KR102060407B1 - Colored curable composition, colored cured film, color filter, method for producing color filter, display device, solid-state imaging device, and compound - Google Patents

Abstract

(Problem) The colored curable composition which is excellent in storage stability and which is excellent in heat resistance, brightness | luminance, contrast, and pattern shape is obtained is obtained.
(Solution means) The said colored curable composition contains a polymeric compound, at least 1 sort (s) chosen from the group which consists of a compound represented by following General formula (I), and its tautomer.

Description

Colored curable composition, colored cured film, color filter, manufacturing method of color filter, display device, solid-state image sensor, and compound IMAGING DEVICE, AND COMPOUND}

This invention relates to a colored curable composition, a colored cured film, a color filter, the manufacturing method of a color filter, a display apparatus, a solid-state image sensor, and a compound.

Conventionally, a color filter uses a photolithography method or an inkjet using a pigment dispersion composition in which an organic pigment or an inorganic pigment as a coloring agent is dispersed, a polymerizable compound, a polymerization initiator, an alkali-soluble resin, and a colored curable composition containing other components. It is manufactured by forming a coloring pattern by pattern formation methods, such as a method.

In recent years, color filters tend to be used not only for monitors but also for televisions for display element uses such as liquid crystal display devices (LCDs). As the use expands, color filters require high color characteristics in terms of chromaticity, contrast, and the like. In addition, also in the color filter for image sensor (solid-state image sensor) use, high color characteristics, such as a reduction of a nonuniformity and an improvement of color resolution, are calculated | required.

In the colored curable composition containing the conventional pigment dispersion composition, problems, such as generation | occurrence | production of the scattering by the coarse particle of a pigment, or viscosity rise by poor dispersion stability, are easy to arise, and it is difficult to further improve contrast and brightness.

Therefore, using dye instead of a pigment as a coloring agent is examined (for example, refer Unexamined-Japanese-Patent No. 6-75375). The use of the dye is advantageous in that the color and luminance of the display image when the image is displayed by the color purity of the dye itself or the vividness of the color thereof can be increased, and the contrast is improved because coarse particles are lost.

As a dye which can be used for the said use, it is preferable to have the following properties. That is, the thing which has a color suitable for color reproduction, the thing with optimal spectral absorption, the fastness, such as heat resistance and light resistance, and the solubility to a solvent are mentioned.

For example, Japanese Patent Application Laid-Open No. 2008-292970 discloses a dipyrromethene-based dye having excellent color purity, high molar extinction coefficient, and excellent fastness, which is useful for the colored curable composition for color filters. In addition, Japanese Patent Application Laid-Open No. 2010-85454 discloses a dipyrromethene-based dye having a high molar extinction coefficient useful for a color curable composition for color filters and obtaining a color curable composition excellent in developability.

However, as a dye contained in the colored curable composition used in the production of the color filter of the display element or the solid-state image sensor, it has a high molar extinction coefficient as well as a new pigment having improved solubility and heat resistance. to be.

In addition, it is desirable to have excellent storage stability as compared with the colored curable composition containing the above-mentioned dyes, and also to be excellent in heat stability (heat resistance), luminance, contrast, and pattern shape in color filters produced using the same. have.

According to one embodiment of the present invention, it is made in view of the above situation, and an object of the present invention is to provide a colored curable composition in which a colored cured film excellent in storage stability and excellent in heat resistance, brightness, contrast, and pattern shape is formed.

According to another aspect of the present invention, it is an object to provide a colored cured film using the colored curable composition, a color filter provided with the colored cured film, a manufacturing method thereof, a display device using the color filter, and a solid-state imaging device.

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

Examples of embodiments of the present invention are as follows.

The colored curable composition containing a <1> polymeric compound, at least 1 sort (s) chosen from the group which consists of a compound represented by the following general formula (I), and its tautomer.

[In General Formula (I), R <^2> -R <^5> represents a hydrogen atom or a monovalent substituent each independently. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. M represents a metal or a metal compound, X ¹ represents a group necessary for neutralizing the charge of M, and a represents 0, 1 or 2. When a is 2, some X <^1> may be the same or different. R ⁸ to R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent. Provided that 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, and R ¹⁶ is Hydrogen atom or monovalent substituent]

<2> In <1>, at least 1 sort (s) selected from the group which consists of a compound represented by said general formula (I) and its tautomers is a compound represented by the following general formula (II), and its tautomer It is at least 1 sort (s) selected The coloring curable composition characterized by the above-mentioned.

[In General Formula (II), R <^3> and R <^4> represents a hydrogen atom or a monovalent substituent each independently. X ¹ represents a group necessary for neutralizing the charge of Zn. R ⁸ to R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent. Provided that 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>, further comprising a photopolymerization initiator.

<4> The colored curable composition in any one of <1>-<3> which further contains at least 1 sort (s) chosen from the group which consists of a pigment and an anthraquinone compound.

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

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

<6> The content of at least one selected from the group consisting of a compound represented by the general formula (I) and a tautomer thereof according to any one of <1> to <5> is 0.1% by mass based on the total solid of the composition It is the range of 30 mass% or more or more, The colored curable composition characterized by the above-mentioned.

<7> The colored cured film obtained by hardening | curing the colored curable composition in any one of <1>-<6>.

<8> The color filter provided with the colored cured film as described in <7>.

<9> The process of apply | coating the coloring curable composition in any one of <1>-<6> on a support body, and forming a colored curable composition layer, and exposing and developing the said colored curable composition layer in a pattern form, and coloring a pattern. A manufacturing method of a color filter comprising the step of forming.

<10> The display apparatus provided with the color filter as described in <8> or the manufacturing method of the color filter as described in <9>.

<11> The solid-state imaging device characterized by including the color filter produced by the color filter as described in <8>, or the manufacturing method of the color filter as described in <9>.

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

[In General Formula (I), R <^2> -R <^5> represents a hydrogen atom or a monovalent substituent each independently. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. M represents a metal or a metal compound, X ¹ represents a group necessary for neutralizing the charge of M, and a represents 0, 1 or 2. When a is 2, some X <^1> may be the same or different. R ⁸ to R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent. Provided that 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, and R ¹⁶ is Hydrogen atom or monovalent substituent]

<13> A compound characterized by being selected from the group consisting of a compound represented by the following general formula (II) and tautomers thereof.

[In General Formula (II), R <^3> and R <^4> represents a hydrogen atom or a monovalent substituent each independently. X ¹ represents a group necessary for neutralizing the charge of Zn. R ⁸ to R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent. Provided that 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]

(Effects of the Invention)

ADVANTAGE OF THE INVENTION According to this invention, the coloring curable composition which forms the colored cured film which is excellent in storage stability and excellent in heat resistance, brightness | luminance, contrast, and a pattern shape is provided.

According to this invention, the colored cured film using the said colored curable composition, the color filter provided with the said colored cured film, its manufacturing method, the display apparatus using the said color filter, and a solid-state image sensor are further provided.

According to this invention, the pigment | dye which has a high molar extinction coefficient useful for the colored curable composition used for manufacture of a color filter, and is excellent in solubility and heat resistance is further provided.

Hereinafter, the colored curable composition, colored cured film, a color filter, the manufacturing method of a color filter, a liquid crystal display device, a solid-state image sensor, and a pigment by this invention are explained in full detail. Although description of the element | module described below was made | formed based on typical embodiment of this invention, this invention is not limited to such embodiment.

In addition, the numerical range displayed using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

In this specification, all solid content means the total content of all components of the colored curable composition except the solvent which is one component of a colored curable composition.

In the present specification, for example, an "alkyl group" represents an alkyl group of "linear, branched and cyclic". In addition, in description of group (atom group) in this specification, the description which is not describing substitution and unsubstitution means including what has a substituent with the thing which does not have a substituent. For example, an "alkyl group" includes not only the alkyl group (unsubstituted alkyl group) which does not have a substituent but the alkyl group (substituted alkyl group) which has a substituent. The same applies to groups other than alkyl groups.

In addition, in this specification, "(meth) acrylate" shows both or one of acrylate and methacrylate, and "(meth) acryl" shows both or both of acryl and methacryl, and " (Meth) acryloyl "represents both or both of acryloyl and methacryloyl.

In addition, in this specification, a "monomer" and a "monomer" have the same meaning. The monomer in this specification is distinguished from an oligomer and a polymer, and a weight average molecular weight says 2,000 or less compound. In this specification, a polymeric compound means the compound which has a polymerizable functional group, and may be a monomer, an oligomer, or a polymer. The polymerizable functional group refers to a group involved in the polymerization reaction.

In this specification, the word "process" is included in this term, if the action of the expectation of the process is achieved even if it is a case where it cannot distinguish clearly from another process as well as another process.

In the present invention, "radiation" means containing visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like.

(Color curable composition)

The colored curable composition by this invention contains at least 1 sort (s also called "a specific dipyrromethene metal complex" hereafter) chosen from the group which consists of a compound represented by the following general formula (I), and its tautomer, and is preferable. Preferably a polymerizable compound and a photopolymerization initiator.

In addition, the said colored curable composition may be comprised further including an alkali-soluble binder and an organic solvent, or may be comprised using various additives.

The colored curable composition may further include at least one colorant selected from the group consisting of dyes and pigments having a structure different from the specific dipyrromethene metal complex.

(Compound represented by General Formula (I) and tautomers thereof)

The specific dipyrromethene metal complex according to the present invention is at least one compound selected from compounds represented by the following general formula (I) and tautomers thereof.

In general formula (I), R <^2> -R <^5> represents a hydrogen atom or a monovalent substituent each independently; R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group; M represents a metal or metal compound; X ¹ represents a group necessary to neutralize the charge of M; a represents 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; Provided that 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.

Tautomers may be sufficient as the compound represented by the said general formula (I).

In the present invention, the tautomer may be any compound having a structure which can be formed by moving one hydrogen atom in a molecule, and as the tautomer of the compound represented by the general formula (I), for example, The compound etc. which have a structure of (a)-general formula (f) are contained.

In said general formula (a)-(f), R <^2> -R <^5> , R <^7> -R <^14> , R <^16> , X <^1> , X <^2> , M, and a are the same as those in general formula (I), respectively. It is meaning, and the preferable range is also the same.

The structure may take various isomeric structures by the structures of R ² to R ⁵ , R ⁷ to R ¹⁴ , R ¹⁶ , X ¹ , X ² , and M as examples of tautomeric structures.

For example, when X <^1> is a monovalent group derived from succinic acid imide, the two types of isomer structures represented by the following general formula (g) and general formula (h) are further considered.

In the formulas (g) and (h), R ² to R ⁵ , R ⁷ to R ¹⁴ , R ¹⁶ , X ¹ , X ² , and M have the same meanings as those in general formula (I). to be.

The chemical structural feature of the specific dipyrromethene metal complex according to the present invention lies in that it simultaneously has two groups, -CR ⁸ R ⁹ R ¹⁰ and -X ² -R ¹⁶ . Having these two groups at the same time results in excellent properties of high solubility and high heat resistance.

Hereinafter, it demonstrates below using the compound which has a structure represented by general formula (I) about the specific dipyrromethene metal complex by this invention on behalf of.

About R ² to R ⁵ in General Formula (I)

As a monovalent substituent represented by R <^2> -R <^5> in general formula (I), a halogen atom (for example, a fluorine atom, a chlorine atom, or a bromine atom), an alkyl group (preferably C1-C48), More preferably, Is a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group , 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, or 1-adamantyl group), alkenyl group (preferably 2 to 48 carbon atoms) Alkenyl groups having 2 to 18 carbon atoms, for example, a vinyl group, an allyl group, or a 3-buten-1-yl group, an aryl group (preferably 6 to 48 carbon atoms), and more preferably Aryl groups having 6 to 24 carbon atoms, for example, a phenyl group or a naphthyl group),

Heterocyclic group (preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1 -Pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, or benzotriazol-1-yl group), silyl group (preferably 3 to 38 carbon atoms), more preferably Silyl groups having 3 to 18 carbon atoms, for example trimethylsilyl group, triethylsilyl group, tributylsilyl group, t-butyldimethylsilyl group, or t-hexyldimethylsilyl group), hydroxy group, cyano group, nitro group, alkoxy Group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methoxy group, ethoxy group, 1-butoxy group, 2-butoxy group, isopropoxy group, t-butoxide) A time period, a dodecyloxy group, or a cycloalkyloxy group is mentioned, As a specific example of a cycloalkyloxy group, cyclopentyl octa Group or a cyclohexyloxy group), an aryloxy group (preferably an aryloxy group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, for example, a phenoxy group or 1-naphthoxy group) , Heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, a 1-phenyltetrazol-5-oxy group or a 2-tetrahydropyranyloxy group). ),

Silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, trimethylsilyloxy group, t-butyldimethylsilyloxy group, or diphenylmethylsilyloxy group) , An alkylcarbonyloxy group (preferably an alkylcarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, an acetoxy group, pivaloyloxy group, or dodecanoyloxy group), Arylcarbonyloxy group (preferably an arylcarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, for example, a benzoyloxy group), and an alkoxycarbonyloxy group (preferably 2 to carbon atoms) 48, more preferably alkoxycarbonyloxy groups having 2 to 24 carbon atoms include, for example, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, or a cycloalkyloxycarbonyloxy group, and cyclo Alkyloxycarbonyl Specific examples of the oxy group include a cyclohexyloxycarbonyloxy group, an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms), Phenoxycarbonyloxy group),

Carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group or N-ethyl-N-phenylcarbamoyloxy group, sulfamoyloxy group (preferably sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms) For example, an N, N-diethylsulfamoyloxy group or an N-propylsulfamoyloxy group, an alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, For example, a methylsulfonyloxy group, a hexadecylsulfonyloxy group, or a cyclohexylsulfonyloxy group, an arylsulfonyloxy group (preferably C6-C32, more preferably C6-C24 arylsulfonyloxy group) , For example, a phenylsulfonyloxy group),

Alkylcarbonyl group (preferably an alkylcarbonyl group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, formyl group, acetyl group, pivaloyl group, tetradecanoyl group, or cyclohexanoyl group), aryl Carbonyl group (preferably arylcarbonyl group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, for example, benzoyl group), alkoxycarbonyl group (preferably 2 to 48 carbon atoms, more preferably 24 alkoxycarbonyl groups, for example, methoxycarbonyl group, ethoxycarbonyl group, octadecyloxycarbonyl group, cyclohexyloxycarbonyl group, or 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group), aryloxycarbonyl group (Preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, for example, a phenoxycarbonyl group) and a carbamoyl group (preferably Is a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, a carbamoyl group, N, N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N , N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, or N, N-dicyclohexylcarbamoyl group),

Amino group (preferably with 32 or less carbon atoms, more preferably with 24 or less carbon atoms, for example, amino, methylamino, N, N-dibutylamino, tetradecylamino, 2-ethylhexylamino or cyclo Hexylamino group), an anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, for example, an alino group or an N-methylanilino group) and a heterocyclic amino group (preferably Is a heterocyclic amino group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, a 4-pyridylamino group, a carbonamide group (preferably 2 to 48 carbon atoms), and more preferably 2 to 24 carbon atoms. Carbonamide groups, for example, acetamide group, benzamide group, tetradecanamide group, pivaloylamide group, or cyclohexaneamide group, ureido group (preferably 1 to 32 carbon atoms, more preferably1 to 24 minority ureido groups, for example, a ureido group, an N, N-dimethyl ureido group, or an N-phenyl ureido group, an imide group (preferably 36 or less carbon atoms, more preferably 24 or less carbon atoms) As an imide group of, for example, an N-succinimide group or an N-phthalimide group, an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms) For example, methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, octadecyloxycarbonylamino group, or cyclohexyloxycarbonylamino group), aryloxycarbonylamino group (preferably Preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, for example, a phenoxycarbonylamino group),

Sulfonamide groups (preferably sulfonamide groups of 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methane sulfonamide groups, butane sulfonamide groups, benzene sulfonamide groups, hexadecane sulfonamide groups, Or a cyclohexanesulfonamide group), a sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N, N-dipropylsulfamoylamino group or N- Ethyl-N-dodecylsulfamoylamino group), azo group (preferably an azo group of 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, a phenylazo group or 3-pyrazolyl azo group), an alkylthio group (Preferably an alkylthio group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methylthio group, ethylthio group, octylthio group, or cyclohexylthio group), arylthio group (preferably Preferably 6 to 4 carbon atoms 8, more preferably an arylthio group having 6 to 24 carbon atoms, for example, a phenylthio group, a heterocyclic thi group (preferably having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms) As the group, for example, 2-benzothiazolylthio group, 2-pyridylthio group, or 1-phenyltetrazolylthio group), an alkylsulfinyl group (preferably 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms) Alkylsulfinyl groups, for example, a dodecanesulfinyl group, an arylsulfinyl group (preferably an arylsulfinyl group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, for example, a phenylsulfinyl group),

Alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropylsulfonyl group) , 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, octylsulfonyl group, or cyclohexylsulfonyl group), arylsulfonyl group (preferably 6 to 48 carbon atoms, more preferably 6 to 24 arylsulfonyl groups) , For example, a phenylsulfonyl group or 1-naphthylsulfonyl group, sulfamoyl group (preferably sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, for example sulfamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, or N-cyclohexyl sulfamoyl group), sulfo group, phosphonyl group (preferably Preferably, the phosphor of 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms As the group, for example, a phenoxyphosphonyl group, octyloxyphosphonyl group, or phenylphosphonyl group), phosphinoylamino group (preferably 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms) For example, diethoxy phosphinoylamino group or dioctyloxy phosphinoylamino group) is shown.

When the monovalent substituent represented by R ^{2 ~} R ⁵ in the above general formula (I) can further be substituted, the it may further be substituted by any of the above-described respective groups. In addition, when they have two or more new substituents, those substituents may be same or different.

When the monovalent substituent further has a substituent, the new substituent includes a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a silyl group, a cyano group, a nitro group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkyl carbo Nyloxy group, alkoxycarbonyloxy group, arylcarbonyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, alkylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic thi group, alkylsulfyl It is preferable that it is selected from a silyl group, an arylsulfinyl group, an alkylsulfonyl group, and an arylsulfonyl group, and also it is 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 , Alkoxycarbonyloxy group, arylcarbonyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, alkylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio It is more preferable that it is a substituent selected from group, an arylthio group, a heterocyclic thi group, an alkylsulfonyl group, and an arylsulfonyl group.

R <^3> and R <^4> in general formula (I) is respectively independently preferably an alkyl group, an aryl group, or a heterocyclic group, and more preferably an alkyl group or an aryl group.

As said alkyl group in said R <^3> and R <^4> , a C1-C12 alkyl group is preferable, For example, a methyl group, an ethyl group, n-propyl group, i-propyl group, a cyclopropyl group, n-butyl group, i-butyl A group, t-butyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a benzyl group can be mentioned.

Especially, as an alkyl group in R <^3> and R <^4> , a C1-C12 branched or cyclic alkyl group is preferable, For example, i-propyl group, cyclopropyl group, i-butyl group, t-butyl group, cyclo A butyl group, a cyclopentyl group, and a cyclohexyl group are mentioned. Moreover, a C1-C12 secondary or tertiary alkyl group is especially preferable, and isopropyl group, cyclopropyl group, i-butyl group, t-butyl group, cyclobutyl group, and cyclohexyl group Can be mentioned.

As an aryl group in said R <^3> and R <^4> , Preferably, a phenyl group and a naphthyl group are mentioned, Especially, a phenyl group is more preferable.

As a heterocyclic group in said R <^3> and R <^4> , Preferably, 2-thienyl group, 4-pyridyl group, 3-pyridyl group, 2-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 2-benzothia A sleepy group, a 1-imidazolyl group, a 1-pyrazolyl group, a benzotriazol-1-yl group is mentioned, Especially, a 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group Or 1-pyridyl group is more preferable.

R ² and R ⁵ in General Formula (I) are each independently preferably an alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, nitrile group, imide group, or carbamoylsulfonyl group, Among them, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, nitrile group, imide group, or carbamoylsulfonyl group are more preferable, and alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, nitrile group, and imide group Or a carbamoylsulfonyl group is even more preferable, and an alkoxycarbonyl group, an aryloxycarbonyl group, or a carbamoyl group is particularly preferable. Specific examples of these groups are as described above.

About R ⁷ in General Formula (I)

When R ⁷ in General Formula (I) is a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, examples of these groups include the same halogen atoms, alkyl groups, aryl groups, or heterocyclic groups in R ² to R ⁵ described above. These are mentioned, and their preferable one is also the same.

R ⁷ in General Formula (I) is preferably a hydrogen atom, a halogen atom or an alkyl group, and more preferably a hydrogen atom.

About M in General Formula (I)

M in general formula (I) represents a metal atom or a metal compound. M may be any metal atom or metal compound capable of forming a complex, and divalent metal atoms, divalent metal oxides, divalent metal hydroxides, or divalent metal chlorides are included. For example, Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., in addition to AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ , metal chlorides such as GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ .

Among these, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B, or VO is preferable in view of the stability of the complex, spectral characteristics, heat resistance, light resistance, and production suitability. Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferable, and Fe, Zn, Cu, Co, B, or VO (V = O) is even more preferable. In particular, Zn is most preferred.

About "(X ¹ ) _a " in General Formula (I)

X ¹ in General Formula (I) represents a group necessary for neutralizing the charge of M, and as X ¹ , for example, a halogen atom (for example, a fluorine atom, a chlorine atom, or a bromine atom), a hydroxyl group, or an aliphatic imide (For example, succinic acid imide, maleimide, glutarimide, diacetoamide, etc. are mentioned, Preferably succinic acid imide or maleimide is mentioned.) A monovalent group derived from an aromatic imide group, or Heterocyclic imides (for example, phthalimide, naphthalimide, 4-bromophthalimide, 4-methylphthalimide, 4-nitrophthalimide, naphthalenecarboximide, or tetrabromophthal Imides and the like, preferably monovalent groups derived from phthalimide, 4-bromophthalimide, or 4-methylphthalimide, and aromatic carboxylic acids (for example, Benzoic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid, 4-methoxy Benzoic acid, 4-chlorobenzoic acid, 2-naphthoic acid, salicylic acid, 3,4,5-trimethoxybenzoic acid, 4-heptyloxybenzoic acid, or 4-t-butylbenzoic acid, and the like, preferably benzoic acid, 4 Monomethoxy group derived from -methoxy benzoic acid or salicylic acid),

Aliphatic carboxylic acids (e.g. formic acid, acetic acid, acrylic acid, methacrylic acid, ethanic acid, propanoic acid, lactic acid, pivalic acid, hexanoic acid, octanoic acid, 2-ethylhexanoic acid, neodecanoic acid, lauric acid, Myristic acid, palmitic acid, stearic acid, oleic acid, isostearic acid, 2-hexadecyloctadecanoic acid, 2-hexyldecanoic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, 5-norbornene-2 -Carboxylic acid or 1-adamantanecarboxylic acid, and the like, preferably acetic acid, methacrylic acid, lactic acid, pivalic acid, 2-ethylhexanoic acid, or stearyl acid, etc.) Monovalent group derived from monovalent group derived from dithiocarbamic acid (For example, dimethyldithiocarbamic acid, diethyldithiocarbamic acid, or dibenzyldithiocarbamic acid is mentioned), Sulfonamides (e.g. benzenesulfonamide, 4-chlorobenzenesulfonamide, 4-methoxybenzenesulfonamide, 4-methylbenzene Phonamide, 2-methylbenzenesulfonamide, or methanesulfonamide, and preferably a monovalent group derived from benzenesulfonamide or methanesulfonamide, hydroxamic acid (for example, acetohydride). Monovalent groups derived from lactic acid, octanohydric acid, or benzohydric acid, and nitrogen-containing cyclic compounds (eg, hydantoin, 1-benzyl-5-ethoxyhydantoin, 1) Allylhydantoin, 5,5-diphenylhydantoin, 5,5-dimethyl-2,4-oxazolidinedione, barbituric acid, imidazole, pyrazole, 4,5-dicyanoimidazole, 4, 5-dimethylimidazole, benzimidazole, or 1H-imidazole-4,5-dicarboxylic acid diethyl and the like, and preferably 1-benzyl-5-ethoxyhydantoin, 5,5 And monovalent groups derived from -dimethyl-2,4-oxazolidinedione, 4,5-dicyanoimidazole, or 1H-imidazole-4,5-dicarboxylic acid diethyl). .

Among them, a group derived from a halogen atom, an aliphatic carboxylic acid group, an aromatic carboxylic acid group, an aliphatic imide group, an aromatic imide group, a sulfonic acid group, or a nitrogen-containing ring compound from the viewpoint of production is preferable, and a hydroxyl group, an aliphatic carboxylic acid group, or an aromatic group. Groups derived from an imide group or a nitrogen-containing ring compound are more preferred.

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

About R ⁸ to R ¹⁰ in General Formula (I)

In general formula (I), R <^8> -R <^10> respectively independently represents a hydrogen atom or a monovalent substituent. Provided that 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 meaning as the group described for the substituents of R ² to R ⁵ , and among them, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a silyl group, an alkoxy group, an aryloxy group, A heterocyclic oxy group, an alkylthio group, an arylthio group, or a heterocyclic thi group is preferable, and a halogen atom, an alkyl group, an aryl group, an alkoxy group, or an alkylthio group is more preferable.

When R ⁸ to R ¹⁰ are each independently a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a silyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, or a heterocyclic thi group, Specific examples thereof include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a silyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, and an arylthio group described for the substituents represented by R ² to R ⁵ . Or the same group as that of the specific example of a heterocyclic thio group, These are also the same.

About R ¹¹ to R ¹⁴ in General Formula (I)

As an example of the monovalent substituent by R <^11> -R <^14> in general formula (I), the same thing as what was illustrated as said monovalent substituent by R <^2> -R <^5> is mentioned.

R ¹¹ to R ¹⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a silyl group, a cyano group, a nitro group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylcarbonyloxy group, Alkoxycarbonyloxy group, arylcarbonyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, alkylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfinyl group, aryl A sulfinyl group, an alkylsulfonyl group, or an arylsulfonyl group is preferable, and a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, or Heterocyclic thio groups are more preferable, and a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, or a heterocyclic oxy group is especially preferable.

About X ² in General Formula (I)

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

The alkyl group by R is preferably a linear, branched, or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, and for example, methyl, ethyl, propyl, isopropyl and butyl. Group, isobutyl group, t-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, or 1-adamantyl group.

As an alkenyl group by said R, Preferably it is a C2-C24 alkenyl group, More preferably, it is a C2-C12 alkenyl group, For example, a vinyl group, an allyl group, or 3-buten-1-yl group etc. are mentioned. have.

As an aryl group by said R, Preferably it is a C6-C36, More preferably, it is a C6-C18 aryl group, For example, a phenyl group, a naphthyl group, etc. are mentioned.

The heterocyclic group by R is preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and containing at least one element selected from a nitrogen atom, an oxygen atom, and a sulfur atom as a hetero atom. It is preferable.

Specific examples of the heterocyclic group by R include 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1 -Pyrazolyl group, benzotriazol-1-yl group, etc. are mentioned.

The alkylcarbonyl group by R is preferably an alkylcarbonyl group having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms. For example, an acetyl group, pivaloyl group, 2-ethylhexyl group, cyclohexanoyl group, or the like is used. Can be mentioned.

As an arylcarbonyl group by said R, it is a C7-C22 alkyl group, More preferably, it is a C7-C16 alkyl carbonyl group, For example, a benzoyl group etc. are mentioned.

The alkylsulfonyl group by R is preferably an alkylsulfonyl group having 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, for example, methylsulfonyl group, ethylsulfonyl group, isopropylsulfonyl group, or cyclohexyl. And sulfonyl groups.

As said alkylsulfonyl group by said R, Preferably, it is C6-C24, More preferably, C6-C18 arylsulfonyl group, For example, a phenylsulfonyl group, a naphthylsulfonyl group, etc. are mentioned.

In addition, the monovalent substituent by R may be further substituted by the substituent, and when substituted by several new substituents, those substituents may be same or different.

When the monovalent substituent further has a substituent, the new substituent includes 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 arylcarbonyloxy group, It is preferably selected from alkylsulfonyloxy group, arylsulfonyloxy group, alkylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic thi group, alkylsulfonyl group, and arylsulfonyl group, and also halogen A substituent selected from an atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyl group, an alkylthio group, an arylthio group, a heterocyclic thi group, an alkylsulfonyl group, and an arylsulfonyl group It is more preferable.

X ² is preferably an oxygen atom or a sulfur atom, particularly preferably an oxygen atom.

About R ¹⁶ in General Formula (I)

As a monovalent substituent by R <^16> in General formula (I), the same thing as what was illustrated as a monovalent substituent by said R <^2> -R <^5> is mentioned. Especially, alkyl group, alkenyl group, aryl group, heterocyclic group, alkylcarbonyl group, arylcarbonyl group, carbamoyl group, ureido group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl group is preferable. , 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 is more preferable, and an alkyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, or an arylcarbonyl group is more preferable.

Unsubstituted may be sufficient as the said monovalent substituent, and may have a substituent further. When further having a substituent, as the new substituent, 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 arylcarbonyloxy group, an alkylsulfonyloxy group, An arylsulfonyloxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, a heterocyclic thi group, an alkylsulfonyl group, and an arylsulfonyl group are preferable, and also a halogen atom, an alkyl group, an aryl group It is more preferable that they are a substituent selected from the heterocyclic group, the alkoxy group, the aryloxy group, the heterocyclic oxy group, the alkylcarbonyl group, the alkylthio group, the arylthio group, the heterocyclic thi group, the alkylsulfonyl group, and the arylsulfonyl group.

The preferable thing which is a compound represented by general formula (I) is demonstrated below.

The specific dipyrromethene metal complex according to the present invention is preferably one of R ² to R ⁵ , R ⁷ to R ¹⁴ , R ¹⁶ , X ¹ , a, X ² , and M according to general formula (I). Compound.

That is, R ² and R ⁵ 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, a heterocyclic oxy group, Alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkoxycarbonylamino group, sulfonamide group, azo group, alkylthio group, arylthio group, heterocyclic thi group, alkylsulfonyl group, arylsulfo Nil group or sulfamoyl group;

R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylcarbonyl group , Arylcarbonyl group, alkoxycarbonyl group, carbamoyl group, anilino group, carbonamide group, ureido group, imide group, alkoxycarbonylamino group, sulfonamide group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkyl Sulfonyl group, arylsulfonyl group, sulfamoyl group, or phosphinoylamino 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 are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a silyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, or a heterocyclic tee And at least two of R ⁸ to R ¹⁰ are groups other than a hydrogen atom;

R ¹¹ to R ¹⁴ 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, an aryloxy group, a heterocyclic oxy group, or an acyl group , Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkoxycarbonylamino group, sulfonamide group, azo group, alkylthio group, arylthio group, heterocyclic thi group, alkylsulfonyl group, arylsulfonyl group, or sulfamo It is a diary;

X ² is an oxygen atom or a sulfur atom;

R ¹⁶ is a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, alkylcarbonyl group, arylcarbonyl group, carbamoyl group, ureido group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl group ego;

M is Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B, or VO;

X ¹ is a group derived from a halogen atom, an aliphatic carboxylic acid group, an aromatic carboxylic acid group, an aliphatic imide group, an aromatic imide group, a sulfonic acid group, or a nitrogen-containing ring compound;

and a form in which a is 0, 1, or 2.

More preferable examples of the specific dipyrromethene metal complex according to the present invention are those in which R ² to R ⁵ , R ⁷ to R ¹⁴ , R ¹⁶ , X ¹ , a, X ² , and M according to general formula (I) are as follows. Phosphorus compound.

That is, R ² and R ⁵ are each independently alkyl, alkenyl, aryl, heterocyclic, cyano, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, imide, alkylsulfonyl, aryl Sulfonyl group or sulfamoyl group;

R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, a carbamoyl group, a carbonamide group, a ureido group, an imide group, an alkoxy Carbonylamino group, sulfonamide group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl 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 are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, or an alkylthio group, and at least two of R ⁸ to R ¹⁰ are groups other than a hydrogen atom;

R ¹¹ to R ¹⁴ each independently represent 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, an alkoxycarbonyl group, Aryloxycarbonyl group, carbamoyl group, imide group, alkoxycarbonylamino group, sulfonamide group, azo group, alkylthio group, arylthio group, heterocyclic thi group, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl group;

X ² is an oxygen atom or a sulfur atom;

R ¹⁶ is a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, alkylcarbonyl group, arylcarbonyl group, carbamoyl group, ureido group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl group ego;

M is Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO;

X ¹ is a group derived from a halogen atom, an aliphatic carboxylic acid group, an aromatic carboxylic acid group, an aliphatic imide group, an aromatic imide group, a sulfonic acid group, or a nitrogen-containing ring compound;

and a form in which a is 0, 1, or 2.

Even more preferred of the specific dipyrromethene metal complex according to the present invention is that R ² to R ⁵ , R ⁷ to R ¹⁴ , R ¹⁶ , X ¹ , a, X ² , and M according to general formula (I) are Compound.

That is, R ² and R ⁵ are each independently alkyl, alkenyl, aryl, heterocyclic, cyano, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, imide, alkylsulfonyl, aryl Sulfonyl group or sulfamoyl group;

R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, a carbamoyl group, a carbonamide group, a ureido group, an imide group, an alkoxy Carbonylamino group, sulfonamide group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl 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 are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, or an alkylthio group, and at least two of R ⁸ to R ¹⁰ are groups other than a hydrogen atom;

R ¹¹ to R ¹⁴ each independently represent 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, an alkoxycarbonyl group, Aryloxycarbonyl group, carbamoyl group, imide group, alkoxycarbonylamino group, sulfonamide group, azo group, alkylthio group, arylthio group, heterocyclic thi group, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl group;

X ² is an oxygen atom or a sulfur atom;

R ¹⁶ is an alkyl group, alkenyl group, aryl group, heterocyclic group, acyl group, alkylsulfonyl group, or arylsulfonyl group;

M is Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B, or VO;

X ¹ is a group derived from a halogen atom, an aliphatic carboxylic acid group, an aromatic carboxylic acid group, an aliphatic imide group, an aromatic imide group, a sulfonic acid group, or a nitrogen-containing ring compound;

and a form in which a is 0, 1, or 2.

As for the compound and tautomer represented by general formula (I) in this invention, it is more preferable to represent with the following general formula (II) from a viewpoint of stability of a complex, spectral characteristics, heat resistance, light resistance, and manufacturing aptitude.

In general formula (II), R <^3> and R <^4> represents a hydrogen atom or a monovalent substituent each independently; X ¹ represents a group necessary to neutralize the charge of Zn; R ⁸ to R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent; Provided that 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.

Preferable ranges, such as each group of the compound represented by general formula (II), are the same as that of general formula (I).

The molar extinction coefficient of the dipyrromethene metal complex or tautomer thereof in the present invention is preferably as high as possible from the viewpoint of the film thickness. Moreover, 520 nm-580 nm are preferable and, as for the maximum absorption wavelength (lambda) _max, from a viewpoint of color purity improvement, 530 nm-570 nm are more preferable. In addition, the maximum absorption wavelength and molar extinction coefficient are measured with the spectrophotometer UV-1800PC (brand name, the product of Shimadzu Corporation).

Next, the specific example of the specific dipyrromethene metal complex by this invention is shown below. However, it is not limited to these.

In the colored curable composition which concerns on this invention, you may use together the dye and pigment which have another structure other than a specific dipyrromethene metal complex in the range which does not impair the effect of this invention.

Dyes with other structures

There is no restriction | limiting in particular as dye which has the said other structure, A well-known dye can be used. For example, Japanese Patent Laid-Open No. 64-90403, Japanese Patent Laid-Open No. 64-91102, Japanese Patent Laid-Open No. 1-94301, Japanese Patent Laid-Open No. 6-11614, Japanese Patent Registration 2592207, U.S. Patent No. 4,808,501, U.S. Patent 5,667,920, U.S. Patent 5,059,500, Japanese Patent Application Laid-Open No. 5-333207, Japanese Patent Application Laid-Open No. 6-35183, Japanese Patent Application Laid-open No. 6-51115 Japanese Patent Laid-Open No. 6-194828, Japanese Patent Laid-Open No. 8-211599, Japanese Patent Laid-Open No. 4-249549, Japanese Patent Laid-Open No. 10-123316, Japanese Patent Laid-Open No. 11-302283 Japanese Patent Laid-Open No. 7-286107, Japanese Patent Laid-Open No. 2001-4823, Japanese Patent Laid-Open No. 8-15522, Japanese Patent Laid-Open No. 8-29771, Japanese Patent Laid-Open No. 8-146215, Japanese Patent Laid-Open No. 11-343437, Japanese Patent Laid-Open No. 8-62416 , Japanese Patent Publication No. 2002-14220, Japanese Patent Publication 2002-14221, Japanese Patent Publication 2002-14222, Japanese Patent Publication 2002-14223, Japanese Patent Publication No. 8-302224, Japanese Patent Publication The pigment | dye described in Unexamined-Japanese-Patent No. 8-73758, Unexamined-Japanese-Patent No. 8-179120, Unexamined-Japanese-Patent No. 8-151531, Unexamined-Japanese-Patent No. 6-230210, etc. are mentioned.

Chemical structures of dyes having other structures include pyrazole azo, anilinoazo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridoneazo, cyanine, Dyes such as phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, squarylium-based, phthalocyanine-based, benzopyran-based, or indigo-based may be used. Especially, xanthene type dye or squarylium type dye is preferable at the point of color.

The dye which has the said other structure may be contained individually by 1 type, and may use 2 or more types of dye together.

As for content in the colored curable composition of the specific dipyrromethene metal complex in this invention, 0.1 mass%-30 mass% are preferable on a mass basis with respect to the total solid of a colored curable composition, and 0.5 mass%-20 mass% More preferred. By making content of dye into the said range, favorable density | concentration (for example, the color density suitable for liquid crystal display) is obtained, and it is advantageous at the point which the patterning of a pixel becomes favorable.

Pigment

A pigment can also be used together with the dye mentioned above for a colored curable composition.

As a pigment, the pigment whose average primary particle diameter is 10 nm-30 nm is preferable. If it is the said form, the colored curable composition excellent in color and contrast will be obtained.

As the pigment, various conventionally known inorganic pigments or organic pigments can be used, but it is preferable to use organic pigments from the viewpoint of reliability. As an organic pigment in this invention, the organic pigment of Paragraph [0093] of Unexamined-Japanese-Patent No. 2009-256572 is mentioned, for example.

Also especially

C. I. Pigment Red 177, 224, 242, 254, 255, 264,

C. I. Pigment Yellow 138, 139, 150, 180, 185,

C. I. Pigment Orange 36, 38, 71,

C. I. Pigment Green 7, 36, 58,

C. I. Pigment Blue 15: 6,

C. I. Pigment Violet 23 is suitable from the viewpoint of color reproducibility, but is not limited thereto. These organic pigments can be used individually or in various combinations in order to raise color purity.

When using a pigment, it is preferable that it is 0.5-50 weight% with respect to the total solid of the said composition, and, as for content in the colored curable composition of this invention, 1-30 weight% is more preferable. If content of a pigment is in the said range, it is effective in ensuring the outstanding color characteristic.

Pigment dispersant

The colored curable composition of this invention can contain a pigment dispersant, when a pigment is included with the compound represented by general formula (I) or its tautomer.

As a pigment dispersant, a polymeric dispersant [for example, a polyamide amine and its salt, a polycarboxylic acid and its salt, a high molecular weight unsaturated acid ester, a modified polyurethane, a modified polyester, a modified poly (meth) acrylate, a (meth) acrylic type, Copolymers, naphthalenesulfonic acid formalin condensates, and surfactants such as polyoxyethylene alkyl phosphate esters, polyoxyethylene alkylamines, alkanolamines, and pigment derivatives.

Polymeric dispersants may be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers from the structure.

As a terminal modified type polymer which has an anchor part to a pigment surface, For example, the polymer which has a phosphoric acid group at the terminal described in Unexamined-Japanese-Patent No. 3-112992, 2003-533455, etc., Unexamined-Japanese-Patent No. 2002-273191 The polymer which has a sulfonic acid group at the terminal described in Unexamined-Japanese-Patent No., etc., the polymer which has the partial skeleton and heterocycle of the organic pigment of Unexamined-Japanese-Patent No. 9-77994, etc. are mentioned. In addition, polymers in which anchor sites (acid groups, basic groups, partial skeletons or heterocycles of organic dyes, etc.) on two or more pigment surfaces are introduced to the polymer terminals described in Japanese Patent Application Laid-Open No. 2007-277514 also have excellent dispersion stability. desirable.

As a graft type polymer which has an anchor site to a pigment surface, polyester type dispersing agent etc. are mentioned, for example, Unexamined-Japanese-Patent No. 54-37082, Unexamined-Japanese-Patent No. 8-507960, Japan Reaction product of poly (lower alkyleneimine) and polyester described in Japanese Patent Application Laid-Open No. 2009-258668, etc., reaction product of polyallylamine and polyester described in Japanese Patent Laid-Open No. Hei 9-169821, etc. A copolymer of a macromonomer and a nitrogen atom-containing monomer described in Japanese Patent Application Laid-Open No. 339949, Japanese Patent Application Laid-Open No. 2004-37986, Japanese Patent Application Laid-Open No. 2003-238837, Japanese Patent Publication No. 2008-9426, Japanese Patent Publication No. 2008-81732 Graft-type polymers having partial skeletons and heterocycles of organic pigments described in publications, etc., macromonomers and acid groups described in Japanese Patent Application Laid-Open No. 2010-106268 And the like copolymers of monomers oil. In particular, the amphoteric dispersing resin having a basic group and an acidic group described in JP-A-2009-203462 is particularly preferable in view of the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the colored curable composition using the pigment dispersion.

As a macromonomer used when producing a graft polymer having an anchor portion on the pigment surface by radical polymerization, a known macromonomer can be used, and TOAGOSEI Co., Ltd. Macromonomer AA-6 (methyl methacrylate whose terminal group is methacryloyl group), AS-6 (polystyrene whose terminal group is methacryloyl group), AN-6S (styrene and acrylic whose terminal group is methacryloyl group) Copolymer of ronitrile), AB-6 (butyl acrylate having terminal methacryloyl group), DAICEL Chemical Industries Ltd. PLACCEL FM5 (5 molar equivalents of ε-caprolactone of 2-hydroxyethyl methacrylate), FA10L (10 molar equivalents of ε-caprolactone of 2-hydroxyethyl acrylate), and Japanese Patent Application Laid-Open The polyester macromonomer etc. of 2-272009 are mentioned. Among these, polyester macromonomers excellent in flexibility and affinity for solvents are particularly preferred in view of dispersibility of the pigment dispersion, dispersion stability, and developability exhibited by the colored curable composition using the pigment dispersion. Most preferred is a polyester-based macromonomer represented by the polyester-based macromonomer described in -272009.

As a block type polymer which has an anchor part to a pigment surface, the block type polymer of Unexamined-Japanese-Patent No. 2003-49110, Unexamined-Japanese-Patent No. 2009-52010, etc. are preferable.

Pigment dispersants are also available as commercially available products, and examples thereof include Kusumoto Chemicals, Ltd. Product "DA-7301", product made by BYK Chemie, "Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), `` BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), EFKA company `` EFKA 4047, 4050, 4010, 4165 (polyurethane), EFKA 4330-4340 (block copolymer), 4400-4440 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (Azo Pigment Derivative) ”, Ajinomoto Fine-Techno Co., Inc. Products `` AJISPER PB821, PB822, PB880, PB881 '', Kyoeisha Chemical Co., Ltd. Products "FLOWLEN TG-710 (urethane oligomer)", "POLYFLOW No.50E, No.300 (acrylic copolymer)", Kusumoto Chemicals, Ltd. Product "DISPARLON KS-860, 873SN, 874, # 2150 (aliphatic polyhydric carboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725", "DEMOL RN" from Kao Corporation , N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate), `` HOMOGENOL L-18 (polymer polycarboxylic acid) '', `` EMULGEN 920, 930, 935, 985 ( Polyoxyethylene nonylphenyl ether) "," ACETAMIN 86 (stearylamine acetate) "," SOLSPERSE 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, by The Lubrizol Corporation 27000 (Polymer with Functional Part at End), 24000, 28000, 32000, 38500 (Graft Polymer)], Nikko Chemicals Co., Ltd. Product "NIKKOL T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)", Kawaken Fine Chemicals Co., Ltd. Product HINOACT T-8000E, etc., Shin-Etsu Chemical Co., Ltd. Products, Organosiloxane Polymer KP341, Yusho Co., Ltd. Product "W001: Cationic surfactant", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate , Nonionic surfactants such as polyethylene glycol distearate, sorbitan fatty acid esters, anionic surfactants such as "W004, W005, W017", "EFKA-46, EFKA-47, EFKA-47EA," manufactured by Morishita Sangyo Corporation, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 '', San Nopco Ltd. Polymeric dispersants such as the products `` DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15, DISPERSE AID 9100 '', and ADEKA Corporation products `` ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84 , F87, P94, L101, P103, F108, L121, P-123 ", and Sanyo Chemical Industries Ltd. A product "IONET (brand name) S-20" etc. are mentioned.

These pigment dispersants may be used independently and may be used in combination of 2 or more type. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant. In addition, you may use the pigment dispersant of this invention together with alkali-soluble resin together with the terminal modified | denatured polymer | macromolecule, graft-type polymer, and block-type polymer which have an anchor site to the said pigment surface. As alkali-soluble resin, it has a (meth) acrylic acid copolymer, itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partial esterified maleic acid copolymer, etc., and an acidic cellulose derivative which has a carboxylic acid in a side chain, and a hydroxyl group. Although the resin which modified the acid anhydride to the polymer is mentioned, A (meth) acrylic acid copolymer is especially preferable. Moreover, the N-position substituted maleimide monomer copolymer of Unexamined-Japanese-Patent No. 10-300922, the ether dimer copolymer of Unexamined-Japanese-Patent No. 2004-300204, and the polymeric group of Unexamined-Japanese-Patent No. 7-319161 Alkali-soluble resins containing are also preferable.

It is preferable that content of the pigment dispersant in a colored curable composition is 1-80 mass parts with respect to 100 mass parts of pigments, 5 mass parts-70 mass parts are more preferable, It is more preferable that they are 10 mass parts-60 mass parts.

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

In addition, when using a pigment derivative together, it is preferable that the usage-amount of a pigment derivative exists in the range of 1-30 parts by mass conversion with respect to 100 mass parts of pigments, It is more preferable to exist in the range of 3-20 parts, and it is 5 parts- It is especially preferable to exist in the range of 15 parts.

Anthraquinone compounds

The colored curable composition by this invention may further contain an anthraquinone compound.

By containing an anthraquinone compound, the color filter which has the contrast which raised more effectively is obtained.

The anthraquinone compound is preferably a compound having an absorption maximum at 400 nm to 700 nm, more preferably an absorption maximum at 500 nm to 700 nm, and particularly preferably an absorption maximum at 550 nm to 700 nm. . If it is an anthraquinone compound which has such absorption maximum, it will not specifically limit in structure, and it is excellent in contrast improvement effect.

Among the anthraquinone compounds in the present invention, Preferably, they are diaminoanthraquinone compounds represented by the following general formula (IX).

Among these diaminoanthraquinone compounds, the compound represented by the following general formula (X) is more preferable from the viewpoint of absorption characteristics, and the compound represented by the following general formula (XI) from the viewpoint of thermal stability is more preferable, Or the compound represented by the following general formula (XII) or the following general formula (XIII) is especially preferable from a viewpoint of both absorption characteristics and thermal stability.

First, the aminoanthraquinone compound represented by the following general formula (IX) is demonstrated.

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

The alkyl group represented by R ^11a and R ^12a is preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, and iso-propyl. The group, tert- butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc. are mentioned.

As an aryl group by R <^11a> , R < ^12a , Preferably it is 6-30 carbon atoms, More preferably, it is 6-20 carbon atoms, Especially preferably, it is a C6-C12 aryl group, For example, a phenyl group, o-methylphenyl Group, p-methylphenyl group, 2,6-dimethylphenyl group, 2,6-diethylphenylbiphenyl group, 2,6-dibromophenyl group, naphthyl group, anthranyl group, phenanthryl group, etc. are mentioned.

The heterocyclic group represented by R ^11a and R ^12a is preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and the hetero atom includes, for example, a nitrogen atom, an oxygen atom, and a sulfur atom. As a heterocyclic group, for example, imidazolyl group, pyridyl group, quinolyl group, furyl group, thienyl group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group, naphthothiazolyl group, benzoxazolyl group , Carbazolyl group, azepinyl group and the like.

The alkyl group, aryl group, and heterocyclic group by R ^11a and R ^12a may each independently have a substituent.

As a new substituent in the case of having a substituent, it is an alkyl group (preferably C1-C30, More preferably, it is C1-C20, Especially preferably, it is a C1-C10 alkyl group, For example, a methyl group, Ethyl group, iso-propyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc. can be mentioned), alkenyl group ( It is preferably an alkenyl group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms, and for example, a vinyl group, allyl group, 2-butenyl group, or 3-pente. And an alkynyl group (preferably an alkynyl group), preferably an alkynyl group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and for example, a propargyl group, Or 3-pentynyl group etc.), an aryl group (preferably carbon number) It is 6-30, More preferably, it is a C6-C20, Especially preferably, it is a C6-C12 aryl group, For example, a phenyl group, p-methylphenyl group, a biphenyl group, a naphthyl group, anthranyl group, or phenanthryl And the like),

Amino group (preferably 0-30 carbon atoms, more preferably 0-20 carbon atoms, particularly preferably 0-10 carbon atoms, and include an alkylamino group, an arylamino group, or a heterocyclic amino group. , Methylamino group, dimethylamino group, diethylamino group, dibenzylamino group, diphenylamino group, ditolylamino group, etc.), alkoxy group (preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms) Especially preferably, they are a C1-C10 alkoxy group, For example, a methoxy group, an ethoxy group, butoxy group, or 2-ethylhexyloxy group etc. are mentioned, An aryloxy group (preferably C6-C10) 30, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, for example, a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, or the like. Aromatic heterocyclic oxy group (preferably an aromatic heterocyclic oxy group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, for example, A diloxy group, a pyrazyloxy group, a pyrimidyloxy group, or a quinolyloxy group, etc.),

Acyl group (preferably an acyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, for example, an acetyl group, benzoyl group, formyl group, or pivalo) Diary, etc.), an alkoxycarbonyl group (preferably a C2-C30, More preferably, it is a C2-C20, Especially preferably, it is a C2-C12 alkoxycarbonyl group, For example, a methoxycarbonyl group or An ethoxycarbonyl group, etc.) and an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and particularly preferably 7 to 12 carbon atoms). Phenyloxycarbonyl group, etc.), acyloxy group (preferably C2-C30, More preferably, it is C2-C20, Especially preferably, it is the C2-C10 acyloxy group, For example, For example, an acetoxy group, a benzoyloxy group, etc.), an acylamino group (preferably C2-C30, More preferably, it is C2-C20, Especially preferably, it is the C2-C10 acylamino group, For example, an acetylamino group, a benzoylamino group, etc. are mentioned, The alkoxy carbonylamino group (preferably C2-C30, More preferably, it is C2-C20, Especially preferably, it is the C2-C12 alkoxy carbon A carbonylamino group, for example, a methoxycarbonylamino group, etc.);

Aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and particularly preferably 7 to 12 carbon atoms, for example, a phenyloxycarbonylamino group) And sulfonylamino group (preferably a sulfonylamino group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, for example, a methanesulfonylamino group). Or a benzenesulfonylamino group, etc.), a sulfamoyl group (preferably a 0 to 30 carbon atoms, more preferably a 0 to 20 carbon atoms, and particularly preferably a 0 to 12 carbon sulfamoyl group) Sulfamoyl group, methyl sulfamoyl group, dimethyl sulfamoyl group or phenyl sulfamoyl group);

Carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, for example, a carbamoyl group, methyl carbamoyl group, di An ethyl carbamoyl group, or a phenylcarbamoyl group, etc.), an alkylthio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms). It is a thi group, For example, a methylthio group, an ethylthio group, etc. are mentioned, An arylthio group (preferably C6-C30, More preferably, C6-C20, Especially preferably, C6 It is -12 arylthio groups, For example, a phenylthio group etc. are mentioned),

Aromatic heterocyclic thi group (preferably an aromatic heterocyclic thi group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, for example, a pyridylthio group, 2- Benzimizolylthio group, 2-benzoxazolylthio group, 2-benzthiazolylthio group, etc.), sulfonyl group (preferably 1-30 carbon atoms, More preferably, 1-20 carbon atoms) Especially preferably, it is a C1-C12 sulfonyl group, For example, a mesyl group or a tosyl group etc. are mentioned, A sulfinyl group (preferably C1-C30, More preferably, it is C1-C20) Especially preferably, it is a C1-C12 sulfinyl group, For example, methane sulfinyl group, a benzene sulfinyl group, etc. are mentioned, A ureido group (preferably C1-C30, More preferably, it is C1-C12) 20, particularly preferably 1 to 12 carbon atoms And a ureido group, for example, a ureido group, a methyl ureido group, or a phenyl ureido group, etc.), a phosphate amide group (preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms), in particular Preferably it is a C1-C12 phosphate amide group, For example, a diethyl phosphate amide group, a phenyl phosphate amide group, etc. are mentioned),

Hydroxy group, mercapto group, halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, or iodine atom, etc.), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group , A hydrazino group, an imino group, a heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms), and the hetero atom includes, for example, a nitrogen atom, an oxygen atom, or a sulfur atom As a specific example, an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a thienyl group, a piperidyl group, a morpholino group, a benzoxazolyl group, a benzimidazolyl group, a benz, for example Thiazolyl group, carbazolyl group, azepinyl group, etc.), silyl group (preferably 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms) Silyl group, for example trimes Tyl silyl group, a triphenyl silyl group, etc. are mentioned), etc. are mentioned. These substituents may further be substituted.

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

Next, the diaminoanthraquinone compound represented by general formula (X) is demonstrated.

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

The alkyl group represented by R ^21a and R ^22a is preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, and iso-propyl. Group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc. are mentioned.

As an aryl group by R <^21a> and R <^22a> , Preferably it is a C6-C30, More preferably, it is a C6-C20, Especially preferably, it is a C6-C12 aryl group, For example, a phenyl group, o-methylphenyl Group, p-methylphenyl group, 2,6-dimethylphenyl group, 2,6-diethylphenylbiphenyl group, 2,6-dibromophenyl group, naphthyl group, anthranyl group, or phenanthryl group.

The alkyl group and aryl group by R ^21a and R ^22a may further have a substituent, and examples of the new substituent include the above-described substituents of the alkyl group, aryl group and heterocyclic group represented by R ^11a and R ^12a in General Formula (IX). For example. Among these, examples of the new substituent are preferably alkyl group, aryl group, amino group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, sulfonylamino group, sulfamoyl group, Sulfonyl group, ureido group, hydroxy group, halogen atom, sulfo group, carboxyl group and the like. These details and a preferable aspect are the same as the above-mentioned example.

Next, the diaminoanthraquinone compound represented by general formula (X) is demonstrated.

In said general formula (XI), ^R31a , ^R32a , ^R33a , and ^R34a respectively independently represent an alkyl group or a halogen atom.

As said alkyl group, Preferably, it is C1-C10, More preferably, it is C1-C5, Especially preferably, it is C1-C2 alkyl group, For example, A methyl group, an ethyl group, iso-propyl group, tert- butyl group and n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, or cyclohexyl group.

As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A chlorine atom or a bromine atom is preferable.

In said general formula (XI), ^R35a and ^R36a respectively independently represent an alkyl group, an alkoxy group, an aryloxy group, a sulfo group, or its salt, an aminosulfonyl group, an alkoxysulfonyl group, or a phenoxysulfonyl group.

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

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

The aryloxy group represented by R ^35a and R ^36a is preferably an aryloxy group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, for example, a phenyloxy group. , 1-naphthyloxy group, 2-naphthyloxy group and the like.

As sulfo groups by R ^35a and R ^36a and salts thereof, groups derived from alkylsulfonic acids, arylsulfonic acids, and salts thereof are preferable. The sulfonate is preferably a quaternary ammonium salt or a salt of an amine, and preferably has 4 to 30 carbon atoms (preferably 10 to 30 carbon atoms, more preferably 15 to 30 carbon atoms) or an alkyl sulfonate having 6 to 30 carbon atoms. Particularly preferred is an aryl sulfonate (preferably having 10 to 30 carbon atoms, more preferably 15 to 30 carbon atoms).

The aminosulfonyl group according to R ^35a and R ^36a preferably has 1 to 30 carbon atoms, more preferably an alkyl aminosulfonyl group having 2 to 20 carbon atoms, particularly preferably an alkyl aminosulfonyl group having 2 to 15 carbon atoms, or carbon atoms. 6-30, More preferably, it is a C6-C20 aryl aminosulfonyl group, Especially preferably, it is a C6-C15 aryl aminosulfonyl group. Specific examples include ethyl aminosulfonyl group, propyl aminosulfonyl group, isopropyl aminosulfonyl group, butyl aminosulfonyl group, isobutyl aminosulfonyl group, sec-butyl aminosulfonyl group, pentyl aminosulfonyl group, isopentyl aminosulfonyl group, hexyl amino Sulfonyl group, cyclohexyl aminosulfonyl group, 2-ethylhexyl aminosulfonyl group, decyl aminosulfonyl group, dodecyl aminosulfonyl group, phenyl aminosulfonyl group, and the like. Examples of the dialkylaminosulfonyl group include dimethylaminosulfonyl group, Diethylaminosulfonyl group, dipropylaminosulfonyl group, diisopropylaminosulfonyl group, dibutylaminosulfonyl group, disec-butylaminosulfonyl group, disec-propylaminosulfonyl group, dihexylaminosulfonyl group, methylethylamino Sulfonyl group, methylbutylaminosulfonyl group, ethylbutylaminosulfonyl group, phenylmethylaminosulfonyl group and the like. Among them, dialkylaminosulfonyl groups having 4 to 15 carbon atoms are particularly preferred.

The alkoxysulfonyl group represented by R ^35a and R ^36a is preferably 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, still more preferably 2 to 15 carbon atoms, and particularly preferably 4 to 15 alkoxysulfonyl groups. As a specific example, a butyl sulfonyl group, a hexane sulfonyl group, a decyl sulfonyl group, a dodecyl sulfonyl group, etc. are mentioned.

The phenoxysulfonyl group according to R ^35a and R ^36a is preferably 6 to 30 carbon atoms, more preferably 6 to 20, particularly preferably 6 to 15 phenoxysulfonyl groups, and as a specific example, a phenoxysulfonyl group And a tolyl sulfonyl group.

Each group by R ^35a and R ^36a may further have a substituent, and examples of the new substituent include the examples described above as substituents of an alkyl group, an aryl group, and a heterocyclic group represented by R ^11a and R ^12a in General Formula (IX). Can be mentioned.

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

In the general formula (XII), R ^41a , R ^42a , R ^43a and R ^44a each independently represent an alkyl group or a halogen atom, and the details thereof are R ^31a , R ^32a , R ^33a and R in the general formula (X). ^It is the same as the alkyl group and halogen atom by ^34a , and its preferable form is also the same.

In said general formula (XII), ^R45a , ^R46a , ^R47a, and ^R48a respectively independently represent an alkyl group, a sulfo group, its salt, or an aminosulfonyl group. Any one of R ^45a and R ^47a and one of R ^46a and R ^48a represents a sulfo group or a salt thereof, or an aminosulfonyl group. ^Details of the alkyl group, sulfo group or salt thereof, and aminosulfonyl group for R ^45a , R ^46a , R ^47a , and R ^48a are the same as those for R ^35a and R ^36a in General Formula (XI), and a preferred form thereof is also provided. same.

Wherein the general formula ^{(XIII), R 51a, R} 52a, R 53a, and R ^54a is R ^31a, R ^32a, R ^33a in each independently is an alkyl group or a halogen atom, and their detailed formulas (XI), R ^34a group, like in the case of the halogen atom on, as a preferred form.

In the general 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 alkyl groups represented by R ^31a , R ^32a , R ^33a and R ^34a in the general formula (XI). The same as in the case of, and the preferred form is also the same.

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

In said general formula (XIII), L <^51a> and L <^52a> represent a bivalent coupling group each independently, a C1-C10 alkylene group, a C6-C20 arylene group, -O-, -S-, -NR- , -SO _2- , -CO-, or a divalent linking group formed by combining a plurality of these is preferable. As L ^51a and L ^52a , More preferably, they are a C1-C10 alkylene group, a C6-C12 phenylene group, a sulfonylamino group, or a bivalent coupling group formed by combining these plurality, Especially preferably, it is C1-C10. It is a divalent linking group formed by combining two alkylene groups, a sulfonylamino group, or these plurality.

The C1-C10 alkylene group or the divalent linking group formed by combining this with -O- and the like may be unsubstituted or may have a substituent, for example, an ethylene group, a propylene group, a butylene group, an ethyleneoxy group, and a propylene jade. A time period, an ethylene aminosulfonyl group, a propylene aminosulfonyl group, a butylene aminosulfonyl group, a pentylene aminosulfonyl group, 1-methylethylene sulfonyl group, etc. are mentioned. Especially, a C2-C10 alkylene aminosulfonyl group (for example, ethylene aminosulfonyl group, propylene aminosulfonyl group, butylene aminosulfonyl group, or pentylene aminosulfonyl group) is preferable. As said C6-C20 arylene group or the bivalent coupling group formed by combining this and -O- etc., even if it is unsubstituted, it may have a substituent, For example, a phenylene group, a biphenylene group, a phenylene aminosulfonyl group, etc. are mentioned. Among these, arylene aminosulfonyl groups having 6 to 12 carbon atoms (for example, phenylene aminosulfonyl group and the like) are preferable.

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

In said general formula (XIII), ^L53a and ^L54a respectively independently represent an oxygen atom or -NH- group.

Among the above, preferred anthraquinone compounds in the present invention are compounds selected from diaminoanthraquinone compounds represented by the general formula (XII) or the general formula (XIII), and the following cases are particularly preferable.

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

In 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 a hydrogen atom or a methyl group, and R ^57a and R ^58a are each independently a hydrogen atom or a methyl group, and L ^51a and L ^52a are each independently a C1-C10 alkylene aminosulfonyl group, a C7-C12 aralkylene aminosulfonyl group, or C2-C10 Is an alkyleneoxy group, and L ^53a and L ^54a are preferably oxygen atoms.

In this case, the effect of the present invention is more effective when the following dye compound is used in combination with a compound represented by the general formula (I) or a tautomer thereof in combination with a dipyrromethene metal complex coordinated with a metal atom or a metal compound. It is preferable at the point which is exhibited.

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

It is preferable that the quantity of the said anthraquinone compound contained in a colored curable composition is 50 mass% or less with respect to the total amount of the compound represented by General formula (I) or its tautomer, and is 2 mass%-50 mass%. It is more preferable to set it as the range, and it is more preferable to set it as the range of 10 mass%-50 mass%. When the ratio of the anthraquinone compound is 50% by mass or less, the color of the colored image is good while maintaining the fastness, and the contrast can be increased more effectively.

Polymerizable compound

The colored curable composition according to the present invention contains at least one polymerizable compound.

As a polymeric compound, it is a polymeric compound which has at least 1 ethylenically unsaturated double bond, for example, It can select and use from the component which comprises a well-known composition. As an example of a polymeric compound, the component of Paragraph No. 0010 of Unexamined-Japanese-Patent No. 2006-23696, and the component of Paragraph No. 0027 of Unexamined-Japanese-Patent No. 2006-64921-0053 are mentioned.

Moreover, the urethane addition polymeric compound manufactured using addition reaction of an isocyanate and hydroxyl group is also suitable, Unexamined-Japanese-Patent No. 51-37193, Unexamined-Japanese-Patent No. 2-32293, Unexamined-Japanese-Patent No. 2-16765. Urethane acrylates as described in Japanese Patent Application Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, Japanese Patent Publication No. 62-39418 Also suitable are urethane compounds having an ethylene oxide skeleton described in the publication.

Other examples include polyester acrylates and epoxy resins as described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490; And polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reacting methacrylic acid. In addition, the Journal of the Adhesion Society of Japan vol. 20, No. 7, 300 to 308 pages (1984) can also be used as photocurable monomers and oligomers.

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 ((meth) acrylic) Loyloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate EO modified product, dipentaerythritol hexa (meth) acrylate EO modified product, and the like as NK ester A-TMMT, NK ester A-TMM- 3, NK oligo UA-32P, NK oligo UA-7200 (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), ARONIX M-305, ARONIX M-306, ARONIX M-309, ARONIX M-450, ARONIX M -402, TO-1382 (above, manufactured by TOAGOSEI Co., Ltd.), and V # 802 (manufactured by Osaka Organic Chemical Industry Ltd.) are mentioned as preferable examples.

These polymerizable compounds can be used individually or in combination of 2 or more types.

As content (in the case of 2 or more types, total content) of the polymeric compound in the total solid of colored curable composition, 10 mass%-80 mass% are preferable, 15 mass%-75 mass% are more preferable, 20 mass% 60 mass% is especially preferable.

Photopolymerization initiator

It is preferable that the colored curable composition of this invention contains at least 1 type of photoinitiator. There is no restriction | limiting in particular as long as it can superpose | polymerize the said polymeric compound, It is preferable to select a photoinitiator from a viewpoint of a characteristic, starting efficiency, absorption wavelength, availability, cost, etc.

A photoinitiator is a compound which photosensitizes by exposure light, and starts and accelerates superposition | polymerization of a polymeric compound. The compound which starts and accelerates superposition | polymerization of a polymeric compound in response to actinic light of wavelength 300nm or more is preferable. Moreover, it can use preferably in combination with a sensitizer also about the photoinitiator which does not respond directly to actinic light of wavelength 300nm or more.

Specifically, for example, oxime ester compound, organic halogenated compound, oxydiazole compound, carbonyl compound, ketal compound, benzoin compound, acridine compound, organic peroxide, azo compound, coumarin compound, azide compound, metal Rosene compounds, hexaaryl biimidazole compounds, organic boric acid compounds, disulfonic acid compounds, onium salt compounds, acylphosphine (oxides), benzophenone compounds, acetophenone compounds, and derivatives thereof. Among these, an oxime ester compound and a hexaaryl biimidazole compound are preferable from a viewpoint of a sensitivity.

As the oxime ester compound, Japanese Patent Application Laid-Open No. 2000-80068, Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2004-534797, International Publication No. 2005/080337, International Publication No. 2006/018973, and Japanese Patent Publication The compound of 2007-210991, Unexamined-Japanese-Patent No. 2007-231000, Unexamined-Japanese-Patent No. 2007-269779, Unexamined-Japanese-Patent No. 2009-191061, international publication 2009/131189 can be used.

Specific examples include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4- (Phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyloxime) -1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethyl phenylthio) phenyl] -1,2-butanedione, 2 -(O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methyl Benzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane On, 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl) -9H- Le carbazole-3-yl] ethanone, and the like. However, it is not limited to these.

Moreover, in this invention, the compound represented by following General formula (1) is also suitable as an oxime type compound from a viewpoint of a sensitivity, time-lapse stability, and coloring at the time of post-heating.

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

Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull. Chem. Soc. 42, 2924 (1969), US Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Publication No. 48-36281, Japanese Patent Publication No. 55-32070, Japanese Patent Publication 60-239736, Japanese Patent Laid-Open No. 61-169835, Japanese Patent Laid-Open No. 61-169837, Japanese Patent Laid-Open No. 62-58241, Japanese Patent Laid-Open No. 62-212401, Japanese Patent Laid-Open 63-70243, Japanese Patent Laid-Open No. 63-298339, and the compounds described in MPHutt "Journal of Heterocyclic Chemistry" 1 (No 3), (1970), and the like, and in particular, an oxa substituted with a trihalomethyl group Sol compounds or s-triazine compounds.

As an example of a hexaaryl biimidazole compound, the various compounds described in each specification, such as Unexamined-Japanese-Patent No. 6-29285, US Patent 3,479,185, 4,311,783, 4,622,286, are mentioned, for example. Specifically, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) -4,4' , 5,5'-tetraphenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis ( o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5 , 5'-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, etc. are mentioned. Can be.

A photoinitiator can be used 1 type or in combination of 2 or more types. Moreover, when using the initiator which does not have absorption in an exposure wavelength, it is necessary to use a sensitizer.

It is preferable that it is 0.5-30 weight% with respect to the total solid in colored curable resin composition, As for the total content of a photoinitiator, it is more preferable that it is 2-20 weight%, and 5 mass%-18 mass% are the most preferable. If it is in this range, the sensitivity at the time of exposure is high, and color characteristic is also favorable.

Alkali soluble binder

The colored curable composition by this invention may contain the alkali-soluble binder. An alkali-soluble binder is not specifically limited except having alkali solubility, Preferably, it can select from a viewpoint of heat resistance, developability, water availability, etc ..

As an alkali-soluble binder, it is preferable that it is a linear organic polymer, and it is soluble in an organic solvent and enables development in a weak alkali aqueous solution. Such linear organic polymers include polymers having a carboxylic acid in the side chain, for example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, and Japanese Patent Publication 54 Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, males as described in each of Japanese Patent Application Laid-Open No. 59-53836 and Japanese Patent Laid-Open No. 59-53836; Acid copolymers, partially esterified maleic acid copolymers, and the like, and acidic cellulose derivatives having a carboxylic acid in the side chain are likewise useful.

In addition to the above, the alkali-soluble binder in the present invention includes an acid anhydride added to a polymer having a hydroxyl group, a polyhydroxystyrene resin, a polysiloxane resin, and a poly (2-hydroxyethyl (meth) acrylic). Rate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol and the like. In addition, the linear organic polymer may be a copolymer of a monomer having hydrophilicity. Examples include alkoxyalkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, glycerol (meth) acrylates, (meth) acrylamides, N-methylolacrylamides, secondary or tertiary alkylacrylamides, di Alkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) Acrylate, a branched or linear propyl (meth) acrylate, a branched or linear butyl (meth) acrylate, or phenoxyhydroxypropyl (meth) acrylate etc. are mentioned. In addition, examples of the hydrophilic monomer include a tetrahydrofurfuryl group, a phosphoric acid group, a phosphate ester group, a quaternary ammonium base group, an ethyleneoxy chain, a propyleneoxy chain, a sulfonic acid group or a group derived from a salt thereof, or a morpholine ethyl group. Monomers are also useful.

Moreover, an alkali-soluble binder may have a polymeric group in a side chain in order to improve crosslinking efficiency, For example, the polymer etc. which contain an allyl group, a (meth) acryl group, or an aryloxyalkyl group etc. in a side chain are also useful. Examples of the polymer containing the polymerizable group described above include commercially available KS resist-106 (manufactured by Osaka Organic Chemical Industry Ltd.), CYCLOMER P series (manufactured by DAICEL Chemical Industries, Ltd.), and the like. In addition, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane, epichlorohydrin, etc. are also useful in order to raise the strength of a hardened film.

Among these various alkali-soluble binders, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, or acrylic / acrylamide copolymer resins are preferable from the viewpoint of heat resistance, and acrylic resins, Acrylamide type resin or acryl / acrylamide copolymer resin is preferable.

As said acrylic resin, the copolymer consisting of a monomer chosen from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, etc., and KS resist-106 which is a commercial item (Osaka Organic) Chemical Industry Ltd.), or CYCLOMER P series (product of DAICEL Chemical Industries, Ltd.) and the like.

The alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by the GPC method) of 1000 to 2 × 10 ⁵ from the viewpoint of developability, liquid viscosity, and the like, and more preferably 2000 to 1 × 10 ⁵ . And, the polymer of 5000-5 * 10 <^4> is especially preferable.

Alkali-soluble binder may be contained independently or may contain 2 or more types.

Photosensitizer

A photosensitizer can also be added to the colored curable composition of this invention. Typical sensitizers for use in the present invention include Krivelo [J. V. Crivello, Adv. in Polymer Sci, 62, 1 (1984)], specifically, pyrene, perylene, acridine, thioxanthone, 2-chloro thioxanthone, benzoflavin, N-vinyl Carbazole, 9,10-dibutoxy anthracene, anthraquinone, benzophenone, coumarin, ketokumirin, phenanthrene, camphorquinone, and phenothiazine derivatives. It is preferable to add a photosensitizer in the ratio of 50 to 200 weight% with respect to a photoinitiator.

Chain transfer agent

A chain transfer agent can also be added to the colored curable composition of this invention. Examples of the chain transfer agent used in the present invention include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, N-phenylmercaptobenzoimidazole, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H Mercapto compounds having a heterocycle such as, 3H, 5H) -trione, and aliphatic such as pentaerythritol tetrakis (3-mercaptobutylate) and 1,4-bis (3-mercaptobutyryloxy) butane And polyfunctional mercapto compounds.

A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.

The addition amount of the chain transfer agent is preferably in the range of 0.01% by weight to 15% by weight with respect to the total solids of the composition of the present invention from the viewpoint of reducing the sensitivity unevenness, more preferably 0.1% by weight to 10% by weight, and 0.5% by weight. %-5 weight% are especially preferable.

Polymerization inhibitor

The colored curable resin composition of this invention may contain a polymerization inhibitor.

The polymerization inhibitor is hydrogenated (or hydrogen donated), energy donated (or energy donated), electron donated (or electron donated), or the like for polymerization initiation species such as radicals generated in the colored curable resin composition by light or heat. It is a substance which inactivates a starting species and suppresses initiation of polymerization unintentionally. The polymerization inhibitor etc. of Paragraph 0154 of Unexamined-Japanese-Patent No. 2007-334322-0173, etc. can be used. Among these, p-methoxyphenol is mentioned preferably as a polymerization inhibitor.

As for content of the polymerization inhibitor in the colored curable resin composition of this invention, 0.0001-5 weight% is preferable with respect to the total weight of an ethylenically unsaturated compound, 0.001-5 weight% is more preferable, 0.001-1 weight% Particularly preferred.

Organic solvent

The colored curable composition of this invention can contain the organic solvent.

The organic solvent is not particularly limited as long as it can satisfy the solubility of each component to be coexisted and the coating property when the colored curable composition is used, and in particular, the organic solvent is preferably selected in consideration of solubility, coating property and safety of solid content. .

As the organic solvent, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoam acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, lactic acid Ethyl, oxyacetic acid alkyl esters (e.g. methyl oxyacetic acid, ethyl oxyacetic acid, butyl oxyacetic acid (specifically methyl methoxyacetic acid, methoxyacetic acid ethyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl, etc.) 3-oxypropionic acid alkyl esters, 2-oxypropionic acid alkyl esters, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, and pyruvic acid Propyl, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoic acid, 2-oxobutanoic acid There may be mentioned naphthyl and the like.

As the ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like.

As ketones, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc. are mentioned, for example.

As aromatic hydrocarbons, toluene, xylene, etc. are mentioned suitably, for example.

When these organic solvents contain the solubility of each component mentioned above, and an alkali-soluble binder, it is also preferable to mix 2 or more types from a viewpoint of the solubility, the improvement on a coating surface, etc. In this case, particularly preferably methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone , Cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

The amount in which the total solid concentration in a composition becomes 10 mass%-80 mass% is preferable, and, as for content in the colored curable composition of an organic solvent, the amount which becomes 15 mass%-60 mass% is more preferable.

Surfactants

The colored curable resin composition of this invention may contain surfactant.

As surfactant, any of anionic surfactant, cationic surfactant, nonionic surfactant, or amphoteric surfactant can be used, but a preferable surfactant is a nonionic surfactant. Specifically, the nonionic surfactant of Paragraph 0058 of Unexamined-Japanese-Patent No. 2009-098616 is mentioned, Especially, a fluorine-type surfactant is preferable.

As other surfactant which can be used for this invention, it is a commercial item MEGAFACE F142D, copper F172, copper F173, copper F176, copper F177, copper F183, copper F479, copper F482, copper F554, copper F780, copper F781, copper, for example. F781-F, copper R30, copper R08, copper F-472SF, copper BL20, copper R-61, copper R-90 (manufactured by DIC Corporation), FLUORAD FC-135, copper FC-170C, copper FC-430, copper FC -431, Novec FC-4430 (manufactured by Sumitomo 3M Ltd.), ASAHI GUARD AG 7105, 7000, 950, 7600, SURFLON S-112, copper S-113, copper S-131, copper S-141, copper S-145 , S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), EFTOP EF351, 352, 801, 802 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), FTERGENT 250 (manufactured by Neos Company Ltd.), and the like.

Moreover, the air containing the structural unit A and structural unit B represented by following formula (1) as surfactant, and whose weight average molecular weight (Mw) of polystyrene conversion measured by gel permeation chromatography as THF as a solvent is 1,000 or more and 10,000 or less. The coalescence is mentioned as a preferable example.

In said formula (1), R <^1> and R <^3> represents a hydrogen atom or a methyl group each independently, R <^2> represents a C1 or more linear alkylene group of 4 or more, R <^4> represents a hydrogen atom or 1 or more carbon atoms 4 or less alkyl group, L represents a C3 or more and 6 or less alkylene group, p and q are the weight percentages which show a polymerization ratio, p is a numerical value of 10 weight% or more and 80 weight% or less Q represents a numerical value of 20% by weight or more and 90% by weight 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 formula (1) is preferably a branched alkylene group represented by the following formula (2).

In said formula (2), R <^5> represents a C1-C4 alkyl group, A C1-C3 alkyl group is preferable at the point of compatibility and the wettability with respect to a to-be-coated surface, and C2 or 3 Alkyl groups are more preferred.

It is preferable that sum (p + q) of p and q in said Formula (1) is p + q = 100, ie, 100 weight%.

As for the weight average molecular weight (Mw) of the said copolymer, 1,500 or more and 5,000 or less are more preferable.

Surfactant can be used individually by 1 type or in mixture of 2 or more types. 0.01 weight%-2.0 weight% are preferable in solid content, and, as for the addition amount of surfactant in the colored curable composition of this invention, 0.02 weight%-1.0 weight% are especially preferable. If it is this range, applicability | paintability and the uniformity of a cured film become favorable.

Adhesion improver

The colored curable resin composition of this invention may contain an adhesion improving agent.

An adhesion improving agent is a compound which improves the adhesiveness of the inorganic substance used as a base material, for example, silicon compounds, such as glass, a silicon, a silicon oxide, and silicon nitride, gold, copper, aluminum, etc., and a cured film. Specifically, a silane coupling agent, a thiol type compound, etc. are mentioned. The silane coupling agent as an adhesion improving agent aims at modification of an interface, A well-known thing can be used without a restriction | limiting in particular.

As a silane coupling agent, the silane coupling agent of Paragraph 0048 of Unexamined-Japanese-Patent No. 2009-98616 is preferable, and (gamma)-glycidoxy propyl trialkoxysilane and (gamma) -methacryloxypropyl trialkoxysilane are especially preferable. These can use 1 type individually or in combination of 2 or more types.

0.1 weight%-20 weight% are preferable with respect to total solid, and, as for content of the adhesion | attachment improving agent in the colored curable resin composition of this invention, 0.2 weight%-5 weight% are more preferable.

Crosslinking agent

A crosslinking agent may be used in addition to the colored curable composition of the present invention, and the hardness of the colored cured film formed by curing the colored curable composition may be further increased.

The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, the crosslinking agent is substituted with at least one substituent selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Phenol compounds, naphthol compounds or hydroxyanthracene compounds substituted with at least one substituent selected from the selected melamine compound, guanamine compound, glycoluril compound or urea compound, (c) methylol group, alkoxymethyl group, and acyloxymethyl group Can be. Especially, polyfunctional epoxy resin is preferable.

For details, such as the specific example of a crosslinking agent, the description of Paragraph [0134]-[0147] of Unexamined-Japanese-Patent No. 2004-295116 can be referred.

A development accelerator

When the alkali solubility of a non-exposed area | region is accelerated and the developability of a colored curable composition is aimed at further improving, the image development promoter can also be added to the colored curable composition of this 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 phenolic compound having a molecular weight of 1000 or less.

Specific examples include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brasilic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethyl succinic acid Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid and camphoronic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid; Phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamildeacetic acid, coumaric acid, umbelic acid and the like.

Other additives

Various additives, for example, a filler, a high molecular compound other than the above, an ultraviolet absorber, antioxidant, an aggregation inhibitor, etc. can be mix | blended with the colored curable composition of this invention as needed. Examples of these additives include those described in paragraphs [0155] to [0156] of JP-A-2004-295116.

In the colored curable composition of this invention, the light stabilizer of Paragraph [0078] of Unexamined-Japanese-Patent No. 2004-295116, and the heat polymerization inhibitor of Paragraph [0081] of the same publication can be contained.

Preparation of colored curable composition

The colored curable composition of this invention is prepared by mixing arbitrary components with each component mentioned above as needed.

In addition, in preparation of a colored curable composition, you may mix | blend each component which comprises a colored curable composition, and you may mix | blend sequentially, after melt | dissolving and disperse | distributing each component to a solvent. In addition, the addition order and working conditions at the time of compounding are not restrict | limited. For example, a composition may be prepared by dissolving and dispersing all the components in a solvent at the same time. If necessary, each component may be appropriately prepared in two or more solutions and dispersions, and mixed at the time of use (at the time of application) to prepare a composition. You may also

The colored curable composition prepared as mentioned above can be used for use, after filtering-separating using the filter etc. which are preferably about 0.01 micrometer-about 3.0 micrometers of pore diameters.

The colored curable composition of the present invention is at least one selected from the group consisting of a compound represented by the above general formula (I) and a tautomer thereof having excellent solubility in a solvent (such as an organic solvent to be contained if desired) contained in the colored curable composition. Species are contained as colorants. Therefore, even if the content rate of a coloring agent is made high, the colored curable composition excellent in storage stability is obtained. And the colored cured film obtained by hardening | curing a colored curable composition has a high optical density even if it is thin layer, and can form the colored cured film excellent in color and contrast. Therefore, for forming colored pixels, such as a color filter used for a display apparatus, such as a liquid crystal display device (LCD), and a solid-state image sensor (for example, CCD, CMOS, etc.), printing ink, an inkjet ink, a paint, etc. It can be used suitably as a manufacturing use of. In particular, it is suitable for the coloring pixel formation use for display apparatuses.

Color filter and manufacturing method

The color filter of this invention has a board | substrate (henceforth "a support body"), and the colored area | region which consists of the colored curable composition of this invention on the said board | substrate. The colored area | region on a board | substrate is comprised by the coloring film which consists of each pixel of a color filter, for example, red (R), green (G), chuck color (B).

The manufacturing method of the color filter of this invention apply | coats the above-mentioned colored curable composition on a support body, forms a colored layer (also called a colored curable composition layer), and the colored curable composition layer formed at the process (A). The process (B) of exposing and developing in a pattern form and forming a colored area | region (coloring pattern) is included. Moreover, the manufacturing method of the color filter of this invention especially the process (C) of irradiating an ultraviolet-ray to the coloring pattern formed in the process (B), and the process of heat-processing the coloring pattern irradiated with an ultraviolet-ray at the process (C). It is preferable that it is a form containing (D) further.

Hereinafter, the manufacturing method of the color filter of this invention is demonstrated more concretely.

Process (A)

In the manufacturing method of the color filter of this invention, the coloring curable composition of this invention mentioned above was first apply | coated by the apply | coating methods, such as rotation coating, slit coating, cast coating, roll coating, bar coating, or inkjet, on a support body. A layer is formed, and then the colored curable composition layer is dried by heating (prebaking) or vacuum drying or the like.

As a support body, the soda glass, alkali free glass, borosilicate glass, quartz glass, a silicon substrate, a resin substrate, etc. which are used for a display apparatus etc. are mentioned, for example. Moreover, you may form a primer layer on these support bodies in order to improve adhesion with an upper layer, to prevent the spread of a substance, or to planarize a surface as needed.

As conditions for prebaking, the conditions of heating at 70 degreeC-130 degreeC for 0.5 to 15 minutes using a hotplate or oven are mentioned.

In addition, the thickness of the colored curable composition layer formed of a colored curable composition is suitably selected according to the objective. In the color filter for display devices, the range of 0.2 micrometer-5.0 micrometers is preferable, and the range of 1.0 micrometer-4.0 micrometers is more preferable. Moreover, in the color filter for solid-state image sensors, the range of 0.2 micrometer-5.0 micrometers is preferable, and the range of 0.3 micrometer-2.5 micrometers is more preferable. In addition, the thickness of a colored curable composition layer is a film thickness after drying.

Process (B)

Next, in the manufacturing method of the color filter of this invention, pattern exposure is performed with respect to the colored curable composition layer formed on the support body. As light or radiation which can be applied to exposure, g line | wire, h line | wire, i line | wire, and various laser beams are preferable, and i line | wire is especially preferable. When i line | wire is used for irradiation light, it is preferable to irradiate with the exposure amount of 5mJ / cm <2> -500mJ / cm <2>.

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

Exposure process using a laser light source

In the exposure method using a laser light source, an ultraviolet light laser of the wavelength range whose wavelength is 300 nm-410 nm is preferable, More preferably, it is a wavelength of the range of 300 nm-360 nm. Specifically, the third harmonic (355 nm) of the Nd: YAG laser of a solid laser having a large output and relatively low cost, and the XeCl (308 nm) and XeF (353 nm) of the excimer laser can be suitably used. As a pattern exposure amount, the range of 1mJ / cm <2> -100mJ / cm <2> is preferable from a viewpoint of productivity, and the range of 1mJ / cm <2> -50mJ / cm <2> is more preferable.

Although there is no restriction | limiting in particular as an exposure apparatus, As what is marketed, Callisto (made by V Technology Co., Ltd.), EGIS (made by V Technology Co., Ltd.), and DF2200g (made by Dainippon Screen Mfg. Co., Ltd.) Etc. can be used. Moreover, the apparatus of that excepting the above is also used suitably.

Next, image development is performed with a developing solution with respect to the colored curable composition layer after exposure. Thereby, a coloring pattern can be formed. As long as the developing solution melt | dissolves the uncured part of a colored curable composition layer, and does not melt a hardened part, the combination of various organic solvents and alkaline aqueous solution can be used. When the developing solution is an alkaline aqueous solution, it is preferable to adjust so that alkali concentration may become pH10-13 preferably. As said alkaline aqueous solution, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl Alkaline aqueous solutions such as ammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo- [5,4,0] -7-undecene.

As for image development time, 30 second-300 second are preferable, More preferably, they are 30 second-120 second. As for image development temperature, 20 degreeC-40 degreeC are preferable, More preferably, it is 23 degreeC.

The development can be performed by a paddle method, a shower method, a spray method, or the like.

Moreover, after image development using alkaline aqueous solution, it is preferable to wash with water.

Process (C)

In the manufacturing method of the color filter of this invention, postexposure by ultraviolet irradiation can also be performed with respect to the coloring pattern (pixel) formed using the colored curable composition especially.

Process (D)

It is preferable to heat-process further about the coloring pattern in which the post exposure by the above-mentioned ultraviolet irradiation was performed. The colored pattern can be further cured by heat treatment (so-called post-baking treatment) of the formed colored pattern. This heat treatment can be performed by, for example, a hot plate, various heaters, or an oven.

As temperature at the time of heat processing, it is preferable that it is 100 degreeC-300 degreeC, More preferably, it is 150 degreeC-250 degreeC. Moreover, as for heating time, about 10 to 120 minutes are preferable.

The coloring pattern thus obtained constitutes a pixel in the color filter. In the production of a color filter having pixels of a plurality of colors, the steps (A) and (B) and, if necessary, the steps (C) and (D) may be repeated in accordance with the desired number of colors.

In addition, whenever the formation, exposure, and development of a monochromatic colored curable composition layer are completed (every one color), the step (C) and / or step (D) may be performed, and all the colored curable composition layers having a desired color number. After the formation, the exposure, and the development are completed, the step (C) and / or the step (D) may be performed collectively.

Since the color filter (color filter of this invention) obtained by the manufacturing method of the color filter of this invention uses the colored curable composition of this invention, it is excellent in color and contrast. When used for a display device, image display excellent in spectral characteristics and contrast can be achieved while achieving good color.

Display device

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

When the color filter of this invention is used for a display apparatus, the voltage retention rate at the time of applying voltage, containing the metal complex dye which is excellent in spectral characteristics and heat resistance as a coloring agent does not fall, and also the liquid crystal molecule accompanying the fall of a specific resistance There are few orientation defects, the color tone of a display image is favorable, and it is excellent in display characteristics.

For this reason, the display apparatus provided with the color filter of this invention can display the high quality image which was favorable in the color tone of a display image, and was excellent in display characteristics.

About the definition of a display apparatus and the detail of each display apparatus, for example, "Electronic display device (Aki Sasaki by Kogyo Chosakai Publishing Co., Ltd. 1990 issuance)," Display device (Ibuki Sumiaki by Tosho Publishing Co., Ltd.) ., Ltd. (1989)), etc. In addition, the display device is, for example, in "Next-generation liquid crystal display technology (Tatsuo Uchida editing, Kogyo Chosakai Publishing Co., Ltd. 1994 issuance)". There is no restriction | limiting in particular in the display apparatus which can apply this invention, For example, it can apply to the display apparatus of various systems described in the said "next-generation liquid crystal display technique."

You may use the color filter in this invention for the display apparatus of a color TFT system. The display device of the color TFT system is described, for example, in "Color TFT liquid crystal display (Kyoritsu Shuppan Co., Ltd., issued in 1996)". In addition, the present invention provides a display device having an enlarged viewing angle, such as a lateral electric field driving method such as IPS (In-Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), or a super twisted nematic (STN). The present invention can also be applied to twisted nematic (TN), vertical alignment (VA), optically compensated splay (OCS), fringe field switching (FFS), reflective optically compensated bend (R-OCB), and the like.

Furthermore, the color filter in this invention can also be provided also in a bright and high-definition color-filter on array (COA) system. In the COA display device, the required characteristics for the color filter layer may be required for the interlayer insulating film, that is, low dielectric constant and peeling liquid resistance, in addition to the usual required characteristics as described above. In the color filter of the present invention, since a dye multimer having excellent color is used, color purity, light transmittance, and the like are good, so that the color pattern (pixel) is excellent in color, and thus, a COA display device having high resolution and excellent long-term durability can be provided. Can be. Moreover, in order to satisfy the required characteristic of low dielectric constant, you may form a resin film on a color filter layer.

These image display methods are described, for example, on page 43 of "EL, PDP, LCD Display Technology and the Latest Trends in the Market (Issued by Toray Research Center Inc., Research and Research Division 2001)".

In addition to the color filter in this invention, the display apparatus provided with the color filter in this invention consists of various members, such as an electrode substrate, a polarizing film, retardation film, a backlight, a spacer, and a viewing angle compensation film. The color filter of this invention can be applied to the display apparatus comprised from these well-known members. For these members, for example, the '94 liquid crystal display peripheral materials and chemical market (Kentaro Shima, CMC Publishing Co., Ltd. 1994 issuance), the 2003 liquid crystal related market and the future prospects (the lower volume) (Omotes Ryokuchi, Fuji Chimera Research Institute, Inc., 2003).

Backlighting is described in SID meeting Digest 1380 (2005) (A. Konno et.al), pages 18-24 (Shima Hiroyasu), pages 25-30 (Yagi Takaaki), etc. of the December 2005 issue of Monthly DISPLAY. have.

When the color filter of the present invention is used in a display device, high contrast can be realized when combined with the three wavelength tubes of a conventionally known cold cathode tube, but the red, green, and blue LED light source (RGB-LED) is used as a backlight. A display device having high brightness, high color purity and good color reproducibility can be provided.

Solid-state imaging device

The solid-state imaging device of the present invention includes the color filter of the present invention described above. As a structure of the solid-state image sensor of this invention, if it is a structure with the color filter of this invention, and it is a structure which functions as a solid-state image sensor, there is no limitation in particular, For example, the following structures are mentioned.

It has a transfer electrode which consists of a several photodiode, polysilicon, etc. which comprise the light receiving area of a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) on a support body, and the light-receiving part of a photodiode on the said photodiode and the said transfer electrode It has a light shielding film made of tungsten or the like opened only, a device protective film made of silicon nitride or the like formed on the light shielding film to cover the entire surface of the light shielding film and the photodiode light receiving portion, and has the color filter of the present invention on the device protective film.

Moreover, the structure which has a light concentrating means (for example, a microlens etc .. is the same below) on the said device protective layer and below a color filter (side close to a support body), may be a structure which has a light converging means on a color filter.

Example

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the acclaim is exceeded. In addition, "part" and "%" are mass references | standards unless there is particular notice.

Example 1 Synthesis of Specific Dipyrromethene Metal Complexes

The specific dipyrromethene metal complex according to the present invention can be synthesized by the following scheme A or scheme B, for example. In addition, in the following schemes A and B, R _x and R _y each represent R ¹⁷ and R ¹⁸ in compounds A-1 to A-96 and the like which are specific examples of the specific dipyrromethene metal complex according to the present invention.

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

(Synthesis of Intermediate 1)

Intermediate 1 was synthesized by the method described in the specification of US Patent Application Publication No. 2008/0076044.

(Synthesis of Intermediate 2)

To 60 ml of N, N-dimethylacetamide, 30.6 g (0.3 mol) of pivalic acid was added and stirred under an ice bath. To this solution, 35.7 g (0.3 mol) of thionyl chloride was added dropwise, followed by stirring under an ice bath for 1 hour at room temperature for 1 hour to obtain an acid halide solution.

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

After completion | finish of reaction, after adding 700 ml of acetonitrile to the reaction liquid and stirring for 1 hour, it filtered and dried the obtained solid. Thus, 92 g of an intermediate 2 (yield: 93%) was obtained.

Further, 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), 1.25-0.97 (m, 5H), 0.83 (s, 18H), 0.71-0.69 (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 an ice bath, and 18.6 g of phosphorus oxychloride was added dropwise. It stirred at 5 degrees C or less for 1 hour after completion | finish of dripping. A small amount of intermediate 2 was added to this solution. Then, it stirred for 1 hour and room temperature for 2 hours in an ice bath. After completion of the reaction, the reaction solution was poured into 300 ml of water and 300 ml of ethyl acetate and extracted. The ethyl acetate solution was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off. The obtained solid was washed with 500 ml of methanol, filtered and dried. Thus, 36g (yield: 86%) of intermediate 3 was obtained.

Further, 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), and 7.35 to 7.26 (m). , 2H), 5.90 (s, 1H), 1.37 (s, 9H), 1.27-0.98 (m, 5H), 0.82 (s, 18H), 0.71-0.69 (d, 3H), 0.45-0.33 (q, 2H Was.

(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 82.9 g (0.6 mol) of potassium carbonate were added. And it stirred at 120 degreeC for 16 hours.

After the reaction solution was cooled, 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 then the solvent was distilled off. Thereafter, 40 g of a 50% NaOH aqueous 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 | finish of reaction, water hydrochloric acid was added, it neutralized, and ethyl acetate was added and extracted. This ethyl acetate solution was washed with saturated brine, and the solvent was distilled off. Then, the residue was purified by silica gel column chromatography to obtain 59 g of an intermediate 4 (yield 60%).

Further, 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), and 7.07 to 7.04 (m, 1H). , 4.39 to 4.36 (t, 2H), 3.83 to 3.79 (t, 2H), and 3.46 (s, 3H).

(Synthesis of Intermediate 5)

19.6 g (0.1 mol) of Intermediate 4 was added to 20 ml of N, N-dimethylacetamide, followed by stirring under an ice bath. To this solution, 11.9 g (0.1 mol) of thionyl chloride was added dropwise, followed by stirring under an ice bath for 1 hour at room temperature for 1 hour to obtain an acid halide solution.

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

After completion of the reaction, 200 ml of acetonitrile was added to the reaction solution, stirred for 1 hour, and then filtered to dry the obtained solid. In this way, 33g (yield: 85%) of intermediates 5 were obtained.

In addition, 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), and 7.36 to 7.08. (m, 6H), 6.35 (s, 1H), 5.90 (s, 1H), 4.58 to 4.44 (t, 2H), 3.96 to 3.92 (t, 2H), 3.39 (s, 3H), 1.26 to 0.97 (m , 5H), 0.86 (s, 18H), 0.71 to 0.96 (d, 3H), and 0.64 to 0.47 (q, 2H).

(Synthesis of Intermediate 6)

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

The details of ¹ H-NMR (CDCl ₃ ) are δ: 12.50 (s, 1H), 10.96 (s, 1H), 8.48 to 8.45 (d, 1H), 7.53 to 7.47 (m, 1H), and 7.29 to 7.09. (m, 8H), 6.03 (s, 1H), 5.88 (s, 1H), 4.58-4.44 (t, 2H), 3.92-3.89 (t, 2H), 3.39 (s, 3H), 1.44 (s, 9H ), 1.21 to 0.95 (m, 10H), 0.81 (s, 36H), 0.65 to 0.63 (d, 6H), and 0.43 to 0.31 (q, 4H).

Example Synthesis of Compound A-41

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

Further, 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), and 7.28 to 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), and 0.43 to 0.38 (m, 4H).

(Synthesis of Intermediate 7)

34.8 g (0.3 mol) of 2,2-dimethylbutyric acid was added to 60 ml of N, N-dimethylacetamide, and it stirred under an ice bath. To this solution, 35.7 g (0.3 mol) of thionyl chloride was added dropwise, followed by stirring under an ice bath for 1 hour at room temperature for 1 hour to obtain an acid halide solution.

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

After completion of the reaction, 700 ml of acetonitrile was added to the reaction solution, stirred for 1 hour, and then filtered, and the obtained solid was dried. In this way, 91.6g (yield: 90%) of intermediates 7 were obtained.

In addition, 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 to 1.66 (q, 2H), 1.32 (s, 6H), 1.25 to 0.90 (m, 8H), 0.83 (s, 18H), 0.70 to 0.68 (d, 3H), 0.58 to 0.46 (q, 2H) Was.

(Synthesis of Intermediate 8)

70 ml of tetrahydrofuran and 100 ml of dimethylformamide (DMF) were stirred under an ice bath, and 11.8 g (77 mmol) of phosphorus oxychloride was added dropwise. It stirred at 5 degrees C or less for 1 hour after completion | finish of dripping. A small amount of intermediate 7 was added to this solution. Then, it stirred for 1 hour and room temperature for 2 hours in an ice bath. After completion of the reaction, the reaction solution was poured into 300 ml of water and 200 ml of ethyl acetate and extracted. The ethyl acetate solution was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off. The obtained solid was washed with 500 ml of methanol, filtered and dried. Thus, 22.9 g (yield: 83%) of intermediate 8 was obtained.

In addition, 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 to 1.67 (q, 2H), 1.32 (s, 6H), 1.25 to 0.87 (m, 8H), 0.82 (s, 18H), 0.71 to 0.96 (d, 3H), 0.45 to 0.33 (q, 2H) Was.

(Synthesis of Intermediate 9)

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

To this ethyl acetate solution was added 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 solution, followed by stirring under a water bath. Then, 25 wt% sodium hypochlorite was dripped, and it stirred at 50 degreeC for 9 hours. After the reaction was completed, ethyl acetate was added and extracted. The ethyl acetate solution was washed with water and brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off. The obtained solid was recrystallized with an ethyl acetate / hexane mixed solvent and dried.

Thus, 112g of intermediate 4 (yield: 67%) was obtained.

Further, 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), and 4.17. It was -4.15 (d, 2H), 1.89-1.79 (m, 1H), 1.55-1.29 (m, 8H), and 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 the mixture was stirred under an ice bath. To this solution, 42.8 g (0.36 mol) of thionyl chloride was added dropwise, followed by stirring under an ice bath for 1 hour at room temperature for 1 hour to obtain an acid halide solution.

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

450 ml of acetonitrile were added to the reaction liquid after completion | finish of reaction, and after stirring for 1 hour, it filtered and dried the obtained solid. Thus, 179.0 g (yield: 93%) of intermediate 10 was obtained.

In addition, 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 to 7.28 (m, 5H), 7.10 to 7.04 (m, 2H), 6.34 (s, 1H), 5.89 (s, 1H), 4.31 to 4.29 (d, 2H), 2.19 to 2.09 (m, 1H), 1.54 to 1.16 (m, 11H), 1.04-0.82 (m, 26H), 0.71-0.69 (d, 3H), and 0.59-0.46 (m, 2H).

(Synthesis of Intermediate 11)

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

Further, 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 to 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 to 0.97 (m, 69H), 0.65 to 0.62 (m, 6H), and 0.43 to 0.31 (q, 4H).

Example Synthesis of Compound A-55

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

In addition, 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), and 7.26 to 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), and 0.43-0.20 (m, 4H).

(Synthesis of Intermediate 12)

About intermediate 12, it synthesize | combined according to the method of Unexamined-Japanese-Patent No. 2012-140586.

(Synthesis of Intermediate 13)

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

Separately, 5.0 g (20 mmol) of intermediate 4, 2.4 g (20 mmol) of thionyl chloride, and 0.1 g of N, N-dimethylformamide were added to 6.4 ml of toluene, stirred at 40 ° C. for 30 minutes, and cooled to acid halide. Solution 1 was obtained.

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

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), and 7.26 to 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) and 0.41-0.34 (m, 4H).

Example Synthesis of Compound A-7

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

In addition, 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 to 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 to 0.63 (d, 6H) and 0.43 to 0.20 (m, 4H).

(Synthesis of Intermediate 14)

To 6.4 ml of toluene, 4.3 g (20 mmol) of 2-phenoxybenzoic acid, 2.4 g (20 mmol) of thionyl chloride, and 0.1 g of N, N-dimethylformamide were added, stirred at 40 ° C. for 30 minutes, and cooled to acid Halide solution 2 was obtained.

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

In addition, 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 to 6.67 (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 ) And 0.41 to 0.29 (m, 4H).

Example Synthesis of Compound A-1

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

In addition, 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), and 6.82 to 6.69 (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 to 0.62 (m, 6H) and 0.43 to 0.31 (m, 4H).

About each obtained compound, the molar extinction coefficient (epsilon) in the chloroform solution was measured using the spectrophotometer UV-1800PC (brand name, the Shimadzu Corporation make). Maximum absorption wavelength (lambda) max of Exemplified Compound A-7 was 560.5 nm, and molar extinction coefficient (epsilon) was 128000.

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

In addition, the results of the maximum absorption wavelength [lambda] max, the molar extinction coefficient ([epsilon]), the solubility and the weight loss rate for propylene glycol monomethyl ether acetate are shown in Table 1 below.

Example 2

By the method similar to the reaction scheme in Example 1, the Example compound (compound represented by General formula (I) or its tautomer) shown in following Table 1 was further synthesize | combined, and it identified by the method similar to Example 1 And the maximum absorption wavelength (lambda) max and the molar extinction coefficient (epsilon) were measured, the solubility with respect to propylene glycol monomethyl ether acetate, and the weight loss rate were evaluated. The results are shown in Table 1 below.

evaluation

(Solubility in propylene glycol monomethyl ether acetate)

The sample was weighed, and propylene glycol monomethyl ether acetate was added to the following concentration, respectively, and after 30 minutes stirring at room temperature, the dissolution state was visually confirmed.

＊ Judgment method

5wt% or more dissolved: A

1 wt% to less than 5 wt%: B

Less than 1wt%: C

(Weight loss rate)

The weight reduction rate (%) at the time of heating up a sample 10 degreeC every minute from 35 degreeC to 230 degreeC, and heating at 230 degreeC for 30 minutes was evaluated.

＊ Judgment method

Less than 5%: A

5% to less than 10%: B

More than 10%: C

In addition, the detail of the comparative compounds 1, 2, 3 is as follows. The structural formula of each comparative compound is shown below.

Comparative Compound C1 (Compound III-61 described in Japanese Patent Application Laid-Open No. 2008-292970)

Comparative Compound C2 (Compound A-29 described in Japanese Patent Application Laid-Open No. 2010-85454)

Comparative Compound C3 (Compound III-45 described in Japanese Patent Application Laid-Open No. 2008-292970)

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

Hereinafter, the specific example which produces colored curable composition and a color filter is shown.

Example 3

First, each component used for preparation of a colored curable composition is shown below.

(S-1): pigment dispersion obtained by mixing 12.8 parts of C.I. pigment blue 15: 6 and 7.2 parts of an acrylic pigment dispersant with 80.0 parts of propylene glycol monomethyl ether acetate and sufficiently dispersing the pigment using a bead mill.

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

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

(V-1): Photoinitiator: 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone

(V-2): Photoinitiator: 2- (acetoxyimino) -4- (4-chlorophenylthio) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3- Japanese] -1-butanone

(W-1): sensitizer: 4,4'-bis (diethylamino) benzophenone

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

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

(Y-1): Surfactant: MEGAFAC F781-F (manufactured by DIC Corporation)

B1. Preparation of colored curable composition (coating liquid)

The component in the following composition was mixed and the colored curable composition 1 was prepared.

<Composition>

Example compound A-1, 6.9 parts

     (Specific Dipyrromethene Metal Complex)

Pigment dispersion liquid: (S-1) above 43.0 parts

Polymerizable compound: Said (T-1) 103.4 parts

Alkali-soluble binder: said (U-1) ... 212.2 parts (solid content conversion value: 84.9 parts)

Photoinitiator: said (V-1) ... 21.2 parts

Sensitizer: (W-1) above 3.5 parts

Organic solvents: (X-1) above 71.9 parts

Organic solvents: (X-2) above 3.6 parts

Surfactant: (Y-1) above 0.06 parts

B2. Preparation and Evaluation of Color Filters by Colored Curable Compositions

The colored curable composition (color resist liquid) obtained in the above B1. Was coated on a 100 mm × 100 mm glass substrate (trade name: 1737, manufactured by Corning) so that the x value, which is an index of color concentration, became 0.150, and then in an oven at 90 ° C. It was dried for 60 seconds (prebaking). Then, it exposed at 200 mJ / cm <2> (roughness 20mW / cm <2>) with a high pressure mercury lamp through the photomask which has a mask hole width of 10 micrometers-100 micrometers for resolution evaluation. The coating film after exposure was developed using the 1% aqueous solution of alkali developing solution CDK-1 (brand name: Fuji Film Electronics Materials Co., Ltd. product), the pure water was sprayed on the shower, and the developing solution was wash | cleaned. Then, the coating film subjected to the exposure and development as described above was heated in an oven at 220 ° C. for 1 hour (post baking), and a patterned colored cured film (color layer) for color filters was formed on the glass substrate to form a colored filter. Substrate 1 (color filter 1) was produced.

evaluation

The following evaluation was performed about the obtained color filter 1. The evaluation results are shown in Table 2 below.

1. Preservation stability

After storing the said colored resist liquid for 1 month in refrigeration (5 degreeC), the precipitation degree of the foreign material was visually evaluated according to the following criteria.

Criteria

A: Precipitation was not confirmed.

B: Precipitation was confirmed slightly.

C: Precipitation was confirmed.

2. Heat resistance

The color filter 1 was heated at 230 ° C. for 30 minutes by a hot plate as a heat resistance test, and the ΔE * ab value of the color difference before and after the heat test was measured with a colorimeter MCPD-1000 (trade name: Otsuka Electronics Co., Ltd.). It evaluated according to the following criteria. The smaller the ΔE * ab value is, the better the heat resistance is, which shows good performance as a color filter.

Criteria

5: ΔE * ab value <3

4: 3≤ΔE * ab value <5

3: 5≤ΔE * ab value <10

2: 10≤ΔE * ab value <20

1: 20≤ΔE * ab value

3. Luminance

The luminance of the color filter 1 was measured using a microscopic spectrometer OSP-SP200 (trade name) manufactured by Olympus Corporation, and evaluated by the Y value. The higher the Y value, the better the color filter for the liquid crystal display.

4. Contrast

The obtained color filter 1 was sandwiched between two polarizing films, and the luminance value when the polarization axes of the two polarizing films were parallel and vertical was measured using a color luminance meter (manufactured by TOPCON Corporation, model number: BM-5A). It measured using it, divided | segmented the brightness | luminance at the time of perpendicular | vertical when the polarization axis of two polarizing films is parallel, and calculated | required the obtained value as contrast. Higher contrast indicates better performance as a color filter for liquid crystal displays.

Criteria

5: contrast is more than 20,000

4: contrast is more than 15,000 and less than 20,000

3: contrast of more than 10,000 and less than 15,000

2: contrast of 5,000 or more but less than 10,000

1: contrast less than 5,000

5. Pattern Shape

A colored film was prepared in the same manner as in Example 1, and then exposed to 50 mJ / cm 2 (roughness 20 mW / cm 2) over the entire surface of the coating film through a mask, and the coated film after exposure was alkali developer CDK-1 (Fuji Film Electronics Materials Co. , Ltd.) was sprayed onto a shower to develop. Thereafter, pure water was sprayed onto the shower to wash off the developer. Then, as described above, the coating film subjected to the photocuring treatment and the developing treatment was heated in an oven at 220 ° C. for 30 minutes (post-baking), and a colored resin film for color filter construction was formed on the glass substrate to form a colored resin film. The board | substrate (colored board | substrate) which has is produced.

The said colored board | substrate was cut out using the glass cutter, and the cross section was observed at 15,000 times using the scanning electron microscope (S-4800 (brand name) by Hitachi Co. Ltd.). Evaluation criteria are as follows.

Evaluation standard

A: The pattern end part has a gentle slope shape.

B: The pattern end is rectangular.

C: An incision has arisen in the pattern edge part.

[Examples 4 to 18]

In preparation of the colored curable composition 1 of Example 3, Example compound A-1 is substituted by the above-mentioned example compound (specific dipyrromethene metal complex) shown in Table 1, respectively, and an example compound and a pigment dispersion liquid so that chromaticity may be matched ( The colored curable composition 2-the colored curable composition 16 were prepared like Example 3 except having adjusted the ratio of S-1), and the color filter 2-the color filter 16 were produced subsequently.

It evaluated like Example 3 using colored curable composition 2-colored curable composition 16, and color filter 2-color filter 16. It evaluated. The results are shown in Table 2 below.

Example 19

In Example 3, the color filter 17 was obtained like Example 3 except having mixed the component in the following composition, and preparing the colored curable composition 17, and using the colored curable composition 17 instead of the colored curable composition 1.

It evaluated like Example 3 using the colored curable composition 17 and the color filter 17. The results are shown in Table 2.

Furtherance

Example compound A-7, 6.9 parts

Pigment dispersion liquid: (S-1) above 43.0 parts

Polymerizable compound: Said (T-1) 103.4 parts

Alkali-soluble binder: said (U-1) ... 212.2 parts (solid content conversion value: 84.9 parts)

Photoinitiator: said (V-2) ... 21.2 parts

Sensitizer: (W-1) above 3.5 parts

Organic solvents: (X-1) above 71.9 parts

Organic solvents: (X-2) above 3.6 parts

Surfactant: (Y-1) above 0.06 parts

[Examples 20-23]

In preparation of the colored curable composition 17 of Example 19, Example compound A-7 is substituted by the above-mentioned example compound (specific dipyrromethene metal complex) shown in Table 2, respectively, and an example compound and a pigment dispersion liquid so that chromaticity may be matched ( In the same manner as in Example 19, except that the ratio of S-1) was changed, the colored curable composition 18 to the colored curable composition 20 were prepared, and then the color filter 18 to the color filter 20 were obtained.

It evaluated like Example 3 using the colored curable composition 17-the colored curable composition 20, and the color filter 17-the color filter 20. The results are shown in Table 2.

Example 24

In Example 3, the color filter 21 was obtained like Example 3 except having mixed the component in the following composition, and preparing the colored curable composition 18, and using the colored curable composition 21 instead of the colored curable composition 1.

It evaluated like Example 3 using the colored curable composition 21 and the color filter 21. The results are shown in Table 2.

Furtherance

Example compound A-7, above 4.7 parts

Pigment dispersion: (S-1) above 42.1 parts

Compound (5): 2.3 parts

Polymerizable compound: Said (T-1) 103.4 parts

Alkali-soluble binder: said (U-1) ... 212.2 parts (solid content conversion value: 84.9 parts)

Photoinitiator: said (V-2) ... 21.2 parts

Sensitizer: (W-1) above 3.5 parts

Organic solvents: (X-1) above 71.9 parts

Organic solvents: (X-2) above 3.6 parts

Surfactant: (Y-1) above 0.06 parts

In addition, compound (5) is a diaminoanthraquinone compound represented by general formula (X) mentioned above.

Example 25

In the preparation of the colored curable composition 21 of Example 24, the example compound A-7 was changed to A-41 to prepare the colored curable composition 22, except that the colored curable composition 22 was used instead of the colored curable composition 21. In the same manner as in 21, a color filter 22 was obtained.

It evaluated like Example 3 using the colored curable composition 19 and the color filter 19. It evaluated. The results are shown in Table 2.

Comparative Example 1-Comparative Example 5

In preparation of the colored curable composition 1 of Example 3, Example compound A-1 is substituted by the comparative compound C1-comparative compound C5 shown in Table 2, respectively, and the chromaticity of a comparative compound and a pigment dispersion (S-1) is matched. The colored curable composition 101-the colored curable composition 105 were prepared similarly except having changed the ratio. In addition, the color filter 101-the color filter 105 were obtained like Example 3 except having used the colored curable composition 101-the colored curable composition 105 instead of the colored curable composition 1.

It evaluated like Example 3 using the colored curable composition 101-the colored curable composition 105, and the color filter 101-the color filter 105. The results are shown in Table 2.

In addition, comparative compound C1-the comparative compound C3 are the above-mentioned, and comparative compound C4 and C5 are as follows.

Comparative compound C4 C. I. Acid Violet 17

Comparative compound C5 C. I. Acid Violet 49

From the above result, the colored curable composition produced using the specific dipyrromethene metal complex by this invention has high storage stability, and the color filter produced using the said colored curable composition is excellent in heat resistance, a color, contrast, and the pattern Since the shape can also be improved, the specific dipyrromethene metal complex according to the present invention can be said to be a highly versatile dye.

Claims (15)

Colored curable composition containing a polymeric compound, and at least 1 sort (s) chosen from the group which consists of a compound represented by the following general formula (I), and its tautomer.

[In General Formula (I), R <^2> -R <^5> represents a hydrogen atom or a monovalent substituent each independently; R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group; M represents a metal or metal compound; X ¹ represents a group that neutralizes 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 each independently represent a hydrogen atom or a monovalent substituent; Provided that at least two of R ⁸ to R ¹⁰ are a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a silyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, and a heterocyclic thio Selected from the group consisting of groups; 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 is a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, alkylcarbonyl group, arylcarbonyl group, carbamoyl group, ureido group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl group Indicates The method of claim 1,
At least one selected from the group consisting of a compound represented by the general formula (I) and tautomers thereof is at least one selected from the group consisting of a compound represented by the following general formula (II) and tautomers thereof Curable composition.

[In General Formula (II), R <^3> and R <^4> represents a hydrogen atom or a monovalent substituent each independently; X ¹ represents a group that neutralizes the charge of Zn; R ⁸ to R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent; Provided that at least two of R ⁸ to R ¹⁰ are a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a silyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, and a heterocyclic thio Selected from the group consisting of groups; 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 is a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, alkylcarbonyl group, arylcarbonyl group, carbamoyl group, ureido group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl group Indicates The method of claim 1,
It further contains a photoinitiator, The colored curable composition characterized by the above-mentioned. The method of claim 1,
The colored curable composition further containing at least 1 sort (s) chosen from the group which consists of a pigment and an anthraquinone compound. The method of claim 4, wherein
The said anthraquinone compound is a compound represented by the following general formula (IX), The coloring curable composition characterized by the above-mentioned.

[In Formula (IX), R ^11a and R ^12a each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, but R ^11a and R ^12a do not represent hydrogen atoms at the same time; n ¹¹ represents an integer of 1 to 4] The method of claim 1,
The content of at least one selected from the group consisting of a compound represented by the general formula (I) and a tautomer thereof is in the range of 0.1% by mass to 30% by mass with respect to the total solid of the composition. It is obtained by hardening | curing the colored curable composition in any one of Claims 1-6, The colored cured film characterized by the above-mentioned. The colored cured film of Claim 7 is provided, The color filter characterized by the above-mentioned. The process of apply | coating the coloring curable composition in any one of Claims 1-6 on a support body, and forming a colored curable composition layer,
And exposing and developing said colored curable composition layer in a pattern form to form a colored pattern. A display device comprising the color filter according to claim 8. A display device comprising the color filter produced by the manufacturing method of the color filter of Claim 9. A solid-state imaging device comprising the color filter according to claim 8. A solid-state imaging device comprising the color filter produced by the method for producing a color filter according to claim 9. A compound characterized by being selected from the group consisting of a compound represented by the following general formula (I) and tautomers thereof.

[In General Formula (I), R <^2> -R <^5> represents a hydrogen atom or a monovalent substituent each independently; R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group; M represents a metal or metal compound; X ¹ represents a group that neutralizes 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 each independently represent a hydrogen atom or a monovalent substituent; Provided that at least two of R ⁸ to R ¹⁰ are a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a silyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, and a heterocyclic thio Selected from the group consisting of groups; 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 is a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, alkylcarbonyl group, arylcarbonyl group, carbamoyl group, ureido group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl group Indicates A compound represented by the following general formula (II) and a tautomer thereof.

[In General Formula (II), R <^3> and R <^4> represents a hydrogen atom or a monovalent substituent each independently; X ¹ represents a group that neutralizes the charge of Zn; R ⁸ to R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent; Provided that at least two of R ⁸ to R ¹⁰ are a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a silyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, and a heterocyclic thio Selected from the group consisting of groups; 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 is a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, alkylcarbonyl group, arylcarbonyl group, carbamoyl group, ureido group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl group Indicates