pigment derivative is used in combination, the amount of the pigment derivative used is preferably in the range of 1 part by weight to 30 parts by mass, more preferably in the range of 3 parts to 20 parts, per 100 parts by mass of the pigment. , especially good in the range of 5 to 15 parts.

Bismuth compound

The colored curable composition of the present invention may further contain a ruthenium compound.

By containing a ruthenium compound, a color filter having a more effectively improved contrast can be obtained.

The ruthenium compound is preferably a compound having an absorption maximum at 400 nm to 700 nm, more preferably a compound having an absorption maximum at 500 nm to 700 nm, and particularly preferably a compound having an absorption maximum at 550 nm to 700 nm. The ruthenium compound having such an absorption maximum is not particularly limited in structure, and is excellent in contrast enhancement effect.

Among the ruthenium compounds in the present invention, an amine ruthenium compound represented by the following formula (IX) is preferred.

Among the amine-based oxime compounds, from the viewpoint of absorption characteristics, the compound represented by the following formula (X) is more preferable, and from the viewpoint of thermal stability, it is more preferable to have the following formula ( Further, in view of the coexistence of absorption characteristics and thermal stability, the compound represented by the following formula (XII) or the following formula (XIII) is particularly preferable.

First, an aminoguanidine compound represented by the following formula (IX) will be described.

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

The alkyl group of R ^11a and R ^12a is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, particularly preferably an alkyl group having 1 to 10 carbon atoms, for example. Examples thereof include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an n-octyl group, a n-decyl group, a n-hexadecyl group, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.

The aryl group of R ^11a or R ^12a is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms, particularly preferably an aryl group having 6 to 12 carbon atoms, for example, There may be mentioned a phenyl group, an o-methylphenyl group, a p-methylphenyl group, a 2,6-dimethylphenyl group, a 2,6-diethylphenylbiphenyl group, a 2,6-dibromophenyl group, Naphthyl, anthracenyl, phenanthryl and the like.

The heterocyclic group of R ^11a and R ^12a is preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably a heterocyclic group having 1 to 12 carbon atoms, and as a hetero atom, for example, a nitrogen atom or an oxygen atom. , sulfur atom. Examples of the heterocyclic group include imidazolyl, pyridyl, quinolyl, furyl, thienyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, naphthylthiazolyl, oxazolyl, and nitrogen. Azepinyl and the like.

The alkyl group, the aryl group and the heterocyclic group of R ^11a and R ^12a are each independently and may further have a substituent.

Further examples of the substituent having a substituent include an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, particularly preferably a carbon number of Examples of the alkyl group of 1 to 10 include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an n-octyl group, a n-decyl group, a n-hexadecyl group, a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group. And an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms, more preferably an alkenyl group having 2 to 20 carbon atoms, particularly preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, Allyl, 2-butenyl, or 3-pentenyl, etc., alkynyl (preferably an alkynyl group having 2 to 30 carbon atoms, more preferably an alkynyl group having 2 to 20 carbon atoms) Examples of the alkynyl group having 2 to 10 carbon atoms include a propargyl group or a 3-pentynyl group, and an aryl group (preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 carbon atoms). The aryl group of ~20, particularly preferably an aryl group having a carbon number of 6 to 12, and examples thereof include a phenyl group, a p-methylphenyl group, a biphenyl group, a naphthyl group, a fluorenyl group, or a phenanthryl group), and an amine group ( Preferably, it is an amine group having a carbon number of 0 to 30, more preferably an amine group having a carbon number of 0 to 20, particularly preferably an amine group having a carbon number of 0 to 10, including an alkylamino group and an arylamino group. Or a heterocyclic amine group. Specific examples thereof include an amine group, a methylamino group, a dimethylamino group, a diethylamino group, a dibenzylamino group, a diphenylamino group, a xylylamino group, and the like, and an alkoxy group ( Preferably, it is an alkoxy group having a carbon number of 1 to 30, more preferably an alkoxy group having a carbon number of 1 to 20, particularly preferably an alkoxy group having a carbon number of 1 to 10, and examples thereof include a methoxy group and a An oxy group (e.g., an oxy group, a butoxy group or a 2-ethylhexyloxy group), preferably an aryloxy group having 6 to 30 carbon atoms, more preferably an aryloxy group having 6 to 20 carbon atoms. Particularly preferred is an aryloxy group having 6 to 12 carbon atoms, and examples thereof include a phenoxy group, a 1-naphthyloxy group, or a 2-naphthyloxy group, and an aromatic heterocyclic oxy group (preferably having a carbon number of 1). ~30 aromatic heterocyclic oxy group, more preferably 1 to 20 carbon atoms The aromatic heterocyclic oxy group is particularly preferably an aromatic heterocyclic oxy group having 1 to 12 carbon atoms, and examples thereof include a pyridyloxy group, a pyrazinyloxy group, a pyrimidinyloxy group, or a quinolineoxy group. The base (preferably a fluorenyl group having a carbon number of 1 to 30, more preferably a fluorenyl group having a carbon number of 1 to 20, particularly preferably a fluorenyl group having a carbon number of 1 to 12, and examples thereof include an ethyl fluorenyl group and a benzoic acid group. An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms, more preferably an alkoxy group having 2 to 20 carbon atoms), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms) The carbonyl group is particularly preferably an alkoxycarbonyl group having 2 to 12 carbon atoms, and examples thereof include a methoxycarbonyl group or an ethoxycarbonyl group, and an aryloxycarbonyl group (preferably an aryloxy group having a carbon number of 7 to 30). The carbonyl group is more preferably an aryloxycarbonyl group having 7 to 20 carbon atoms, particularly preferably an aryloxycarbonyl group having 7 to 12 carbon atoms, and examples thereof include a phenoxycarbonyl group and the like, and a decyloxy group (preferably The decyloxy group having a carbon number of 2 to 30 is more preferably a decyloxy group having a carbon number of 2 to 20, particularly preferably a decyloxy group having a carbon number of 2 to 10, and examples thereof include an ethoxylated group or a benzoic acid group. a fluorenyloxy group, a mercaptoamine group (preferably a mercaptoamine group having a carbon number of 2 to 30, more preferably a mercaptoamine group having a carbon number of 2 to 20) Particularly preferred is a mercaptoamine group having 2 to 10 carbon atoms, and examples thereof include an ethyl hydrazino group or a benzhydrylamino group, and an alkoxycarbonylamino group (preferably having a carbon number of 2 Å). The alkoxycarbonylamino group of 30 is more preferably an alkoxycarbonylamino group having 2 to 20 carbon atoms, particularly preferably an alkoxycarbonylamino group having 2 to 12 carbon atoms, and examples thereof include a methoxycarbonyl group. An amine group or the like, an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having a carbon number of 7 to 30, more preferably an aryloxycarbonylamino group having a carbon number of 7 to 20, particularly preferably carbon The aryloxycarbonylamino group having 7 to 12 may, for example, be a phenoxycarbonylamino group or the like, or a sulfonylamino group (preferably a sulfonylamino group having 1 to 30 carbon atoms), more preferably a sulfonylamino group having 1 to 20 carbon atoms, particularly preferably a sulfonylamino group having 1 to 12 carbon atoms, and for example, methylsulfonate a mercaptoamine group or a phenylsulfonylamino group, an aminesulfonyl group (preferably an amidoxime group having a carbon number of 0 to 30, more preferably an amidoxime group having a carbon number of 0 to 20, Particularly preferred is an amidoxime group having a carbon number of 0 to 12, and examples thereof include an aminesulfonyl group, a methylaminesulfonyl group, a dimethylaminesulfonyl group, or a phenylaminesulfonyl group, and the like. A mercapto group (preferably an amine carbenyl group having a carbon number of 1 to 30, more preferably an amine carbenyl group having a carbon number of 1 to 20, particularly preferably an amine carbenyl group having a carbon number of 1 to 12, for example, Illustrative of an amine methyl sulfhydryl group, a methylamine methyl sulfonyl group, a diethylamine methyl sulfonyl group, or a phenylamine methyl fluorenyl group, etc., an alkylthio group (preferably an alkylthio group having a carbon number of 1 to 30, more Preferably, the alkylthio group having a carbon number of 1 to 20, particularly preferably an alkylthio group having 1 to 12 carbon atoms, for example, a methylthio group or an ethylthio group, or an arylthio group (preferably a carbon number) The arylthio group of 6 to 30 is more preferably an arylthio group having 6 to 20 carbon atoms, particularly preferably an arylthio group having 6 to 12 carbon atoms, for example, a phenylthio group, etc., an aromatic heterocyclic ring. Sulfur-based (preferably an aromatic heterocyclic thio group having 1 to 30 carbon atoms, more preferably an aromatic heterocyclic thio group having 1 to 20 carbon atoms, particularly preferably an aromatic heteropoly group having 1 to 12 carbon atoms) Cycylthio Examples thereof include a pyridylthio group, a 2-benzimidazolylthio group, a 2-benzoxazolethio group, or a 2-benzothiazolylthio group, and a sulfonyl group (preferably having a carbon number of 1 to 30). The sulfonyl group is more preferably a sulfonyl group having a carbon number of 1 to 20, particularly preferably a sulfonyl group having a carbon number of 1 to 12, and examples thereof include a methylsulfonyl group or a toluenesulfonyl group, and a sulfinic acid. Sulfhydryl (preferably a sulfinyl group having a carbon number of 1 to 30, more preferably a sulfinyl group having a carbon number of 1 to 20, particularly preferably a sulfinyl group having a carbon number of 1 to 12, for example, Examples include a sulfinyl group or a sulfinyl group, a urea group (preferably a ureido group having a carbon number of 1 to 30, more preferably a ureido group having a carbon number of 1 to 20, particularly preferably a carbon number) a ureido group of 1 to 12, for example, a urea group, a methylurea group, or a phenylureido group, or a guanidinium phosphate group (preferably a guanidinium phosphate group having a carbon number of 1 to 30, more preferably a guanamine phosphate having a carbon number of 1 to 20) The base is particularly preferably a guanidinium phosphate group having a carbon number of 1 to 12, and examples thereof include a diethylphosphonium amide group or a phenylphosphonium phosphinate group, a hydroxyl group, a fluorenyl group, and a halogen atom (for example, a fluorine atom is exemplified). , chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfinic acid group, mercapto group, imido group, heterocyclic group (preferably having a carbon number of 1) The heterocyclic group of ～30 is more preferably a heterocyclic group having 1 to 12 carbon atoms, and examples thereof include a nitrogen atom, an oxygen atom or a sulfur atom as a hetero atom. Specific examples thereof include an imidazole group and a pyridine. Base, quinolyl, furyl, thienyl, piperidinyl, morpholinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, oxazolyl, nitrogen heptacyclyl, etc.) Preferably, it is a decyl group having a carbon number of 3 to 40, more preferably a decyl group having a carbon number of 3 to 30, particularly preferably a decyl group having a carbon number of 3 to 24, and examples thereof include a trimethyldecyl group or a trisole. Phenyl decyl, etc.)These substituents may also be further substituted.

In the above formula (IX), n ¹¹ represents an integer of 1 to 4, and when n ¹¹ is an integer of 2 to 4, the plurality of NR ^11a R ^12a may be the same or different.

Next, the diamino sulfonium compound represented by the general formula (X) will be described.

In the above formula (X), R ^21a and R ^22a each independently represent an alkyl group or an aryl group.

The alkyl group of R ^21a and R ^22a is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, particularly preferably an alkyl group having 1 to 10 carbon atoms, for example. Examples thereof include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an n-octyl group, a n-decyl group, a n-hexadecyl group, a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group.

The aryl group of R ^21a and R ^22a is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms, particularly preferably an aryl group having 6 to 12 carbon atoms, for example There may be mentioned a phenyl group, an o-methylphenyl group, a p-methylphenyl group, a 2,6-dimethylphenyl group, a 2,6-diethylphenylbiphenyl group, a 2,6-dibromophenyl group, Naphthyl, anthracenyl, or phenanthryl.

The alkyl group and the aryl group of the above R ^21a and R ^22a may further have a substituent. Examples of the further substituent include an alkane represented by R ^11a and R ^12a in the above formula (IX). Examples of the substituents of the aryl group, the aryl group and the heterocyclic group. Among them, as examples of the further substituent, an alkyl group, an aryl group, an amine group, an alkoxy group, an aryloxy group, a decyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a decyloxy group or a decyl group is preferred. Amine group, sulfonylamino group, amine sulfonyl group, sulfonyl group, ureido group, hydroxyl group, halogen atom, sulfo group, carboxyl group and the like. The details and preferred forms of the substituents are as described above.

Next, the diamino sulfonium compound represented by the general formula (XI) will be described.

In the above formula (XI), R ^31a , R ^32a , R ^33a and R ^34a each independently represent an alkyl group or a halogen atom.

The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, particularly preferably an alkyl group having 1 to 2 carbon atoms, and examples thereof include a methyl group. Ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecanyl, cyclopropyl, cyclopentyl, or cyclohexyl.

The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a chlorine atom or a bromine atom.

In the above formula (XI), R ^35a and R ^36a each independently represent an alkyl group, an alkoxy group, an aryloxy group, a sulfo group or a salt thereof, an aminosulfonyl group, an alkoxysulfonyl group, or a phenoxy group. Sulfosyl group.

Preferred examples, more preferred examples, and particularly preferred examples of the alkyl group are the same as those in the above R ^31a , R ^32a , R ^33a and R ^34a .

The alkoxy group of R ^35a and R ^36a is preferably an alkoxy group having 1 to 30 carbon atoms, more preferably an alkoxy group having 1 to 20 carbon atoms, particularly preferably an alkane having 1 to 10 carbon atoms. Examples of the oxy group include a methoxy group, an ethoxy group, a butoxy group, a 2-ethylhexyloxy group and the like.

The aryloxy group of R ^35a and R ^36a is preferably an aryloxy group having a carbon number of 6 to 30, more preferably an aryloxy group having a carbon number of 6 to 20, particularly preferably an aromatic having a carbon number of 6 to 12. Examples of the oxy group include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group.

The sulfo group of R ^35a and R ^36a and a salt thereof are preferably a group derived from an alkylsulfonic acid, an arylsulfonic acid, and a salt thereof. The above sulfonate is preferably a quaternary ammonium salt or an amine salt, particularly preferably an alkyl sulfonate having a carbon number of 4 to 30 (preferably having a carbon number of 10 to 30, more preferably a carbon number of 15 to 30). An acid salt or an arylsulfonate having a carbon number of 6 to 30 (preferably having a carbon number of 10 to 30, more preferably a carbon number of 15 to 30).

The aminosulfonyl group of R ^35a and R ^36a is preferably an alkylaminosulfonyl group having 1 to 30 carbon atoms, more preferably an alkylaminosulfonyl group having 2 to 20 carbon atoms, particularly preferably An alkylaminosulfonyl group having 2 to 15 carbon atoms, or an arylaminosulfonyl group having 6 to 30 carbon atoms, more preferably an arylaminosulfonyl group having 6 to 20 carbon atoms, An arylaminosulfonyl group having a carbon number of 6 to 15 is preferred. Specific examples thereof include an ethylaminosulfonyl group, a propylsulfonyl group, an isopropylaminosulfonyl group, a butylaminosulfonyl group, an isobutylaminosulfonyl group, and a second butylaminosulfonyl group. , pentaaminosulfonyl, isoamylsulfonyl, hexylaminosulfonyl, cyclohexylaminosulfonyl, 2-ethylhexylsulfonyl, decylsulfonyl, ten A diaminoaminosulfonyl group, an anilinosulfonyl group, etc., and, as the dialkylaminosulfonyl group, a dimethylaminosulfonyl group, a diethylaminosulfonyl group, a dipropylaminesulfonyl group , diisopropylaminosulfonyl, dibutylaminosulfonyl, di-butylaminosulfonyl, di-second propylsulfonyl, dihexylaminosulfonyl, methylethylamine Sulfhydryl group, methylbutylaminosulfonyl group, ethylbutylaminosulfonyl group, phenylmethylaminosulfonyl group and the like. Among them, a dialkylaminosulfonyl group having 4 to 15 carbon atoms in the alkyl moiety is particularly preferred.

The alkoxysulfonyl group of R ^35a and R ^36a is preferably an alkoxysulfonyl group having 1 to 30 carbon atoms, more preferably an alkoxysulfonyl group having 2 to 20 carbon atoms, and still more preferably The alkoxysulfonyl group having 2 to 15 carbon atoms is particularly preferably an alkoxysulfonyl group having 4 to 15 carbon atoms. Specific examples thereof include butoxysulfonyl group and hexyloxysulfonate. A group, a decyloxysulfonyl group, a dodecyloxysulfonyl group or the like.

The phenoxysulfonyl group of R ^35a and R ^36a is preferably a phenoxysulfonyl group having a carbon number of 6 to 30, more preferably a phenoxysulfonyl group having a carbon number of 6 to 20, particularly preferably carbon. The phenoxysulfonyl group having a number of 6 to 15 may, for example, be a phenoxysulfonyl group or a tolylsulfonyl group.

Each of R ^35a and R ^36a may further have a substituent. Examples of the further substituent include an alkyl group or an aryl group which is represented by R ^11a and R ^12a in the above formula (IX). An example of a substituent of a heterocyclic group.

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

Among the above ruthenium compounds, a compound selected from the group consisting of diamino sulfonium compounds represented by the following general formula (XII) and the following general formula (XIII) is particularly preferred.

In the above formula (XII), R ^41a , R ^42a , R ^43a and R ^44a each independently represent an alkyl group or a halogen atom, and the details thereof are in the above formula (XI), R ^31a , R ^32a , R The alkyl group and the halogen atom of ^33a and R ^34a are the same, and the preferred embodiment is also the same.

In the above formula (XII), R ^45a , R ^46a , R ^47a and R ^48a each independently represent an alkyl group, a sulfo group or a salt thereof, or an aminosulfonyl group. Any one of R ^45a and R ^47a and any one of R ^46a and R ^48a represents a sulfo group or a salt thereof or an aminosulfonyl group. The details of the alkyl group, the sulfo group or the salt thereof and the aminosulfonyl group of R ^45a , R ^46a , R ^47a and R ^48a are the same as those of R ^35a and R ^36a in the above formula (XI). The sulfo group or its salt and the aminosulfonyl group are the same, and the preferred embodiment is also the same.

In the above formula (XIII), R ^51a , R ^52a , R ^53a and R ^54a each independently represent an alkyl group or a halogen atom, and the details thereof are in the case of R ^31a and R ^32a in the formula (XI). The alkyl group and the halogen atom of R ^33a and R ^34a are the same, and the preferred embodiment is also the same.

In the above formula (XIII), R ^55a and R ^56a each independently represent a hydrogen atom or an alkyl group, and the details of the alkyl group are the same as those of R ^31a , R ^32a , R ^33a and R ^34a in the above formula (XI). The case of the alkyl group is the same, and the preferred form is also the same.

Further, R ^57a and R ^58a each independently represent a hydrogen atom or an alkyl group, and the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, particularly preferably A. base.

In the above formula (XIII), L ^51a and L ^52a each independently represent a divalent linking group, preferably an alkylene group having 1 to 10 carbon atoms, an extended aryl group having 6 to 20 carbon atoms, and -O. -, -S-, -NR-, -SO ₂ -, -CO-, or a divalent linking group in which a plurality of these groups are combined. As L ^51a and L ^52a , more preferably an alkylene group having a carbon number of 1 to 10, a phenylene group having a carbon number of 6 to 12, a sulfonylamino group, or a combination of a plurality of these groups. The divalent linking group is particularly preferably an alkylene group having a carbon number of 1 to 10, a sulfonylamino group, or a divalent linking group obtained by combining a plurality of these groups.

The divalent linking group having a carbon number of 1 to 10 or a combination of -O- or the like may be unsubstituted or may have a substituent, and examples thereof include an ethyl group and a potassium group. Base, butyl, ethoxy, propyloxy, ethylaminosulfonyl, propylaminosulfonyl, butylaminosulfonyl, pentylaminosulfonyl Base, 1-methyl-ethyl sulfonyl group, and the like. Among them, an alkylaminosulfonyl group having a carbon number of 2 to 10 is preferable (for example, an ethylaminosulfonyl group, a propylaminosulfonyl group, a butylaminosulfonyl group, Or pentylaminosulfonyl).

The divalent linking group having a carbon number of 6 to 20 or a divalent linking group which is combined with -O- or the like may be unsubstituted or may have a substituent, and examples thereof include a stretching phenyl group and a stretching group. A biphenyl group, a phenylaminosulfonyl group or the like is preferable, and among them, an exoarylaminosulfonyl group having a carbon number of 6 to 12 (e.g., a phenylaminosulfonyl group) is preferable.

Further, R of -NR- represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, and a 2-ethylhexyl group.

In the above formula (XIII), L ^53a and L ^54a each independently represent an oxygen atom or an -NH- group.

Among the above, the ruthenium compound which is preferable in the present invention is a compound selected from the group consisting of the diamino sulfonium compound represented by the above formula (XII) or the above formula (XIII), and further preferably Said the situation.

That is, it is preferred that in the above formula (XII), R ^41a , R ^42a , R ^43a , and R ^44a are each independently a methyl group, an ethyl group, or a bromine atom, and R ^45a and R ^46a are each independently. It is an aminosulfonyl group having 2 to 15 carbon atoms, and R ^47a and R ^48a are a methyl group.

Further, in the above formula (XIII), R ^51a , R ^52a , R ^53a and R ^54a are each independently a methyl group, an ethyl group or a bromine atom, and R ^55a and R ^56a are each independently. R ^57a and R ^58a are each independently a hydrogen atom or a methyl group, and L ^51a and L ^52a are each independently an alkylamine sulfonyl group having a carbon number of 1 to 10, and the carbon number is 7~. An aralkylaminosulfonyl group of 12 or an alkoxy group having a carbon number of 2 to 10, and L ^53a and L ^54a are oxygen atoms.

In this case, from the viewpoint of more effectively obtaining the effects of the present invention, it is preferred to equip the following dye compound with a compound represented by the formula (I) or a tautomer thereof in a metal atom. Or a combination of dipyrromethene metal complexes formed on a metal compound.

Specific examples of the ruthenium compound in the present invention are shown below. However, in the present invention, it is not limited by these specific examples.

The above-mentioned coloring curable composition is contained in the total amount of all the dye compounds containing the compound represented by the formula (I) or a tautomer thereof. The amount of the ruthenium compound is preferably 50% by mass or less, more preferably 2% by mass to 50% by mass, and still more preferably 10% by mass to 50% by mass. When the ratio of the ruthenium compound is 50% by mass or less, the firmness can be maintained, and the color tone of the colored image is good, and the contrast can be more effectively improved.

Polymeric compound

The color hardening composition of the present invention contains at least one polymerizable compound.

The polymerizable compound is, for example, a polymerizable compound having at least one ethylenically unsaturated double bond, and can be selected from known components constituting the composition. Examples of the polymerizable compound include a component described in Paragraph No. 0010 to Paragraph No. 0020 of JP-A-2006-23696, or a paragraph No. 0027-paragraph No. 2006-64921 of JP-A-2006-64921 The component described in 0053.

Further, a urethane addition polymerizable compound produced by an addition reaction of an isocyanate and a hydroxyl group is also suitable, as disclosed in Japanese Patent Laid-Open No. Hei 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent. Japanese Patent Publication No. Sho-58-49860, Japanese Patent Publication No. SHO-58-17654, Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-39417 A urethane compound having an oxirane skeleton described in Japanese Patent Publication No. 62-39418 is also suitable.

For example, the polyester acrylates described in each of the publications of Japanese Patent Publication No. Sho-49-43191, Japanese Patent Publication No. SHO-49-43191, and Japanese Patent Publication No. Sho 52-30490 a polyfunctional acrylate or methyl group such as an epoxy acrylate obtained by reacting an epoxy resin with (meth)acrylic acid Acrylate. Further, it can also be used as a photocurable monomer and oligomer in Journal of the Adhesion Society of Japan vol. 20, No. 7, page 300 to page 308 (1984). Introducer.

Specific examples of the polymerizable compound include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tri (( Preferred examples of (meth)acrylomethoxyethyl)isophthalocyanate, pentaerythritol tetra(meth)acrylate EO modified product, dipentaerythritol hexa(meth)acrylate EO modified body, and the like are preferable. In addition, as a commercial item, NK ESTER A-TMMT, NK ESTER A-TMM-3, NK OLIGO UA-32P, NK OLIGO UA-7200 (above, Shin-Nakamura Chemical Co., Ltd.) .,Ltd.)), ARONIX M-305, ARONIX M-306, ARONIX M-309, ARONIX M-450, ARONIX M-402, TO-1382 (above, East Asia Synthetic (Stock) (TOAGOSEI Co., Ltd .) Manufacturing), V#802 (manufactured by Osaka Organic Chemical Industry Ltd.) is a preferred example.

These polymerizable compounds may be used alone or in combination of two or more.

The content of the polymerizable compound in the total solid content of the colored curable composition (the total content in the case of two or more kinds) is preferably 10% by mass to 80% by mass, more preferably 15% by mass to 75% by mass. %, particularly preferably 20% by mass to 60% by mass.

Photopolymerization initiator

The color hardening composition of the present invention preferably contains at least one photopolymerization initiator. The photopolymerization initiator may be any one which can polymerize the above polymerizable compound. There is no particular limitation, and it is preferred to select from the viewpoints of characteristics, initial efficiency, absorption wavelength, availability, cost, and the like.

The photopolymerization initiator is a compound which is photosensitive by exposure light to start and promote polymerization of a polymerizable compound. It is preferably a compound which induces and accelerates polymerization of a polymerizable compound by irradiating an actinic ray having a wavelength of 300 nm or more. Further, a photopolymerization initiator which does not directly induce actinic rays having a wavelength of 300 nm or more may be preferably used in combination with a sensitizer.

Specific examples thereof include an oxime ester compound, an organic halide, an oxydiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, an acridine compound, an organic peroxide, an azo compound, and a coumarin. Compound, azide compound, metallocene compound, hexaarylbiimidazole compound, organoboric acid compound, disulfonic acid compound, phosphonium salt compound, mercaptophosphine (oxide), diphenylketone compound, acetophenone compound And its derivatives. Among these, from the viewpoint of sensitivity, an oxime ester compound and a hexaarylbiimidazole compound are preferable.

As the oxime ester compound, Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open Publication No. 2001-233842, Japanese Patent Publication No. 2004-534797, International Publication No. 2005/080337, International Publication No. 2006/ Japanese Patent Laid-Open No. 2007-210991, Japanese Patent Laid-Open No. 2007-231000, Japanese Patent Laid-Open No. Hei. No. 2007-269779, Japanese Patent Laid-Open No. 2009-191061, No. 2009/131189 The compound described in the above.

As a specific example, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)benzene is exemplified. 1,1,2-butanedione, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-pentanedione, 2-(O- Benzyl hydrazino)-1-[4-(phenylthio)phenyl]-1,2-hexanedione, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio) Phenyl]-1,2-heptanedione, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 2-( O-benzylidene hydrazide)-1-[4-(methylphenylthio)phenyl]-1,2-butanedione, 2-(O-benzylidene fluorenyl)-1-[4- (ethylphenylthio)phenyl]-1,2-butanedione, 2-(O-benzylidene fluorenyl)-1-[4-(butylphenylthio)phenyl]-1,2 -butanedione, 1-(O-ethylindenyl)-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone, 1 -(O-acetylhydrazine)-1-[9-methyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone, 1-(O-acetamidine) (肟)-1-[9-propyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1- [9-Ethyl-6-(2-ethylbenzylidenyl)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-ethyl- 6-(2-butylbenzylidene)-9H-indazol-3-yl]ethanone. However, it is not limited to these specific examples.

In addition, in the present invention, a compound represented by the following formula (1) is also suitable as the oxime compound from the viewpoint of sensitivity, temporal stability, and coloration upon post-heating.

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

Specific examples of the organic halide include, for example, "National Chemical Society Bulletin (Bull Chem. Soc. Japan)" 42, 2924 (1969), U.S. Patent No. 3,905,815, and Japanese Patent Publication No. Sho 46-4605. Japanese Patent Laid-Open Publication No. SHO-48-36281, Japanese Patent Laid-Open Publication No. Sho 55-32070, Japanese Patent Laid-Open Publication No. SHO-60-239736, Japanese Patent Laid-Open No. 61-169835 Japanese Laid-Open Patent Publication No. SHO-62- 582 837, Japanese Patent Laid-Open No. Hei. The compound described in the publication of the Journal of Heterocyclic Chemistry 1 (No. 3), (1970), and the like, in particular, an oxazole compound or a s-triazine compound substituted with a trihalomethyl group.

Examples of the hexaarylbiimidazole compound include various compounds described in the respective specifications, such as Japanese Patent Publication No. Hei. 6-29285, U.S. Patent No. 3,479,185, U.S. Patent No. 4,311,783, and U.S. Patent No. 4,622,286. Specifically, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-bromophenyl)-4 , 4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-,p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2 '-Bis(o-chlorophenyl)-4,4',5,5'-tetrakis(m-methoxyphenyl)biimidazole, 2,2'-bis(o-,o-di-dichlorophenyl)- 4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-nitrophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2' - bis(o-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-trifluorophenyl)-4,4',5,5'- Tetraphenylbiimidazole and the like.

The photopolymerization initiator may be used alone or in combination of two or more. In addition, when an initiator having no absorption at the exposure wavelength is used, it is necessary to use a sensitizer.

The total content of the photopolymerization initiator is preferably from 0.5% by weight to 30% by weight, more preferably from 2% by weight to 20% by weight, most preferably from 5% by weight to 18% by weight, based on the total solid content of the colored curable resin composition. If it is in this range, the sensitivity at the time of exposure is high, and the color characteristic is also favorable.

Alkali soluble binder

The colored curable composition of the present invention may also contain an alkali-soluble binder. The alkali-soluble binder is not particularly limited as long as it has alkali solubility, and is preferably selected from the viewpoints of heat resistance, developability, and availability.

As the alkali-soluble binder, a linear organic high molecular polymer which is soluble in an organic solvent and which can be developed by a weakly basic aqueous solution is preferred. Examples of such a linear organic high molecular polymer include a polymer having a carboxylic acid in a side chain. For example, Japanese Patent Laid-Open No. Sho 59-44615, Japanese Patent Publication No. Sho 54-34327, and Japanese Patent Publication No. Sho-58- A methacrylic acid copolymer, an acrylic copolymer, and a clothing disclosed in each of the publications of Japanese Patent Laid-Open Publication No. Sho 59-53836, and Japanese Patent Laid-Open No. 59-71048 An acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, or the like, and an acidic cellulose derivative having a carboxylic acid in a side chain are also useful.

In addition to the above-mentioned alkali-soluble binder, as an alkali-soluble binder in the present invention, an acid anhydride is added to a polymer having a hydroxyl group, or a polyhydroxy group. A styrene resin, a polyoxyalkylene resin, poly(2-hydroxyethyl (meth)acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, or the like is also useful. Further, the linear organic high molecular polymer may be obtained by copolymerizing a monomer having hydrophilicity. Examples thereof include alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, glycerol (meth)acrylate, (meth)acrylamide, and N-methylol. Acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinyl pyrrolidone, N-ethylene Amidoxime, vinylimidazole, vinyltriazole, methyl (meth)acrylate, ethyl (meth)acrylate, branched or linear propyl (meth)acrylate, branched or linear ( Butyl methacrylate, phenoxy hydroxypropyl (meth) acrylate, and the like. Further, as the hydrophilic monomer, it contains a tetrahydroindenyl group, a phosphoric acid group, a phosphate group, a quaternary ammonium salt group, an extended ethoxy chain, a propoxy chain, a sulfonic acid group or a salt thereof. A monomer such as a morpholinoethyl group or the like is also useful.

Further, in order to improve the crosslinking efficiency, the alkali-soluble binder may have a polymerizable group in the side chain, for example, an allyl group, a (meth)acryl fluorenyl group, or an allyloxyalkyl group in the side chain. Polymers and the like are also useful. Examples of the polymer containing the above polymerizable group include commercially available KS RESIST-106 (manufactured by Osaka Organic Chemical Industry Ltd.), and CYCLOMERP series (Daisai Chemical Industry Co., Ltd. ( (manufactured by DAICEL Chemical Industries, Ltd.) and the like. Further, in order to increase the strength of the hardened film, alcohol-soluble nylon or a polyether of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin may also be useful.

Among the above various alkali-soluble binders, from the viewpoint of heat resistance, Preferably, it is a polyhydroxy styrene resin, a polyoxyalkylene resin, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin, and acrylic acid is preferred from the viewpoint of controlling developability. A resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin.

The acrylic resin preferably contains a copolymer of a monomer selected from the group consisting of benzyl (meth)acrylate, (meth)acrylic acid, hydroxyethyl (meth)acrylate, and (meth)acrylamide. KS RESIST-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) or CYCLOMER P series (manufactured by Daicel Chemical Industries Co., Ltd.).

The alkali-soluble binder is preferably a weight average molecular weight (polystyrene-converted value measured by Gel Permeation Chromatography (GPC)) from the viewpoint of developability, liquid viscosity, and the like. The polymer of 2 × 10 ⁵ is more preferably a polymer having a weight average molecular weight of from 2,000 to 1 × 10 ⁵ , particularly preferably a polymer having a weight average molecular weight of from 5,000 to 5 × 10 ⁴ .

It may contain an alkali-soluble binder alone or two or more alkali-soluble binders.

Light sensitizer

A photosensitizer can also be added to the colored curable composition of the present invention. As a typical sensitizer which can be used in the present invention, those disclosed in Crivello [JVCrivello, Adv. in Polymer Sci, 62, 1 (1984)] can be cited, and specifically, Anthraquinone, anthracene, acridine, thioxanthone, 2-chlorothiazepine, benzoflavin, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthracene, diphenyl ketone, fragrant beans , coumarin, phenanthrene, camphorquinone, and phenothiazine derivatives. The photosensitizer is preferably added in a proportion of 50% by weight to 200% by weight based on the photopolymerization initiator.

Chain transfer agent

A chain transfer agent may also be added to the color hardening composition of the present invention. As the chain transfer agent which can be used in the present invention, for example, N,N-dialkylaminobenzoic acid alkyl ester such as N,N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2 - mercaptobenzoxazole, 2-mercaptobenzimidazole, N-phenylmercaptobenzimidazole, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine- a mercapto compound having a heterocyclic ring such as 2,4,6(1H,3H,5H)-trione, and pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyloxy) butyl An aliphatic polyfunctional fluorenyl compound such as an alkane.

The chain transfer agent may be used singly or in combination of two or more.

From the viewpoint of reducing the sensitivity deviation, the amount of the chain transfer agent added is preferably in the range of 0.01% by weight to 15% by weight, more preferably 0.1% by weight to 10% by weight based on the total solid content of the composition of the present invention. , particularly preferably from 0.5 wt% to 5 wt%.

Polymerization inhibitor

The colored curable resin composition of the present invention may further contain a polymerization inhibitor.

The term "polymerization inhibitor" refers to a substance that supplies hydrogen (or imparts hydrogen), provides energy (or grants energy) to a polymerization starting species such as a radical generated in a colored curable resin composition by light or heat. Providing electrons (or electron donating) and the like, and exerting an effect of inactivating the polymerization starting species and suppressing unintentional initiation of polymerization. The use of paragraphs 0154 to 0173 of JP-A-2007-334322 can be used. Polymerization inhibitors, etc. Among these, p-methoxyphenol is preferably used as a polymerization inhibitor.

The content of the polymerization inhibitor in the color hardening composition of the present invention is preferably 0.0001% by weight to 5% by weight, more preferably 0.001% by weight to 5% by weight, particularly preferably 0.001, based on the total weight of the ethylenically unsaturated compound. Wt%~1wt%.

Organic solvents

The colored curable composition of the present invention may contain an organic solvent.

The organic solvent is not particularly limited as long as it satisfies the solubility of each component and the coloring curable composition, and it is particularly preferable to consider the solubility, coating property, and safety of the solid component. Sex to choose.

As the organic solvent, examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, isobutyl acetate, butyl propionate, and isopropyl butyrate. Ester, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl glycolate (for example: methyl glycolate, ethyl hydroxyacetate, butyl glycolate (specifically, Methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-hydroxypropionate, 2- Alkyl hydroxypropionates, methyl 2-oxy-2-methylpropanoate, ethyl 2-oxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate Ethylacetate, ethyl acetate, ethyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

Further, examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and ethyl cellosolve acetate. , diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like.

Examples of the ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.

Examples of the aromatic hydrocarbons include toluene, xylene, and the like.

From the viewpoints of the solubility of each of the above components, the solubility of the alkali-soluble binder in the case of containing an alkali-soluble binder, the improvement of the coating surface, and the like, it is also preferred to mix two or more kinds of the above organic solvents. In this case, it is particularly preferably a mixed solution comprising 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 Two or more kinds of methyl ether and propylene glycol methyl ether acetate.

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

Surfactant

The colored curable resin composition of the present invention may also contain a surfactant.

As the surfactant, any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant may be used, but a preferred surfactant is a nonionic surfactant. Specifically, the nonionic surfactant described in paragraph 0057 of JP-A-2009-098616 is preferred, and among them, a fluorine-based surfactant is preferred.

As another surfactant which can be used in the present invention, for example, MEGAFACE F142D, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F183, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, MEGAFACE are commercially available. F781, MEGAFACE F781-F, MEGAFACE R30, MEGAFACE R08, MEGAFACE F-472SF, MEGAFACE BL20, MEGAFACE R-61, MEGAFACE R-90 (manufactured by DIC Corporation), FLUORAD FC-135, FLUORAD FC -170C, FLUORAD FC-430, FLUORAD FC-431, Novec FC-4430 (manufactured by Sumitomo 3M Ltd.), ASAHI GUARD AG7105, 7000, 950, 7600, SURFLON S-112, SURFLON S- 113, SURFLON S-131, SURFLON S-141, SURFLON S-145, SURFLON S-382, SURFLON SC-101, SURFLON SC-102, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC- 106 (manufactured by Asahi Glass Co., Ltd.), EFTOP EF351, EFTOP EF352, EFTOP EF801, EFTOP EF802 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.) , FTERGENT 250 (Neo (Shares) (Neos Company Ltd.)) and the like.

In addition, as a surfactant, a copolymer containing a structural unit A and a structural unit B represented by the following formula (1), and a tetrahydrofuran (THF) as a solvent are used as a preferable example. The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography is 1,000 Up, 10,000 or less.

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

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

In the above formula (2), R ⁵ represents an alkyl group having 1 or more and 4 or less carbon atoms, and the carbon number is preferably 1 or more from the viewpoint of compatibility and wettability to a surface to be coated. An alkyl group of 3 or less is more preferably an alkyl group having 2 or 3 carbon atoms.

The sum (p+q) of p and q in the above formula (1) is preferably p+q=100, that is, 100% by weight.

The weight average molecular weight (Mw) of the above copolymer is more preferably 1,500 or more and 5,000 or less.

The surfactant may be used singly or in combination of two or more. The amount of the surfactant added to the colored curable composition of the present invention is preferably from 0.01% by weight to 2.0% by weight, particularly preferably from 0.02% by weight to 1.0% by weight, based on the solid content. When it is this range, the coatability and the uniformity of a cured film become favorable.

Adhesive improver

The colored curable resin composition of the present invention may further contain a adhesion improving agent.

The adhesion improving agent is a compound which improves the adhesion between an inorganic substance (for example, a bismuth compound such as glass, ruthenium, osmium oxide or tantalum nitride, gold, copper, aluminum, etc.) which becomes a substrate and a cured film. Specific examples thereof include a decane coupling agent, a thiol compound, and the like. The decane coupling agent as the adhesion improving agent is not particularly limited as long as it is modified by the interface, and a known decane coupling agent can be used.

The decane coupling agent is preferably a decane coupling agent described in paragraph 0048 of JP-A-2009-98616, wherein γ-glycidoxypropyltrialkoxydecane or γ-甲 is more preferable. Alkyl acryloxypropyl trialkoxy decane. These may be used alone or in combination of two or more.

Adhesion in the color hardening composition of the present invention relative to the total solid content The content of the modifier is preferably from 0.1% by weight to 20% by weight, more preferably from 0.2% by weight to 5% by weight.

Crosslinker

Further, the crosslinking agent may be used in the colored curable composition of the present invention to further increase the hardness of the colored cured film obtained by curing the colored curable composition.

The crosslinking agent is not particularly limited as long as it can be cured by a crosslinking reaction, and examples thereof include (a) an epoxy resin; and (b) a solvent selected from the group consisting of a methylol group and an alkoxy group. a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one substituent in the group and the methoxymethyl group; (c) selected from the group consisting of a methylol group, an alkoxymethyl group, and an anthracene oxygen group A phenol compound, a naphthol compound or a hydroxyquinone compound substituted with at least one substituent of the methyl group. Among them, a polyfunctional epoxy resin is preferred.

For details of specific examples of the crosslinking agent, etc., reference is made to paragraphs [0134] to [0147] of JP-A-2004-295116.

Development accelerator

When the alkali solubility in the non-exposed region is promoted to further improve the developability of the colored curable composition, a development accelerator may be added to the colored curable composition of the present invention. The development accelerator is preferably a low molecular weight organic carboxylic acid compound having a molecular weight of 1,000 or less or a low molecular weight phenol compound having a molecular weight of 1,000 or less.

Specific examples thereof include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, diethylacetic acid, heptanoic acid, and caprylic acid; oxalic acid and malonic acid; , succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, bismuth Fats such as diacid, sebacic acid, tridecanedioic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethyl succinic acid, citraconic acid a dicarboxylic acid; an aliphatic tricarboxylic acid such as 1,2,3-propanetricarboxylic acid, aconitic acid, norbornene tricarboxylic acid; benzoic acid, toluic acid, 4-isopropylbenzoic acid, 2,3-dimethyl Aromatic monocarboxylic acids such as hemellitic acid and 3,5-dimethylbenzoic acid; phthalic acid, isophthalic acid, terephthalic acid, 1,2,4-benzenetricarboxylic acid, Aromatic polycarboxylic acid such as trimellitic acid, 1,2,3,5-benzenetetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid; phenylacetic acid, hydrogen atoic acid, hydrogen cinnamic acid, mandelic acid , phenyl succinic acid, atopic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, phenyl allyl acetic acid, coumaric acid, umbrella acid, and the like.

Other additives

In the color hardening composition of the present invention, various additives such as a filler, a polymer compound other than the above, an ultraviolet absorber, an antioxidant, or an anti-agglomerating agent may be added as needed. As such additives, the additives described in paragraphs [0155] to [0156] of JP-A-2004-295116 may be mentioned.

The light-stable composition of the present invention may contain the light stabilizer described in paragraph [0078] of JP-A-2004-295116, and the heat-resistant polymerization agent described in paragraph [0081] of the above-mentioned publication. .

Preparation of colored curable composition

The colored curable composition of the present invention can be prepared by mixing the above components with any optional components as needed.

Furthermore, when preparing a colored curable composition, it can be formulated in one time to form a color. Each component of the curable composition may be prepared by dissolving and dispersing each component in a solvent. In addition, the order of input or the working conditions at the time of preparation are not particularly restricted. For example, all the components can be simultaneously dissolved and dispersed in a solvent to prepare a composition, and if necessary, each component can be suitably prepared into two or more kinds of solutions. Dispersion, these solutions are used (when applied). The dispersion was mixed to prepare as a composition.

The colored curable composition prepared in the above manner is preferably used after being filtered using a filter having a pore diameter of about 0.01 μm to 3.0 μm.

The colored curable composition of the present invention is excellent in solubility in a solvent (such as an organic solvent contained as necessary) contained in the colored curable composition, and is selected from the compounds represented by the above formula (I) and At least one of the groups consisting of tautomers thereof is used as a colorant. Therefore, even if the content rate of the coloring agent is increased, a color hardening composition excellent in storage stability can be obtained. Further, the colored cured film obtained by curing the colored curable composition can form a colored cured film having high optical density, excellent color tone, and contrast even in a thin layer. Therefore, it can be suitably used as a display device such as a liquid crystal display device (LCD) or a solid-state imaging device (for example, a Charge Coupled Device (CCD), a Complementary Metal Oxide Semiconductor (CMOS), or the like). The color filter used for a color filter or the like is used for forming, and can be suitably used as a printing ink, an inkjet ink, a paint, or the like. In particular, it is suitable for use in the formation of colored pixels for display devices.

Color filter and manufacturing method thereof

The color filter of the present invention has at least a substrate (hereinafter referred to as a "support"), Further, a colored region including the color hardening composition of the present invention is provided on the substrate. The colored region on the substrate includes a colored film such as red (R), green (G), blue (B) or the like which forms each pixel of the color filter.

The method for producing a color filter according to the present invention includes the step (A) of applying the colored curable composition described above to a support to form a colored layer (also referred to as a colored curable composition layer); and a step (B) The colored curable composition layer formed in the step (A) is exposed to a pattern and developed to form a colored region (colored pattern). Further, the method for producing a color filter of the present invention is particularly preferably in the form of a step (C) of irradiating the colored pattern formed by the step (B) with ultraviolet rays; and the step (D) In step (C), the colored pattern irradiated with ultraviolet rays is subjected to heat treatment.

Hereinafter, a method of producing the color filter of the present invention will be described more specifically.

Step (A)

In the method of producing a color filter of the present invention, first, the present invention described above is applied by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, or inkjet. The colored hardening composition is applied onto a support to form a colored curable composition layer, and thereafter, the colored curable composition is heated (pre-baking) or vacuum dried. The layer is dried.

Examples of the support include soda glass, alkali-free glass, borosilicate glass, quartz glass, a ruthenium substrate, and a resin substrate used in a display device and the like. Further, in order to improve the adhesion to the upper layer, prevent the diffusion of substances, or flatten the surface, an undercoat layer may be provided on the supports as needed.

The conditions for prebaking include a hot plate or an oven, and are heated at 70 ° C to 130 ° C for about 0.5 minutes to 15 minutes.

Further, the thickness of the colored curable composition layer formed of the colored curable composition is appropriately selected depending on the purpose. The color filter for a display device preferably has a range of 0.2 μm to 5.0 μm, more preferably 1.0 μm to 4.0 μm. Further, in the color filter for a solid-state imaging device, it is preferably in the range of 0.2 μm to 5.0 μm, more preferably in the range of 0.3 μm to 2.5 μm. Further, the thickness of the colored curable composition layer is the film thickness after drying.

Step (B)

Then, in the method of producing a color filter of the present invention, the colored curable composition layer formed on the support is subjected to pattern exposure. As the light or radiation that can be applied to the exposure, g-rays, h-rays, i-rays, various kinds of laser light, and particularly preferably i-rays are preferable. When i-rays are used for the irradiation of light, it is preferably irradiated with an exposure amount of ⁵ mJ/cm ² to 500 mJ/cm ² .

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

Exposure step using a laser source

In the exposure method using a laser light source, the irradiation light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 410 nm, more preferably a wavelength in the range of 300 nm to 360 nm. Specifically, in particular, a third harmonic (355 nm) of a solid laser Nd:YAG laser having a large output power and a relatively inexpensive output, or XeCl (308 nm) of an excimer laser, XeF (353 nm). The amount of pattern exposure is preferably in the range of 1 mJ/cm ² to 100 mJ/cm ² , and more preferably in the range of 1 mJ/cm ² to 50 mJ/cm ² from the viewpoint of productivity.

The exposure apparatus is not particularly limited, and as a commercially available exposure apparatus, Callisto (manufactured by V Technology Co., Ltd.), EGIS (manufactured by V Technology Co., Ltd.), or DF2200G (large Japan Screen Co., Ltd. (made by Dainippon Screen Mfg. Co., Ltd.) and the like. Further, a device other than the above may be suitably used.

Then, the exposed color-curable composition layer after development is developed with a developing solution. Thereby, a colored pattern can be formed. The developer may be a combination of various organic solvents or an alkaline aqueous solution as long as it dissolves the uncured portion of the colored curable composition layer and does not dissolve the hardened portion. When the developer is an alkaline aqueous solution, it is preferably adjusted so that the alkali concentration becomes preferably pH 10 to 13. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, and hydroxide. An alkaline aqueous solution of tetramethylammonium, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5,4,0]-7-undecene.

The development time is preferably from 30 seconds to 300 seconds, more preferably from 30 seconds to 120 seconds. The developing temperature is preferably from 20 ° C to 40 ° C, more preferably 23 ° C.

Development can be carried out by a puddle method, a shower method, a spray method, or the like.

Further, it is preferred to carry out washing with water after development using an alkaline aqueous solution.

Step (C)

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

Step (D)

It is preferable to carry out heat treatment for the coloring pattern which is subjected to post-exposure by ultraviolet irradiation as described above. The colored pattern can be further hardened by subjecting the formed colored pattern to heat treatment (so-called post-baking treatment). This heat treatment can be performed, for example, by a hot plate, various heaters, an oven, or the like.

The temperature during the heat treatment is preferably from 100 ° C to 300 ° C, more preferably from 150 ° C to 250 ° C. Further, the heating time is preferably from about 10 minutes to about 120 minutes.

The colored pattern obtained in the above manner constitutes a pixel in the color filter. When producing a color filter having a plurality of hues of pixels, the above steps (A), (B), and optionally (C) or (D) are repeated in combination with a desired number of colors. can.

Further, after the formation, exposure, and development of each of the monochromatic coloring-curable composition layers (one color per time), the above steps (C) and/or steps (D) may be performed, or may be performed at all After the formation, exposure, and development of the colored curable composition layer of the desired number of colors are completed, the above step (C) and/or step (D) are performed at one time.

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

Display device

The display device of the present invention includes the color filter of the present invention described above.

When the color filter of the present invention is used in a display device, a metal complex dye having excellent spectral characteristics and heat resistance is used as a colorant, and the voltage holding ratio at the time of voltage application is not lowered, and the specific resistance is The alignment failure of the liquid crystal molecules accompanying the falling phase is small, and the color of the displayed image is good and the display characteristics are excellent.

Therefore, the display device including the color filter of the present invention can display a high-quality image, and the display image of the high-quality image is excellent in color and excellent in display characteristics.

The definition of the display device or the details of each display device is, for example, "Electronic display element (Kogyo Chosakai Publishing Co., Ltd. issued in 1990)", "Display element ( It is described in the book "Sangyo Tosho Publishing Co., Ltd., issued in the first year of Heisei (1989)". In addition, the display device is described in, for example, "Next-generation liquid crystal display technology (edited by Uchida Natsuo, Industrial Research Association (share) issued in 1994). The display device to which the present invention is applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the "next-generation liquid crystal display technology".

The color filter of the present invention can also be used in a display device of a Thin Film Transistor (TFT) type. About the color TFT method The display device is described, for example, in "Color TFT Liquid Crystal Display (Kyoritsu Shuppan Co., Ltd., issued in 1996)". Further, the present invention can also be applied to a display in which a viewing angle such as a transverse electric field driving method such as In-Plane Switching (IPS) or a pixel division method such as Multi-domain Vertical Alignment (MVA) is expanded. Device, or applied to Super Twisted Nematic (STN), Twisted Nematic (TN), Vertical Alignment (VA), Optically Compensated Splay (OCS), edge electric field switching (Fringe Field Switching, FFS), and Reflective Optically Compensated Bend (R-OCB).

In addition, the color filter of the present invention is also available in a bright and high-definition Color-filter On Array (COA) mode. In the COA display device, in addition to the usual required characteristics as described above, the required characteristics of the color filter layer may be required for the interlayer insulating film, that is, low dielectric constant and peeling resistance. In the color filter of the present invention, since a dye multimer having excellent color tone is used, color purity, light transmittance, and the like are excellent, and the color of the colored pattern (pixel) is excellent, so that high resolution and long-term durability can be provided. Excellent COA display device. Further, in order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.

For the image display methods, for example, "EL, PDP, LCD Display - Technology and Market Trends - (Toray Research Center Inc. Research and Research Division, 2001)", page 43, etc. There are records in it.

The display device including the color filter of the present invention includes an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film in addition to the color filter of the present invention. And other components. The color filter of the present invention can be applied to a display device including such well-known members. Regarding these components, for example, "the market of the '94 liquid crystal display peripheral materials and chemicals (issued by CMC Publishing Co., Ltd. in 1994), "the current status and future of the liquid crystal related market in 2003" The Outlook (Vol. 2) (Fuji Chimera Research Institute, Inc., issued in 2003) is documented.

For the backlight, SID meeting Digest 1380 (2005) (A. Konno et al.), or Monthly Display (Monthly Display) December 18th, page 18 ~ page 24 (Island Kang Yu) ), and the 25th to 30th pages of the December 2005 issue of the Display Monthly (Yumu Longming) are recorded.

When the color filter of the present invention is used for a display device, high contrast can be achieved when combined with a conventionally known three-wavelength tube of a cold cathode tube, and further, by using red, green, and blue light-emitting diodes A (Light Emitting Diode, LED) light source (RGB-LED) is used as a backlight to provide a display device with high brightness, high color purity, and good color reproducibility.

Solid photographic element

The solid-state imaging device of the present invention comprises the color filter of the present invention described above. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it has a configuration in which the color filter of the present invention is provided and functions as a solid-state imaging device. For example, the following structures are mentioned.

The configuration includes a plurality of photodiodes constituting a light receiving region of a solid-state imaging device (a CCD image sensor, a CMOS image sensor, or the like) and a transfer electrode including a polysilicon or the like on the support. The light-receiving electrode and the transfer electrode have a light-shielding film containing tungsten or the like that is opened only to the light-receiving portion of the photodiode, and the light-shielding film includes a surface that covers the entire surface of the light-shielding film and the photodiode light-receiving portion. An element protective film such as tantalum nitride has the color filter of the present invention on the element protective film.

Further, a configuration may be adopted in which the light-receiving device (for example, a microlens or the like, the same applies hereinafter) on the element protective layer and under the color filter (on the side close to the support). Or a configuration in which a condensing device is provided on the color filter.

[Examples]

Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited to the following examples as long as the scope of the invention is not exceeded. In addition, "parts" and "%" are quality standards unless otherwise specified.

[Example 1]: Synthesis of a specific dipyrromethene metal complex

The specific dipyrromethene metal complex of the present invention can be synthesized, for example, by the following Scheme A or Scheme B. In the following Schemes A and B, R _x and R _y each represent a compound A-1 to a compound A-96 which are specific examples of the specific dipyrromethene metal complex of the present invention. R ¹⁷ and R ¹⁸ .

According to the above Scheme A, an exemplary compound A-41 and an exemplary compound A-55 of the specific dipyrromethene metal complex of the present invention are synthesized, and the exemplified compound A-7 and the exemplified compound A-1 are respectively synthesized according to the above Scheme B. .

(Synthesis of Intermediate 1)

The intermediate 1 is synthesized by the method described in the specification of the US Patent Application Publication No. 2008/0076044.

(Synthesis of Intermediate 2)

To 60 ml of N,N-dimethylacetamide, 30.6 g (0.3 mol) of trimethylacetic acid was added, and the mixture was stirred under ice bath. To the solution, 35.7 g (0.3 mol) of sulfinium chloride was added dropwise, and the mixture was stirred for 1 hour in an ice bath, and then stirred at room temperature for 1 hour to obtain a hydrazine halide solution.

Further, 82.1 g (0.2 mol) of the intermediate 1 was added to 200 ml of N,N-dimethylacetamide, and the mixture was stirred under ice cooling, and the solution was added dropwise. Thereafter, the mixture was stirred under ice cooling for 1 hour and then at room temperature for 3 hours.

After completion of the reaction, 700 ml of acetonitrile was added to the reaction mixture, and the mixture was stirred for 1 hour, and then filtered, and the obtained solid was dried. Thus, 92 g (yield: 93%) of Intermediate 2 was obtained.

Furthermore, the details of ¹ H-NMR (CDCl ₃ ) are δ: 11.02 (s, 1H), 10.82 (s, 1H), 7.92 (d, 1H), 7.37 to 7.25 (m, 5H), 6.28 (s) , 1H), 5.87 (s, 1H), 5.56 (s, 1H), 1.36 (s, 9H), 1.25 to 0.97 (m, 5H), 0.83 (s, 18H), 0.71 to 0.69 (d, 3H), 0.58~0.46(q, 2H).

(Synthesis of Intermediate 3)

120 ml of tetrahydrofuran and 150 ml of dimethylformamide (DMF) were stirred under ice bath, and 18.6 g of phosphorus oxychloride was added dropwise. After completion of the dropwise addition, the mixture was stirred at 5 ° C or lower for 1 hour. Intermediate 2 was added little by little to the solution. After that, stir in an ice bath Mix for 1 hour and then stir at room temperature for 2 hours. After completion of the reaction, the reaction solution was poured into 300 ml of water and 300 ml of ethyl acetate, and extracted. The ethyl acetate solution was washed with saturated brine and dried over anhydrous magnesium sulfate, and then the solvent was evaporated. The obtained solid was washed with 500 ml of methanol, then filtered and dried. Thus, 36 g (yield: 86%) of Intermediate 3 was obtained.

Furthermore, the details of ¹ H-NMR (CDCl ₃ ) are δ: 11.35 (s, 1H), 11.14 (s, 1H), 8.98 (s, 1H), 7.45 to 7.40 (m, 3H), 7.35 to 7.26. (m, 2H), 5.90 (s, 1H), 1.37 (s, 9H), 1.27 to 0.98 (m, 5H), 0.82 (s, 18H), 0.71 to 0.69 (d, 3H), 0.45 to 0.33 (q , 2H).

(Synthesis of Intermediate 4)

To 250 ml of N-methylpyrrolidone, 76.1 g (0.5 mol) of methyl salicylate, 56.7 g (0.6 mol) of 2-chloromethylethyl ether, 8.3 g (0.05 mol) of potassium iodide, and potassium carbonate 82.9 were added. g (0.6 mol) and stirred at 120 ° C for 16 hours.

After cooling the reaction mixture, 300 ml of water and 300 ml of ethyl acetate were added for extraction, and the ethyl acetate solution was washed with saturated brine, and the solvent was distilled off. Thereafter, 40 g of a 50% aqueous NaOH solution, 40 ml of water, and 40 ml of ethanol were added, and the mixture was stirred at 100 ° C for 1 hour.

After completion of the reaction, hydrochloric acid water was added thereto for neutralization, and then ethyl acetate was added thereto for extraction. The ethyl acetate solution was washed with saturated brine and the solvent was distilled off. Thereafter, purification was carried out by a silica gel column chromatography to obtain 59 g (yield: 60%) of Intermediate 4.

Furthermore, the details of ¹ H-NMR (CDCl ₃ ) are δ: 8.18 to 8.14 (m, 1H), 7.58 to 7.52 (m, 1H), 7.17 to 7.14 (m, 1H), 7.07 to 7.04 (m, 1H), 4.39~4.36(t, 2H), 3.83~3.79(t, 2H), 3.46(s, 3H).

(Synthesis of Intermediate 5)

To 20 ml of N,N-dimethylacetamide, 19.6 g (0.1 mol) of Intermediate 4 was added and stirred under ice bath. To the solution, 11.9 g (0.1 mol) of sulfite chloride was added dropwise, and the mixture was stirred for 1 hour in an ice bath, and then stirred at room temperature for 1 hour to obtain a hydrazine halide solution.

Further, 27.4 g (0.07 mol) of the intermediate 1 was added to 70 ml of N,N-dimethylacetamide, and the mixture was stirred under ice cooling, and the solution was added dropwise. Thereafter, the mixture was stirred under ice cooling for 1 hour and then at room temperature for 3 hours.

After completion of the reaction, 200 ml of acetonitrile was added to the reaction mixture, and the mixture was stirred for 1 hour, and then filtered, and the obtained solid was dried. Thus, 33 g (yield: 85%) of Intermediate 5 was obtained.

Further, the details of ¹ H-NMR (CDCl ₃ ) are δ: 12.47 (s, 1H), 11.29 (s, 1H), 8.23 to 8.20 (m, 1H), 7.54 to 7.48 (m, 1H), 7.36. ~7.08(m,6H),6.35(s,1H),5.90(s,1H),4.58~4.54(t,2H),3.96~3.92(t,2H),3.39(s,3H),1.26~0.97 (m, 5H), 0.86 (s, 18H), 0.71 to 0.69 (d, 3H), 0.64 to 0.47 (q, 2H).

(Synthesis of Intermediate 6)

To 45 ml of acetic anhydride, 7.8 g (15 mmol) of Intermediate 3, 8.8 g (15 mmol) of Intermediate 5 were added and stirred under ice bath. Thereafter, 17.1 g (150 mmol) of trifluoroacetic acid was added, and the mixture was stirred for 1 hour in an ice bath, and then stirred at room temperature for 1 hour. Further, 25.2 g of sodium hydrogencarbonate was added to 40 ml of ethyl acetate and 300 ml of water, and the mixture was stirred, and then the reaction solution was added to the mixed solution and stirred for 2 hours. Thereafter, the precipitated solid was filtered, washed with ethyl acetate, and dried. Thus, 12.5 g (yield 76%) of Intermediate 6 was obtained.

Furthermore, the details of ¹ H-NMR (CDCl ₃ ) are δ: 12.50 (s, 1H), 10.96 (s, 1H), 8.48 to 8.45 (d, 1H), 7.53 to 7.47 (m, 1H), 7.29. ~7.09(m,8H),6.03(s,1H),5.88(s,1H),4.58~4.54(t,2H),3.92~3.89(t,2H),3.39(s,3H),1.44(s , 9H), 1.21~0.95 (m, 10H), 0.81 (s, 36H), 0.65~0.63 (d, 6H), 0.43~0.31 (q, 4H).

(Synthesis of Compound A-41)

To 35 ml of tetrahydrofuran, 10.9 g (10 mmol) of Intermediate 6 and 2.3 g (11 mmol) of zinc acetate dihydrate were added, and the mixture was stirred at 50 ° C for 5 hours. After completion of the reaction, the solvent was distilled off. The obtained solid was stirred at 60 ° C for 1 hour in a methanol/water mixed solvent, and then filtered and dried. Thus, 11.3 g (yield 92%) of the exemplified compound A was obtained.

Further, the details of ¹ H-NMR (CDCl ₃ ) are δ: 12.97 (s, 1H), 11.47 (s, 1H), 8.41 to 8.38 (m, 1H), 7.57 to 7.51 (m, 1H), 7.28. ~7.12(m,8H), 6.24(s,1H),5.86(s,1H),4.64~4.61(t,2H),3.88~3.84(t,2H),3.38(s,3H),1.93(s , 3H), 1.47 (s, 9H), 1.26 to 0.94 (m, 10H), 0.81 (m, 36H), 0.65 to 0.63 (d, 6H), 0.43 to 0.38 (m, 4H).

(Synthesis of Intermediate 7)

Adding 2,2-dimethylbutyric acid to 60 ml of N,N-dimethylacetamide 34.8 g (0.3 mol) and stirred under an ice bath. To the solution, 35.7 g (0.3 mol) of sulfinium chloride was added dropwise, and the mixture was stirred for 1 hour in an ice bath, and then stirred at room temperature for 1 hour to obtain a hydrazine halide solution.

82.1 g (0.2 mol) of the intermediate 1 was added to 200 ml of N,N-dimethylacetamide, and the mixture was stirred under ice cooling, and the solution was added dropwise. Thereafter, the mixture was stirred under ice cooling for 1 hour and then at room temperature for 3 hours.

After completion of the reaction, 700 ml of acetonitrile was added to the reaction mixture, and the mixture was stirred for 1 hour, and then filtered, and the obtained solid was dried. Thus, 91.6 g (yield: 90%) of Intermediate 7 was obtained.

Further, the details of ¹ H-NMR (CDCl ₃ ) are δ: 10.98 (s, 1H), 10.80 (s, 1H), 7.37 to 7.25 (m, 5H), 6.28 (m, 1H), 5.87 (s , 1H), 1.73~1.66(q,2H), 1.32(s,6H), 1.25~0.90(m,8H),0.83(s,18H),0.70~0.68(d,3H),0.58~0.46(q , 2H).

(Synthesis of Intermediate 8)

70 ml of tetrahydrofuran and 100 ml of dimethylformamide (DMF) were stirred under ice bath, and 11.8 g (77 mmol) of phosphorus oxychloride was added dropwise. After completion of the dropwise addition, the mixture was stirred at 5 ° C or lower for 1 hour. Intermediate 7 was added little by little to the solution. Thereafter, the mixture was stirred under an ice bath for 1 hour and then at room temperature for 2 hours. After completion of the reaction, the reaction solution was poured into 300 ml of water and 200 ml of ethyl acetate, and extracted. The ethyl acetate solution was washed with saturated brine and dried over anhydrous magnesium sulfate, and then the solvent was evaporated. The obtained solid was washed with 500 ml of methanol, then filtered and dried. Thus, 22.9 g (yield: 83%) was obtained. Inter-substance 8.

Further, the details of ¹ H-NMR (CDCl ₃ ) are δ: 11.36 (s, 1H), 11.10 (s, 1H), 8.98 (s, 1H), 7.43 to 7.31 (m, 3H), 5.90 (s) , 1H), 1.75~1.67(q,2H), 1.32(s,6H), 1.25~0.87(m,8H),0.82(s,18H),0.71~0.69(d,3H),0.45~0.33(q , 2H).

(Synthesis of Intermediate 9)

Salicylaldehyde 73.3 g (0.6 mol), 2-ethylhexyl bromide 173.8 g (0.9 mol), and sodium hydroxide 36 g (0.9 mol) were added to 300 ml of N-methylpyrrolidone, and stirred at 120 ° C. 4 hours. After cooling the reaction mixture, 360 ml of water and 360 ml of ethyl acetate were added for extraction, and the ethyl acetate solution was washed with saturated brine.

To the ethyl acetate solution, 2.0 g (0.006 mol) of tetrabutylammonium hydrogen sulfate, 18.7 g (0.12 mol) of sodium dihydrogen phosphate dihydrate, and 74.8 g (0.66 mol) of 30% hydrogen peroxide water were added, and Stir under a water bath. Thereafter, 25 wt% of sodium hypochlorite was added dropwise, and the mixture was stirred at 50 ° C for 9 hours. After completion of the reaction, ethyl acetate was added thereto for extraction, and the ethyl acetate solution was washed with water, washed with saturated brine, dried over anhydrous magnesium sulfate, and then the solvent was evaporated. The obtained solid was recrystallized with an ethyl acetate/hexane mixed solvent and dried.

Thus, 112 g (yield: 67%) of Intermediate 9 was obtained.

Furthermore, the details of ¹ H-NMR (CDCl ₃ ) are δ:10.99 (br, 1H), 8.21 to 8.19 (m, 1H), 7.59 to 7.53 (m, 1H), 7.26 to 7.05 (m, 2H). , 4.17~4.15(d,2H), 1.89~1.79(m,1H), 1.55~1.29(m,8H), 1.00~0.89(m, 6H).

(Synthesis of Intermediate 10)

90.1 g (0.36 mol) of Intermediate 9 was added to 100 ml of N,N-dimethylacetamide and stirred under ice bath. To the solution, 42.8 g (0.36 mol) of sulfinium chloride was added dropwise, and the mixture was stirred for 1 hour in an ice bath, and then stirred at room temperature for 1 hour to obtain a hydrazine halide solution.

123.1 g (0.3 mol) of Intermediate 1 was added to 300 ml of N,N-dimethylacetamide, and the mixture was stirred under ice cooling, and the solution was added dropwise. Thereafter, the mixture was stirred under ice cooling for 1 hour and then at room temperature for 3 hours.

After completion of the reaction, 450 ml of acetonitrile was added to the reaction mixture, and the mixture was stirred for 1 hour, and then filtered, and the obtained solid was dried. Thus, 179.0 g (yield: 93%) of Intermediate 10 was obtained.

Furthermore, the details of ¹ H-NMR (CDCl ₃ ) are δ: 12.35 (s, 1H), 11.34 (s, 1H), 8.22 to 8.18 (m, 1H), 7.52 to 7.46 (m, 1H), 7.35. ~7.28(m,5H),7.10~7.04(m,2H),6.34(s,1H),5.89(s,1H),4.31~4.29(d,2H),2.19~2.09(m,1H),1.54 ~1.16 (m, 11H), 1.04~0.82 (m, 26H), 0.71~0.69 (d, 3H), 0.59~0.46 (m, 2H).

(Synthesis of Intermediate 11)

To 45 ml of acetic anhydride, 8.1 g (15 mmol) of Intermediate 8 and 9.6 g (15 mmol) of Intermediate 10 were added and stirred under ice bath. Thereafter, 17.1 g (150 mmol) of trifluoroacetic acid was added, and the mixture was stirred for 1 hour in an ice bath, and then stirred at room temperature for 1 hour. Further, to a solution of 40 ml of ethyl acetate and 300 ml of water, 25.2 g of sodium hydrogencarbonate was added. The mixture was stirred, and then the above reaction solution was added to the mixed solution and stirred for 2 hours. Thereafter, the precipitated solid was filtered, washed with ethyl acetate, and dried. Thus, 13.3 g (yield 76%) of the intermediate 11 was obtained.

Furthermore, the details of ¹ H-NMR (CDCl ₃ ) are δ: 12.39 (s, 1H), 10.87 (s, 1H), 8.45 to 8.42 (d, 1H), 7.51 to 7.46 (m, 1H), 7.30. ~7.02(m,13H),6.04(s,1H),5.88(s,1H),5.86(s,1H), 4.29~4.27(d,2H),2.15(m,1H),1.83~1.75(q , 2H), 1.51~0.79 (m, 69H), 0.65~0.62 (m, 6H), 0.43~0.31 (q, 4H).

(Synthesis of Compound A-55)

11 g (9.4 mmol) of Intermediate 11 and 2.5 g of zinc acetate dihydrate (11.3 mmol) were added to 35 ml of tetrahydrofuran, and the mixture was stirred at 50 ° C for 4 hours. After completion of the reaction, the solvent was distilled off. The obtained solid was stirred at 60 ° C for 1 hour in a methanol/water mixed solvent, and then filtered and dried. Thus, 12.0 g (yield 98%) of the exemplified compound B was obtained.

Furthermore, the details of ¹ H-NMR (CDCl ₃ ) are δ: 12.82 (s, 1H), 11.43 (s, 1H), 8.41 to 8.37 (m, 1H), 7.55 to 7.50 (m, 1H), 7.26. ~7.03(m,13H), 6.24(s,1H),5.86(s,1H), 4.37(m,2H),2.08(m,1H),1.93(s,3H),1.84~1.77(q,2H) ), 1.58~0.80 (m, 69H), 0.65~0.63 (d, 6H), 0.43~0.20 (m, 4H).

(Synthesis of Intermediate 12)

The intermediate 12 is synthesized by the method described in JP-A-2012-140586.

(Synthesis of Intermediate 13)

40 ml of toluene, 6.4 g of a 25% aqueous sodium hydroxide solution, and (20 mmol) of the intermediate 12 were stirred under a water bath, and 3.2 g (20 mmol) of 2-ethylhexyl chloride was added and stirred for 6 hours. Thereafter, 2.5 g of methanol was added and stirred for 30 minutes. The aqueous layer was removed by a liquid separation operation, and then the organic layer was washed with a 5% aqueous sodium hydroxide solution and a 15% aqueous acetic acid solution to obtain a toluene solution 1.

Further, 5.0 g (20 mmol) of the intermediate 4, 2.4 g of sulfite chloride (20 mmol), and 0.1 g of N,N-dimethylformamide were added to 6.4 ml of toluene, and the mixture was stirred at 40 ° C for 30 minutes. The cooling was carried out to obtain a hydrazine solution 1.

To the above toluene solution 1, 43.2 g of a 25% aqueous sodium hydroxide solution was added and stirred under a water bath. Thereafter, the hydrazine halide solution 1 was added dropwise and stirred for 3 hours. Thereafter, 20 g of methanol was added and stirred for 30 minutes, and then the aqueous layer was removed by a liquid separation operation. The organic layer was washed with a 5% aqueous sodium hydroxide solution and a 15% aqueous acetic acid solution, and then the solvent was evaporated. The obtained solid was washed with ethyl acetate, then filtered and dried. Thus, 8.3 g (yield 70%) of Intermediate 13 was obtained.

Furthermore, the details of ¹ H-NMR (CDCl ₃ ) are δ: 12.45 (s, 1H), 10.53 (s, 1H), 8.38 to 8.34 (m, 1H), 7.53 to 7.47 (m, 1H), 7.26. ~7.03(m,13H),6.01(s,1H),5.88(s,2H), 4.30~4.28(d,2H),2.18~2.08(m,1H),1.94~0.80(m,75H),0.67 ~0.62 (m, 6H), 0.41~0.34 (m, 4H).

(Synthesis of Compound A-7)

10.5 g (8.9 mmol) of Intermediate 13 and 2.4 g of zinc acetate dihydrate (10.7 mmol) were added to 35 ml of tetrahydrofuran, and stirred at 50 ° C for 4 hours. After the end, the solvent was distilled off. The obtained solid was stirred at 60 ° C for 1 hour in a methanol/water mixed solvent, and then filtered and dried. Thus, 10.7 g (yield 91%) of the exemplified compound C was obtained.

Furthermore, the details of ¹ H-NMR (CDCl ₃ ) are δ: 12.82 (s, 1H), 11.16 (s, 1H), 8.40 to 8.38 (m, 1H), 7.55 to 7.50 (m, 1H), 7.26. ~7.03(m,12H),6.25(s,1H),5.86(s,2H), 4.37(br,2H),2.66(m,1H),2.01(m,1H),1.91~0.80(m,77H ), 0.65~0.63 (d, 6H), 0.43~0.20 (m, 4H).

(Synthesis of Intermediate 14)

4.3 g (20 mmol) of 2-phenoxybenzoic acid, sulfinium chloride 2.4 g (20 mmol), and N,N-dimethylformamide 0.1 g were added to 6.4 ml of toluene, and stirred at 40 ° C. After a minute, cooling was carried out to obtain a hydrazine solution 2.

To the toluene solution 1 obtained in the same manner as in the synthesis of the intermediate 13, 43.2 g of a 25% aqueous sodium hydroxide solution was added, and the mixture was stirred under a water bath. Thereafter, the hydrazine solution 2 was added dropwise and stirred for 3 hours. Thereafter, 20 g of methanol was added and stirred for 30 minutes, and then the aqueous layer was removed by a liquid separation operation. The organic layer was washed with a 5% aqueous sodium hydroxide solution and a 15% aqueous acetic acid solution, and then the solvent was evaporated. The obtained solid was washed with ethyl acetate, then filtered and dried. Thus, 8.3 g (72% yield) of Intermediate 14 was obtained.

Furthermore, the details of ¹ H-NMR (CDCl ₃ ) are δ: 12.72 (s, 1H), 10.56 (s, 1H), 8.44 to 8.41 (d, 1H), 7.45 to 7.11 (m, 18H), 6.89. ~6.87(m,1H),6.03(s,1H),5.88(s,1H), 5.65(s,1H), 2.24(m,1H), 1.97~0.80(m,60H),0.70~0.63(m , 6H), 0.41~0.29 (m, 4H).

(Exemplified synthesis of compound A-1)

6.0 g (5.2 mmol) of Intermediate 13 and 1.4 g (6.2 mmol) of zinc acetate dihydrate were added to 20 ml of tetrahydrofuran, and the mixture was stirred at 50 ° C for 4 hours. After completion of the reaction, the solvent was distilled off. The obtained solid was stirred at 60 ° C for 1 hour in a methanol/water mixed solvent, and then filtered and dried. Thus, 6.4 g (yield 96%) of the exemplified compound C was obtained.

Furthermore, the details of ¹ H-NMR (CDCl ₃ ) are δ: 13.14 (s, 1H), 11.18 (s, 1H), 8.48 to 8.44 (m, 1H), 7.45 to 7.11 (m, 17H), 6.82. ~6.79(m,1H),6.28(s,1H),5.86(s,1H),5.56(s,1H), 2.49(m,1H),1.97(s,3H),1.78~0.79(m,60H ), 0.67~0.62 (m, 6H), 0.43~0.31 (m, 4H).

With respect to each of the obtained exemplified compounds, the molar absorption coefficient (ε) in a chloroform solution was measured using a spectrophotometer UV-1800PC (trade name, manufactured by Shimadzu Corporation). The maximum absorption wavelength λmax of the exemplified compound A-7 was 560.5 nm, and the molar absorption coefficient (ε) was 128,000.

Further, the solubility of the obtained compound with respect to propylene glycol monomethyl ether acetate and the weight reduction rate when the solid of the obtained compound was heated to 230 ° C were evaluated.

In addition, the results of the maximum absorption wavelength λmax, the molar absorption coefficient (ε), the solubility to propylene glycol monomethyl ether acetate, and the weight reduction ratio are shown in Table 1 to be described later.

[Embodiment 2]

The following Table 1 was synthesized by a method similar to the reaction scheme in Example 1. An exemplified compound (a compound represented by the formula (I) or a tautomer thereof) thereof, and identified in the same manner as in Example 1, and subjected to a maximum absorption wavelength λmax and a molar absorption coefficient (ε) The measurement of propylene glycol monomethyl ether acetate and the weight reduction rate were evaluated. The results are shown in Table 1 which will be described later.

Evaluation

(for the solubility of propylene glycol monomethyl ether acetate)

The sample was weighed and propylene glycol monomethyl ether acetate was added thereto so as to have the following concentrations, and the mixture was stirred at room temperature for 30 minutes, and then the dissolved state was visually confirmed.

*Judgement

More than 5wt% dissolved: A

1wt%~ less than 5wt%: B

Less than 1wt%: C

(weight reduction rate)

From 35 ° C to 230 ° C, the sample was heated to 10 ° C per minute, and the weight reduction rate (%) at 230 ° C for 30 minutes was evaluated.

*Judgement

Less than 5%: A

5%~ less than 10%: B

10% or more: C

Further, the details of Comparative Compound 1, Comparative Compound 2, and Comparative Compound 3 are as follows. The structural formula of each comparative compound is shown below.

. Comparative compound C1 (Japanese Patent Laid-Open Publication No. 2008-292970) Compound III-61)

. Comparative compound C2 (Compound A-29 described in JP-A-2010-85454)

. Comparative compound C3 (Compound III-45 described in JP-A-2008-292970)

From the results of Table 1, it is understood that the compound of the present invention is a compound having a high molar absorption coefficient and excellent solubility and heat resistance.

Hereinafter, specific examples of producing a colored curable composition and a color filter will be described.

[Example 3]

First, each component for preparing a colored curable composition is shown below.

(S-1): Pigment obtained by mixing CI Pigment Blue 15:6 12.8 parts, 7.2 parts of acrylic pigment dispersant, and 80.0 parts of propylene glycol monomethyl ether acetate, and sufficiently dispersing the pigment by a bead mill Dispersions

(T-1): Polymerizable compound: Kayarad DPHA (manufactured by Nippon Kayaku Co., Ltd.; dipentaerythritol hexaacrylate)

(U-1): alkali-soluble binder: benzyl methacrylate/methacrylic acid (75/25 [mass ratio]) copolymer (weight average molecular weight: 12,000) of propylene glycol monomethyl ether acetate solution (solid content) 40.0%)

(V-1): Photopolymerization initiator: 2-(benzylideneoxyimido)-1-[4-(phenylthio)phenyl]-1-octanone

(V-2): Photopolymerization initiator: 2-(ethyloxyimino)-4-(4-chlorophenylthio)-1-[9-ethyl-6-(2-methyl Benzyl hydrazino)-9H-indazol-3-yl]-1-butanone

(W-1): Sensitizer: 4,4'-bis(diethylamino)diphenyl ketone

(X-1): organic solvent: propylene glycol monomethyl ether acetate

(X-2): organic solvent: ethyl 3-ethoxypropionate

(Y-1): Surfactant: Megafac F781-F (Manufactured by Di Ai Sheng Chemical Industry Co., Ltd.)

B1. Preparation of Colored Curable Composition (Coating Liquid)

The colored curable composition 1 was prepared by mixing the components in the following compositions.

B2. Fabrication and evaluation of color filters using colored hardening compositions

The coloring curable composition obtained in the above B1. was applied to a glass substrate of 100 mm × 100 mm (trade name: 1737, manufactured by Corning Co., Ltd.) so that the value of x which is an index of the color density became 0.150. (Color resist), and dried in a 90 ° C oven for 60 seconds (prebaking). Thereafter, a mask having a mask hole width of 10 μm to 100 μm for evaluation of the resolution was used, and exposure was performed at 200 mJ/cm ² (illuminance: 20 mW/cm ² ) using a high pressure mercury lamp. The exposed coating film was developed with a 1% aqueous solution of an alkaline developer CDK-1 (trade name: Fujifilm Electronic Materials Co., Ltd.), and then sprayed with pure water to be rinsed. Developer solution. Then, the coating film subjected to exposure and development as described above was subjected to heat treatment (post-baking) in an oven at 220 ° C for 1 hour, and a patterned colored cured film for color filters was formed on the glass substrate (coloring) Layer), thereby forming the color filter substrate 1 (color filter 1).

Evaluation

The obtained color filter 1 was subjected to the following evaluation. Show the results of the evaluation Table 2 below.

1. Storage stability

After the colored resist liquid was stored under refrigeration (5 ° C) for one month, the degree of precipitation of foreign matter was evaluated by visual observation and according to the following criteria.

Benchmark

A: No precipitation was observed.

B: Slightly saw the precipitation.

C: I saw the precipitation.

2. Heat resistance

As a heat resistance test, the color filter 1 was heated at 230 ° C for 30 minutes using a hot plate, and then the color difference ΔE ^* ab before and after the heat resistance test was measured using a colorimeter MCPD-1000 (trade name: manufactured by Otsuka Electronics Co., Ltd.) ^. Values were evaluated according to the following criteria. A small value of ΔE ^* ab indicates good heat resistance and shows good performance as a color filter.

Benchmark

5: △E ^* ab value <3

4:3≦△E ^* ab value <5

3:5≦△E ^* ab value <10

2:10 ≦△E ^* ab value <20

1:20≦△E ^* ab value

3. Brightness

The brightness of the color filter 1 is a microscopic part manufactured by Olympus (share) The light measuring device OSP-SP200 (trade name) was measured and evaluated by the Y value. The higher the Y value, the better the performance as a color filter for a liquid crystal display.

4. Contrast

The obtained color filter 1 was sandwiched between two polarizing films, and the polarization axes of the two polarizing films were measured in parallel using a color luminance meter (manufactured by TOPCON Corporation, model: BM-5A). In the case of the luminance values at the time of the vertical and the vertical, the value obtained by dividing the luminance when the polarization axes of the two polarizing films are parallel by the luminance at the vertical is obtained as the contrast. The higher the contrast, the better the performance as a color filter for liquid crystal displays.

Benchmark

5: The contrast ratio is 20,000 or more

4: Contrast is 15,000 or more and less than 20,000

3: The contrast ratio is 10,000 or more and less than 15,000.

2: Contrast is 5,000 or more and less than 10,000

1: Contrast is less than 5,000

5. Pattern shape

A colored film was prepared in the same manner as in Example 1, and thereafter, the entire surface of the coating film was exposed at 50 mJ/cm ² (illuminance of 20 mW/cm ² ) through a mask, and the exposed coating film was sprayed. The development was carried out by spraying a 1% aqueous solution of an alkaline developer CDK-1 (manufactured by Fujifilm Electronic Materials Co., Ltd.). Thereafter, pure water was sprayed in a spray form to rinse the developing solution. Then, the coating film subjected to the photohardening treatment and the development treatment as described above was subjected to heat treatment (post-baking) in an oven at 220 ° C for 30 minutes to form a colored resin film for color filter formation on the glass substrate. Thus, a substrate (colored substrate) having a colored resin film is formed.

The colored substrate was cut out using a glass knife, and the cross section was observed at 15,000 times using a scanning electron microscope (S-4800 (trade name) manufactured by Hitachi, Ltd.). The evaluation criteria are as follows.

Evaluation basis

A: The end of the pattern is inclined with a small slope.

B: The end of the pattern is rectangular.

C: A slit was formed at the end of the pattern.

[Example 4 to Example 18]

In the preparation of the color hardening composition 1 of Example 3, the exemplified compound A-1 was replaced with the exemplified compound (specific dipyrromethene metal complex) shown in Table 1, respectively, and The colored curable composition 2 to the colored curable composition 16 were prepared in the same manner as in Example 3 except that the ratio of the exemplified compound to the pigment dispersion liquid (S-1) was adjusted in a chromatic manner, and then, Color filter 2 to color filter 16.

Evaluation was carried out in the same manner as in Example 3, using the colored curable composition 2 to the colored curable composition 16 and the color filter 2 to the color filter 16. The results are shown in Table 2 to be described later.

[Embodiment 19]

In Example 3, the components in the following compositions were mixed to prepare colored curability. The color filter 17 was obtained in the same manner as in Example 3 except that the composition 17 was used instead of the colored curable composition 1 in place of the colored curable composition 17.

Evaluation was carried out in the same manner as in Example 3, using the colored curable composition 17 and the color filter 17. The results are shown in Table 2.

[Example 20 to Example 23]

In the preparation of the color hardening composition 17 of Example 19, the exemplified compound A-7 was replaced with the exemplified compound (specific dipyrromethene metal complex) shown in Table 2, respectively, and A colored curable composition 18 to a colored curable composition 20 was prepared in the same manner as in Example 19 except that the ratio of the exemplified compound to the pigment dispersion liquid (S-1) was changed, and color was obtained. Filter 18 to color filter 20.

Evaluation was carried out in the same manner as in Example 3, using the colored curable composition 17 to the colored curable composition 20 and the color filter 17 to the color filter 20. The results are shown in Table 2.

[Example 24]

In Example 3, the colored curable composition 18 was prepared by mixing the components in the following composition, and the colored curable composition 21 was used instead of the colored curable composition 1, except that the same procedure as in Example 3 was carried out. The color filter 21 is obtained in a manner.

Evaluation was carried out in the same manner as in Example 3, using the colored curable composition 21 and the color filter 21. The results are shown in Table 2.

Further, the compound (5) is a diamine sulfonium compound represented by the formula (X) which has been described.

[Example 25]

In the preparation of the color hardening composition 21 of Example 24, the exemplified compound A-7 was replaced with the exemplified compound A-41 to prepare the colored curable composition 22, and the colored curable composition 22 was used instead of the coloring hardenability. A color filter 22 was obtained in the same manner as in Example 21 except for the composition 21.

Evaluation was carried out in the same manner as in Example 3, using the colored curable composition 19 and the color filter 19. The results are shown in Table 2.

[Comparative Example 1 to Comparative Example 5]

In the preparation of the color hardening composition 1 of Example 3, the exemplified compound A-1 was replaced with the comparative compound C1 to the comparative compound C5 shown in Table 2, respectively, and the comparative compound and the pigment were changed in a chromaticity-compatible manner. In addition to the ratio of the dispersion (S-1), the colored curable composition 101 to the colored curable composition 105 were prepared in the same manner. Further, in the same manner as in the third embodiment, the colored curable composition 101 to the colored curable composition 105 were used instead of the colored curable composition 1. The color filter 101 to the color filter 105 are obtained.

Evaluation was carried out in the same manner as in Example 3, using the colored curable composition 101 to the colored curable composition 105 and the color filter 101 to the color filter 105. The results are shown in Table 2.

Further, Comparative Compound C1 to Comparative Compound C3 are the above-mentioned compounds, and Comparative Compound C4 and Comparative Compound C5 are as follows.

. Comparative Compound C4...C.I.Acid Violet (Acid Violet) 17

. Comparative Compound C5...C.I.Acid Violet (Acid Violet) 49

According to the above results, the coloring curable composition produced by the specific dipyrromethene metal complex of the present invention has high storage stability, and the heat resistance of the color filter produced by using the colored curable composition is high. Excellent color tone and contrast, and can also improve the shape of the pattern, thus the specific dipyrromethene metal complex of the present invention It is called a highly versatile dye.

Claims (15)

A colored hardening composition comprising a polymerizable compound and at least one selected from the group consisting of a compound represented by the following formula (I) and a tautomer thereof: In the formula (I), R ² to R ⁵ each independently represent a hydrogen atom or a monovalent substituent; R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group; and M represents a metal or a metal compound. X ¹ represents a group required for neutralizing the charge of M; a represents 0, 1 or 2; when a is 2, a plurality of X ¹ may be the same or different; R ⁸ to R ¹⁰ are independently represented a hydrogen atom or a monovalent substituent; wherein at least two of R ⁸ to R ¹⁰ represent a monovalent substituent other than a hydrogen atom; and R ¹¹ to R ¹⁴ each independently represent a hydrogen atom or a monovalent substituent; X ² represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or a sulfur An atom; R ¹⁶ represents a hydrogen atom or a monovalent substituent. The colored curable composition according to claim 1, wherein at least one selected from the group consisting of the compound represented by the above formula (I) and a tautomer thereof is selected from the group consisting of At least one of the group consisting of the compound represented by the general formula (II) and its tautomer: In the formula (II), R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent substituent; X ¹ represents a group required for neutralizing the charge of Zn; and R ⁸ to R ¹⁰ each independently represent hydrogen. An atom or a monovalent substituent; wherein at least two of R ⁸ to R ¹⁰ represent a monovalent substituent; R ¹¹ to R ¹⁴ each independently represent a hydrogen atom or a monovalent substituent; and X ² represents NR ( R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or a sulfur atom; R ¹⁶ represents A hydrogen atom or a monovalent substituent. The color hardening composition according to claim 1, which further comprises a photopolymerization initiator. The colored curable composition according to claim 1, further comprising at least one selected from the group consisting of a pigment and a cerium compound. The colored hardening composition according to Item 4, wherein the hydrazine compound is a compound represented by the following formula (IX): In the formula (IX), R ^11a and R ^12a each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, but R ^11a and R ^12a do not simultaneously represent a hydrogen atom; n ¹¹ represents an integer of 1 to 4; . The colored hardening composition according to claim 1, wherein the total solid content of the composition is selected from the group consisting of the compound represented by the above formula (I) and tautomers thereof. The content of at least one of the components is in the range of 0.1% by mass or more and 30% by mass or less. A colored cured film obtained by curing the colored curable composition according to any one of claims 1 to 6. A color filter comprising the same as described in claim 7 Color hardened film. A method of producing a color filter, comprising: applying a color-curable composition according to any one of claims 1 to 6 to a support to form a colored curable composition And a step of exposing the colored curable composition layer to a pattern and developing to form a colored pattern. A display device comprising the color filter of claim 8 of the patent application. A display device comprising a color filter produced by the method of manufacturing a color filter according to claim 9 of the patent application. A solid-state photographic element comprising the color filter of claim 8 of the patent application. A solid-state photographic element comprising a color filter produced by the method of producing a color filter according to claim 9 of the patent application. A compound selected from the group consisting of a compound represented by the following formula (I) and a tautomer thereof: general formula (I) In the formula (I), R ² to R ⁵ each independently represent a hydrogen atom or a monovalent substituent; R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group; and M represents a metal or a metal compound. X ¹ represents a group required for neutralizing the charge of M; a represents 0, 1 or 2; when a is 2, a plurality of X ¹ may be the same or different; R ⁸ to R ¹⁰ are independently represented a hydrogen atom or a monovalent substituent; wherein at least two of R ⁸ to R ¹⁰ represent a monovalent substituent other than a hydrogen atom; and R ¹¹ to R ¹⁴ each independently represent a hydrogen atom or a monovalent substituent; X ² represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or a sulfur An atom; R ¹⁶ represents a hydrogen atom or a monovalent substituent. a compound selected from the group consisting of a compound represented by the following formula (II) and a tautomer thereof: a formula (II) In the formula (II), R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent substituent; X ¹ represents a group required for neutralizing the charge of Zn; and R ⁸ to R ¹⁰ each independently represent hydrogen. An atom or a monovalent substituent; wherein at least two of R ⁸ to R ¹⁰ represent a monovalent substituent; R ¹¹ to R ¹⁴ each independently represent a hydrogen atom or a monovalent substituent; and X ² represents NR ( R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or a sulfur atom; R ¹⁶ represents A hydrogen atom or a monovalent substituent.