KR20150058282A - Coloring composition, color filter and method for producing same, image display device, solid-state imaging element, and novel compound - Google Patents

Abstract

일반식(I) 중, R¹∼R⁸은, 각각 독립적으로, 수소 원자, 또는 1가의 치환기를 나타낸다. R⁹는, 수소 원자, 할로겐 원자, 알킬기, 아릴기, 또는 헤테로환기를 나타낸다. R¹⁰ 및 R¹¹은, 각각 독립적으로, 수소 원자, 할로겐 원자, 알킬기, 또는 알콕시기를 나타낸다. Ma는 금속 또는 금속 화합물을 나타낸다. X는 Ma와 결합 가능한 기를 나타낸다. n1 및 n2는, 각각 독립적으로, 1∼8의 정수를 나타낸다.A coloring composition comprising at least one compound selected from the group consisting of a compound represented by the following general formula (1) and a tautomer thereof.

In the general formula (I), R ¹ to R ⁸ each independently represent a hydrogen atom or a monovalent substituent. R ⁹ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Ma represents a metal or a metal compound. X represents a group capable of bonding with Ma. n1 and n2 each independently represent an integer of 1 to 8;

Description

TECHNICAL FIELD [0001] The present invention relates to a coloring composition, a color filter and a method for producing the same, an image display device, a solid-state image pickup device, a novel compound,

The present invention relates to a coloring composition, a color filter and a method for producing the same, an image display device, a solid-state imaging device, and a novel compound.

Conventionally, a color filter comprises a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed, a coloring composition by containing a polyfunctional monomer, a polymerization initiator, an alkali-soluble resin and, if necessary, other components, A coloring pattern is formed by a lithography method, an ink-jet method, or the like.

[0002] In recent years, color filters tend to be used not only for monitors but also for televisions (TVs) in liquid crystal display (LCD) applications. [0003] Along with the tendency of this application to be widened, color filters are required to have high color characteristics in terms of chromaticity, contrast, and the like. In addition, in color filters for use in image sensors (solid-state image pickup devices), further improvement in color characteristics such as reduction in color unevenness and improvement in color resolution is required more and more.

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

However, conventionally, as a coloring material, it has been studied to use not only a pigment but also a dye (see, for example, Japanese Patent Application Laid-Open No. 6-75375). When the dye is used as the coloring agent, the color purity of the dye itself or the clarity of the color thereof can enhance the hue and brightness of the display image at the time of image display, and the coarse particles can be eliminated, . ≪ / RTI >

Examples of the performance required for the dye include high solubility in a solvent, high fastness (heat resistance, light resistance, etc.) as well as having good spectral absorption. Further, when the dye is used as a coloring composition, the properties which are considered to be further required are increased depending on the usage and form of the coloring composition. Therefore, it is required to change the kind of dyes appropriately depending on the application.

As examples of the dyes, there are known compounds having a variety of different dye bases such as dypyrromethene dyes, pyrimidine dyes dyes, pyrazole dyes dyes, and zanthen dyes (see, for example, JP-A 2008-292970, See Japanese Patent Application Laid-Open No. 2007-039478 and Japanese Patent No. 3387541).

However, when a coloring layer of a color filter or the like is produced by using a coloring composition containing a dye, there is a problem that the fastness (in particular, the light resistance) of the colored layer is liable to be lowered as compared with the case where a conventional pigment is used have. Further, when developing in the production of a coloring pattern using a coloring composition containing a dye, there is a case where a small amount of dye remains as a development residue, and improvement is required.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described circumstances, and an object of the present invention is to provide a coloring composition which is high in color purity, has a thin layer and has a high extinction coefficient and is excellent in fastness (particularly light resistance), high in developability, And a color filter using the coloring composition and a method of manufacturing the same.

It is another object of the present invention to provide an image display apparatus and a solid-state image pickup device which exhibit a clear display of color of a display image and exhibit a high contrast.

The present invention also relates to a novel compound which is a dipyrromethene metal complex compound having excellent color purity, high extinction coefficient, fastness (particularly light resistance) and solvent solubility, and a tin compound And to provide the above-mentioned object.

Means for solving the above problems are as follows.

≪ 1 > A coloring composition comprising at least one compound selected from the group consisting of a compound represented by the following general formula (I) and a tautomer thereof:

In the general formula (I), R ¹ to R ⁸ each independently represent a hydrogen atom or a monovalent substituent. R ⁹ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Ma represents a metal or a metal compound. X represents a group capable of bonding with Ma. n1 and n2 each independently represent an integer of 1 to 8;

&Lt; 2 > The coloring composition according to < 1 >, wherein in the general formula (I), Ma represents Fe, Zn, Co, V = O or Cu.

<3> The coloring composition according to <1> or <2>, further comprising a polymerizable compound and a photopolymerization initiator.

<4> The coloring composition according to any one of <1> to <3>, further comprising a pigment or an anthraquinone compound or a pigment and an anthraquinone compound together.

&Lt; 5 > The coloring composition according to < 4 >, wherein the anthraquinone compound is a compound represented by the following formula (II).

In the general formula (II), R ^11a and R ^12a each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. However, R ^11a and R ^12a do not represent a hydrogen atom at the same time. n11 represents an integer of 1 to 4;

<6> wherein the general formula (I), R ¹ and R ⁴ are, each independently, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a cyano group, already represents a deugi, or carbamoyl sulfonyl, R ² And R ³ each independently represents an alkyl group or an aryl group and R ⁵ and R ⁶ each independently represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group, and R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ represent a hydrogen atom.

<7> A color filter formed using the coloring composition according to any one of <1> to <6>.

&Lt; 8 > A method for producing a colored layer, comprising the steps of: forming a colored composition layer by applying the colored composition according to any one of < 1 > And forming a color filter on the color filter.

<9> An image display device comprising a color filter according to <7> or a color filter manufactured by the method of manufacturing a color filter according to <8>.

&Lt; 10 > A solid-state imaging device comprising a color filter according to < 7 >, or a color filter manufactured by the method of manufacturing a color filter according to < 8 >.

<11> A compound represented by the following general formula (I) or a tautomer thereof.

In the general formula (I), R ¹ to R ⁸ each independently represent a hydrogen atom or a monovalent substituent. R ⁹ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Ma represents a metal or a metal compound. X represents a group capable of bonding with Ma. n1 and n2 each independently represent an integer of 1 to 8;

<12> In the general formula (I), R ¹ and R ⁴ each independently represent an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a cyano group, an imide group or a carbamoylsulfonyl group, and R ² And R ³ each independently represents an alkyl group or an aryl group and R ⁵ and R ⁶ each independently represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group, and R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ represent a hydrogen atom, or a tautomer thereof.

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a coloring composition capable of forming a coloring layer having a high color purity, a thin layer, a high extinction coefficient, a fastness (particularly light resistance) , A color filter using the coloring composition and a process for producing the same.

Further, according to the present invention, there is provided an image display apparatus and a solid-state image pickup device which exhibit clear coloring of a display image and exhibit high contrast.

Further, according to the present invention, there is provided a novel compound which is excellent in color purity, has a high extinction coefficient, fastness (in particular, light resistance) and solvent solubility, and a tributyrate thereof.

Hereinafter, the coloring composition of the present invention, a color filter using the same, an image display apparatus and a solid-state image pickup device, and a novel compound which is a dipyramethylene-based metal complex compound and a tautomer thereof will be described in detail.

The description of the constituent elements of the present invention described below is made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

In the coloring composition of the present invention, the total solid content refers to the total mass of the components excluding the organic solvent from the total composition of the coloring composition.

In the present specification, the numerical range indicated by using &quot; ~ &quot; means a range including numerical values before and after "~" as a lower limit value and an upper limit value.

In the present specification, for example, the "alkyl group" represents an alkyl group of "straight chain, branched and cyclic". In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes those having a substituent and having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, the term "(meth) acrylate" means either or both of acrylate and methacrylate, and " , And "(meth) acryloyl" represents both acryloyl and methacryloyl, or any one of them.

In the present specification, the monomer is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less.

In the present specification, the polymerizable compound means a compound having 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 the coloring composition of the present invention, the amount of each component means the total amount of the plurality of substances present in the composition, unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition.

In this specification, the term &quot; process &quot; is included in the term when the purpose of the process is achieved, not only in independent processes but also in cases where it can not be clearly distinguished from other processes.

In the present invention, the term &quot; radiation &quot; means visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.

A coloring composition, and a compound represented by the general formula (I) or a tautomer thereof

The coloring composition of the present invention contains at least one compound selected from the group consisting of a compound represented by the general formula (I) and a tautomer thereof.

In the general formula (I), R ¹ to R ⁸ each independently represent a hydrogen atom or a monovalent substituent. R ⁹ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Ma represents a metal or a metal compound. X represents a group capable of bonding with Ma. n1 and n2 each independently represent an integer of 1 to 8;

The compound represented by the general formula (I) or a tautomer thereof is a novel pyromethene metal complex compound (hereinafter referred to as "(optionally)" a specific metal complex compound "). The specific metal complex compound is a dye compound useful as a coloring component and contains the coloring composition of the present invention and can be used as a coloring component in various applications.

By containing the specific metal complex compound, the coloring composition of the present invention solves the problems that can not be achieved with a coloring composition using a conventionally known dye. Therefore, the coloring composition of the present invention is particularly useful for color filters used in solid-state image pickup devices and image display devices (for example, liquid crystal display devices, organic EL display devices, and the like).

In the present invention, the mechanism by which the specific metal complex compound contributes is not yet clarified, but the inventors assume the following.

The specific metal complex compound has a structure in which specific substituents (R ⁵ and R ⁶ ) are bonded to the ortho position of the benzoylamino group of the dipyrrhene-1,9 position through an alkylene group as shown by the general formula (I) Is a novel and distinctive structure. The presence of an alkylene group at the ortho position of the benzoylamino group at the dipyrin 1,9 position makes the phenyl ring in the specific metal complex compound largely distort the planarity of the pyromethene skeleton. As a result, it has been found that when a specific metal complex compound has weak aggregation force as a molecule, solubility in a solvent is improved, and a coloring composition containing a specific metal complex compound is used to form a color pattern, Residues are difficult to leave. In addition, the content of the compound having a pyromethene skeleton whose planarity is disrupted as in the case of a specific metal complex compound in the coloring composition suppresses agglomeration with other contained components in the coloring composition. Accordingly, it is considered that the improvement in the surface unevenness (generation of granular material) after the formation of the colored layer by using the coloring composition is thought to result in an improvement.

The coloring composition of the present invention is further preferably a photosensitive coloring composition containing a polymerizable compound and a photopolymerization initiator.

Further, the coloring composition of the present invention preferably further contains a binder such as an alkali-soluble resin and / or an organic solvent, and may contain various additives as required.

A compound represented by the general formula (I) or a tautomer thereof

Hereinafter, the compound represented by the general formula (I) or the tautomer thereof (specific metal complex compound) will be described in detail. Certain metal complex compounds are novel compounds.

Examples of the monovalent substituent represented by R ¹ to R ⁸ in the general formula (I) include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group Is a straight chain, branched chain or cyclic alkyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Cyclohexyl group, 1-norbornyl group, 1-adamantyl group, and the like can be given in the form of a cyclic group, a cyclic alkyl group, a cyclohexyl group, a cyclopentyl group, An alkenyl group (preferably having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, such as a vinyl group, an allyl group and a 3-buten-1-yl group) , An aryl group (preferably an aryl group having 6 to 48 carbon atoms, more preferably a carbon number 6 to 24, such as phenyl, naphthyl, etc.) (Preferably having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, a 2- A 1-pyridyl group, a 2-benzothiazolyl group, a 1-imidazolyl group, a 1-pyrazolyl group, a benzotriazol-1-yl group, etc.), a silyl group Preferably 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, and examples thereof include a trimethylsilyl group, a triethylsilyl group, a tributylsilyl group, a t-butyldimethylsilyl group, A nitro group, an alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably a carbon number of 1 to 24, such as a methoxy group, an ethoxy group, a 1-butoxy group Butoxy group, isopropoxy group, t-butoxy, dodecyloxy group, cycloalkyloxy group (for example, cyclopentyloxy group, cyclo (Preferably 6 to 48 carbon atoms, more preferably an aryloxy group having 6 to 24 carbon atoms, such as a phenoxy group, a 1-naphthoxy group and the like), an aryloxy group (Preferably 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as a 1-phenyltetrazole-5-oxy group, a 2- (Preferably a silyloxy group having 1 to 32 carbon atoms, more preferably a C1 to C18 silyl group, such as a trimethylsilyloxy group, a t-butyl Dimethylsilyloxy group, diphenylmethylsilyloxy group and the like), an acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, and more preferably a 2 to 24 carbon atoms, for example, A pivaloyloxy group, a benzoyloxy group, a dodecanoyloxy group, etc.), an alkoxy carbon (Preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably a carbon number 2 to 24, such as an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, a cycloalkyloxy An alkoxyalkyloxy group (preferably an alkoxyalkyl group having 2 to 48 carbon atoms, more preferably a C2 to 24 carbon alkoxyalkyl group such as a cyclohexyloxycarbonyloxy group) (For example, cyclohexyloxyethoxy group, etc.), and the like, for example, a methoxyethoxy group, an ethoxyethoxy group, a butoxy-1-methylethoxy group, a cycloalkoxyalkyloxy group Lt; / RTI &gt;

An aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably a carbon number 7 to 24, such as phenoxycarbonyloxy group, etc.) (Preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N- Phenylcarbamoyloxy group and N-ethyl-N-phenylcarbamoyloxy group), a sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, (For example, N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy and the like), an alkylsulfonyloxy group (preferably having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms Sulfonyloxy group, for example, a methylsulfonyloxy group, hexadecylsulfonyl An arylsulfonyloxy group (preferably an arylsulfonyloxy group having from 6 to 32 carbon atoms, and more preferably from 6 to 24 carbon atoms, for example, phenylsulfonyloxy group such as phenylsulfonyloxy group, And the like), an acyl group (preferably an acyl group having 1 to 48 carbon atoms, and more preferably a 1 to 24 carbon atoms, such as a formyl group, an acetyl group, a pivaloyl group, A decanoyl group, a cyclohexanoyl group, etc.), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 48 carbon atoms, more preferably a carbon number 2 to 24, such as methoxycarbonyl group, ethoxycarbonyl group, Butyloxycarbonyl group, an aryloxycarbonyl group (preferably having a carbon number of 7 or less), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having a carbon number of 7 ~ 3 (Preferably an aryloxycarbonyl group having 2 to 7 carbon atoms, more preferably an aryloxycarbonyl group having 7 to 24 carbon atoms, such as a phenoxycarbonyl group), a carbamoyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms For example, a carbamoyl group, an N, N-diethylcarbamoyl group, an N-ethyl-N-octylcarbamoyl group, an N, N-dibutylcarbamoyl group, An N-phenylcarbamoyl group, an N-methyl N-phenylcarbamoyl group and an N, N-dicyclohexylcarbamoyl group), an amino group (preferably having a carbon number of 32 More preferably an amino group having not more than 24 carbon atoms such as an amino group, a methylamino group, an N, N-dibutylamino group, a tetradecylamino group, a 2-ethylhexylamino group, a cyclohexylamino group, An anilino group (preferably having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms An anilino group, for example, an anilino group, an N-methylanilino group, etc.),

A heterocyclic amino group (preferably a heterocyclic amino group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, a 4-pyridylamino group, etc.), a carboxyamide group And more preferably 2 to 24 carbon atoms, and examples thereof include an acetamide group, a benzamide group, a tetradecanamide group, a pivaloylamide group, and a cyclohexanamide group); (Preferably an ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as ureido group, N, N-dimethyl ureido group, N-phenylureido group, etc.) (Preferably an imide group having not more than 36 carbon atoms, more preferably not more than 24 carbon atoms, such as an N-succinimide group and an N-phthalimide group), an alkoxycarbonyl An amino group (preferably having 2 to 48 carbon atoms, More preferably an alkoxycarbonylamino group having 2 to 24 carbon atoms, and examples thereof include a methoxycarbonylamino group, an ethoxycarbonylamino group, a t-butoxycarbonylamino group, an octadecyloxycarbonylamino group, a cyclohexyloxycarbonylamino group, An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having a carbon number of 7 to 32, more preferably a carbon number of 7 to 24, such as a phenoxycarbonylamino group Etc.), a sulfonamide group (preferably a sulfonamido group having 1 to 48 carbon atoms, more preferably a carbon number 1 to 24, such as methanesulfonamide group, butanesulfonamide group, benzenesulfonamide A sulfamoylamino group (preferably having 1 to 48 carbon atoms, more preferably a sulfamoylamino group having 1 to 24 carbon atoms), a sulfamoylamino group (preferably a sulfamoylamino group having 1 to 24 carbon atoms, (For example, an N, N-dipropylsulfamoylamino group, an N-ethyl-N-dodecylsulfamoylamino group and the like), an azo group (preferably having 1 to 32 carbon atoms, (For example, phenyl azo group, 3-pyrazolyl azo group and the like), an alkylthio group (preferably having 1 to 48 carbon atoms, more preferably an alkylthio group having 1 to 24 carbon atoms, (For example, methylthio group, ethylthio group, octylthio group and cyclohexylthio group), an arylthio group (preferably having 6 to 48 carbon atoms, more preferably aryl having 6 to 24 carbon atoms (Preferably 1 to 32 carbon atoms, more preferably a heterocyclic thio group having 1 to 18 carbon atoms, such as, for example, phenylthio group and the like), a heterocyclic thio group 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetazolylthio group, etc.), Kill sulfinyl group (preferably having a carbon number of 1 to 32 may be mentioned, more preferably, an alkyl sulfinyl group having a carbon number of 1 to 24, such as for example, dodecane sulfinyl group),

(Preferably an arylsulfinyl group having 6 to 32 carbon atoms, more preferably an arylsulfinyl group having 6 to 24 carbon atoms, such as phenylsulfinyl group, and the like), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 20 carbon atoms, Preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, an isopropylsulfonyl group, a 2-ethylhexylsulfonyl group, An arylsulfonyl group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, more preferably a carbon number of 6 to 24, for example, phenylsulfo group (e.g., phenylsulfoyl group), an arylsulfonyl group Naphthylsulfonyl group and the like), a carbamoylsulfonyl group, a sulfamoyl group (preferably a sulfamoyl group having not more than 32 carbon atoms, more preferably not more than 24 carbon atoms, such as sulfa An imino group, a N, N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group and the like), sulfo group and phosphonyl group (preferably, Preferably 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as a phenoxyphosphonyl group, an octyloxyphosphonyl group, and a phenylphosphonyl group), and a phosphinoylamino group Is a phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, and examples thereof include a diethoxyphosphinoylamino group, a dioctyloxyphosphinoylamino group, etc.) and the like .

In the general formula (I), R ^1, when the monovalent substituent represented by ~R ^8, date possible further substituted, the monovalent substituent represented by R ¹ ~R ⁸ art, the substituents described in the R ¹ ~R ⁸ . When the monovalent substituent represented by R ¹ to R ⁸ has two or more monovalent substituents, the two or more monovalent substituents may be the same or different.

In formula (I), R ¹ and R ² may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring or unsaturated ring, and R ³ and R ⁴ may be bonded to each other To form a 5-membered, 6-membered or 7-membered ring or unsaturated ring.

Examples of the 5-membered, 6-membered or 7-membered ring or unsaturated ring formed by R ¹ and R ² or R ³ and R ⁴ include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring , Imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexane ring, benzene ring, pyridine ring, pyrazine ring and pyridazin ring, Is a benzene ring or a pyridine ring.

A 5-membered, 6-membered or 7-membered ring formed by R ¹ and R ² in the general formula (I) and / or a 5-membered, 6-membered or 7-membered ring formed by R ³ and R ⁴ , A further substitutable group may further have a monovalent substituent described in R ¹ to R ⁸ , and when the 5-membered, 6-membered, or 7-membered ring has two or more monovalent substituents, Two or more monovalent substituents may be the same or different.

In the general formula (I), among R ¹ and R ⁴ , among the above-mentioned monovalent substituents, an alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, cyano group, An aryloxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, a cyano group, an imide group or a carbamoylsulfonyl group is more preferable, and an alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, A cyano group, an imide group, or a carbamoylsulfonyl group is more preferable, and an alkoxycarbonyl group, an aryloxycarbonyl group, or a carbamoyl group is particularly preferable.

In the general formula (I), among R &lt; ² &gt; and R &lt; ³ &gt;, among the above monovalent substituents, an alkyl group, an aryl group or a heterocyclic group is preferable, and an alkyl group or an aryl group is more preferable.

Each of the groups represented by the above preferred embodiments may be unsubstituted or may have a substituent described.

In the general formula (I), when R ² and R ³ represent an alkyl group, the alkyl group is preferably a straight chain, branched chain or cyclic alkyl group having 1 to 12 carbon atoms, and more specifically, , A methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, a t-butyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, have. More preferably, the alkyl group is a branched chain or a cyclic alkyl group having 1 to 12 carbon atoms, and more specifically, for example, an isopropyl group, a cyclopropyl group, an i-butyl group, A cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. More preferably, the alkyl group is a secondary alkyl group having 1 to 12 carbon atoms or a tertiary alkyl group, and more specifically, for example, an isopropyl group, a cyclopropyl group, an i-butyl group, a t -Butyl group, cyclobutyl group, and cyclohexyl group.

The alkyl group represented by the above preferred embodiment may be unsubstituted or may have a substituent described above.

In the general formula (I), when R ² and R ³ represent an aryl group, the aryl group is preferably a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, Is a substituted or unsubstituted phenyl group.

In the general formula (I), when R ² and R ³ represent an aryl group, the aryl group is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.

Each of the aryl groups shown in the above preferred embodiments may be unsubstituted or may have a substituent described.

When R ² and R ³ represent a heterocyclic group, the heterocyclic group is preferably a 2-thienyl group, a 4-pyridyl group, a 3-pyridyl group, a 2-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group and benzotriazol-1-yl group, more preferably 2-thienyl group, 4-pyridyl group, 2 A furyl group, a 2-pyrimidinyl group, and a 1-pyridyl group.

Each of the above-mentioned heterocyclic groups may be unsubstituted or may have a substituent described above.

In the general formula (I), examples of R ⁵ and R ⁶ include an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, , An amino group, an anilino group, a sulfonamide group, an alkylthio group, an arylthio group or a sulfamoyl group is preferable, and an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, Or an arylthio group is more preferable, and an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group is particularly preferable.

It is preferable that R ⁵ and R ⁶ are the same substituent from the viewpoint of the production cost and the production suitability. From the viewpoint of improving the solubility in an organic solvent, it is preferable that R ⁵ and R ⁶ are different substituents.

Examples of R ⁷ and R ⁸ in the general formula (I) include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, An alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, or an amino group is more preferable, and an alkyl group, an alkoxy group, an alkoxy group, Group, or an amino group is particularly preferable.

In the general formula (I), R ⁹ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group.

The halogen atom, the alkyl group, the aryl group and the heterocyclic group represented by R ⁹ each have the same meaning as the halogen atom, the alkyl group, the aryl group and the heterocyclic group described in the monovalent substituent group represented by R ¹ to R ⁸ , The preferred ranges are also the same.

In the general formula (I), when the alkyl group, aryl group or heterocyclic group represented by R ⁹ is a further substitutable group, it may be substituted with a substituent described as a monovalent substituent represented by R ¹ to R ⁸ . When the alkyl group, aryl group or heterocyclic group represented by R ⁹ is further substituted by two or more substituents, the two or more substituents may be the same or different.

The halogen atom, the alkyl group, the aryl group and the heterocyclic group represented by R ¹⁰ or R ¹¹ in the general formula (I) are the same as the halogen atom, the alkyl group, the aryl group, and the halogen atom described in the monovalent substituent group represented by R ¹ to R ⁸ , And the heterocyclic group, respectively, and their preferable ranges are the same.

In the formula (I), R ¹⁰ and R ¹¹ as, n1 and n2 the case 1, preferably a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, and a hydrogen atom or an alkyl group, especially preferred, and most preferably a hydrogen atom Do. On the other hand, when more than n1 and n2 is an integer 2, as the R ¹⁰ and R ^11, is preferably a hydrogen atom.

Ma in the general formula (I) represents a metal or a metal compound.

Ma may be any metal atom or metal compound capable of forming a complex, and examples thereof include divalent metal atoms, divalent metal oxides, divalent metal hydroxides, and divalent metal chlorides.

Examples of the metal represented by Ma include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe and B.

As the metal compound represented by Ma, AlCl, InCl, FeCl, TiCl _2, SnCl _2, SiCl _2, and GeCl _2, such as a metal chloride, metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ .

Among these, from the viewpoints of stability of the complex, spectroscopic characteristics, heat resistance, light resistance, and suitability for production, it is preferable to use Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, More preferably Fe, Zn, Cu, Co, or VO (V = O), more preferably Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, . Of these, Ma is preferably Zn.

X in the general formula (1) is a group capable of bonding with Ma, and neutralizes the charge of Ma. Examples of X include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom), a hydroxyl group, an aliphatic imide (e.g., succinic acid imide, maleimide, glutarimide, diacetamide, etc.) Aromatic imide group or heterocyclic imide (for example, phthalimide, naphthalimide, 4-bromobenzene, and the like) derived from a monovalent group, preferably a succinic acid imide or maleimide, 4-methylphthalimide, 4-nitrophthalimide, naphthalene carboxyimide, tetrabromophthalimide, and the like, preferably phthalimide, 4-bromophthalimide, 2-methoxybenzoic acid, 4-methoxybenzoic acid, 4-chlorobenzoic acid, 2-methoxybenzoic acid, 2-methoxybenzoic acid, -Naphthoic acid, salicylic acid, 3,4,5-trimethoxybenzoic acid, 4-heptyloxybenzoic acid, 4-t-butyl Benzoic acid, and the like, preferably monovalent groups derived from benzoic acid, 4-methoxybenzoic acid, salicylic acid, etc.), aliphatic carboxylic acids (e.g., formic acid, acetic acid, acrylic acid, methacrylic acid, Propionic acid, propionic 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-hexyldecanoic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, 5-norbornene-2-carboxylic acid, 1-adamantanecarboxylic acid and the like can be mentioned, and acetic acid, methacrylic acid, lactic acid (For example, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, trifluoromethanesulfonic acid, and the like) derived from a monovalent group derived from a monovalent organic group Methanesulfonic acid, trifluoroacetic acid, trifluoroacetic acid, Methanesulfonic acid and the like), a monovalent group derived from a dithiocarbamic acid (for example, dimethyldithiocarbamic acid, diethyldithiocarbamic acid and dibenzyldithiocarbamic acid) A monovalent group, a monovalent group, a sulfonic acid group, a monovalent group, a sulfonic acid group, a sulfonic acid group, a sulfonic acid group, a sulfonic acid group, (Preferably, benzene sulfonamide, methanesulfonamide), a hydroxamic acid (e.g., acetohydroxamic acid, octanohydroxamic acid, benzoic hydroxamic acid, etc.) ) And a nitrogen-containing heterocyclic compound (such as hydantoin, 1-benzyl-5-ethoxyhydantoin, 1-allyl hydantoin, 5,5-diphenylhydantoin, - oxazolidinedione, barbituric acid, imidazole, pyrazole, 4,5-dicyanoimidazole, 4,5-dimethylimidazole, benzimide Di-1-benzyl-5-ethoxyhydantoin, 5,5-dimethyl-2,4-oxazolidinedione, Dicyclohexylcarbodiimide, 4,5-dicyanoimidazole, and 1H-imidazole-4,5-dicarboxylate).

Among the above groups, X is preferably a monovalent group derived from a halogen atom, an aliphatic carboxylic acid, a monovalent group derived from an aromatic carboxylic acid, a monovalent group derived from an aliphatic imide, a monovalent group derived from an aromatic imide, A monovalent group derived from an aliphatic sulfonic acid or a monovalent group derived from a zwitterionic ring compound is preferable and a monovalent group derived from a hydroxyl group, a monovalent group derived from an aliphatic carboxylic acid, a monovalent group derived from an aromatic imide, desirable.

n1 and n2 each independently represent an integer of 1 to 8; Among them, n1 and n2 are preferably an integer of 1 to 4, particularly preferably 1 or 2.

N1 and n2 are preferably the same from the viewpoint of the manufacturing cost and the production suitability.

From the viewpoint of solubility in an organic solvent, n1 and n2 are preferably different from each other.

The compound represented by the general formula (I) may be a tautomer. The tautomer according to the present invention may be any compound having a structure capable of forming by the movement of one hydrogen atom in the molecule. For example, the tautomer may be any of the following structures (a) to (f) .

The molar extinction coefficient of the specific metal complex compound is preferably as high as possible from the viewpoint of thinning the coloring film formed by the coloring composition containing the compound.

Further, the maximum absorption wavelength? Max of the specific metal complex compound is preferably 530 nm to 590 nm, more preferably 540 nm to 580 nm, from the viewpoint of color purity improvement.

The maximum absorption wavelength and the molar extinction coefficient are those measured by a spectrophotometer UV-1800PC (Shimadzu Corporation).

Exemplary compounds of specific metal complex compounds are shown below, but the present invention is not limited thereto.

Exemplary compounds (P-1) to (P-45) are shown below.

Examples of the compounds (P-1) to (P-45) are those wherein R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and X ¹⁰¹ and M ¹ in the compound represented by the following formula (A) / RTI &gt;

Exemplary compounds (P-46) to (P-50) are shown below.

Specific metal complex compounds are disclosed in, for example, U.S. Patent No. 4,774,339, U.S. Patent No. 5,433,896, JP-A-2001-240761, JP-A-2002-155052, JP-A-2008-0076044, Japanese Patent No. 3614586, Aust. J. Chem., 1965, 11, 1835-1845, J.H. Boger et al., Heteroatom Chemistry, Vol. 1, No. 5, 389 (1990), and the like.

The coloring composition of the present invention may contain one kind of the specific metal complex compound or two or more kinds thereof.

The content of the specific metal complex compound in the coloring composition of the present invention varies depending on the molecular weight and the extinction coefficient of the specific metal complex compound, but is preferably from 0.1 to 70 mass%, more preferably from 1 to 50 mass% % By mass is more preferable. When the content of the specific metal complex compound in the coloring composition of the present invention is 0.1% by mass or more, a better color density (for example, a color density suitable for liquid crystal display) is obtained. When the content is 70% by mass or less, It is advantageous in that the patterning of the pixel becomes better in the case of using it in the production of a color filter.

In the coloring composition of the present invention, a dye and / or pigment having other structure than the specific metal complex compound may be used in combination with the specific metal complex compound within a range that does not impair the effect of the present invention.

A dye having another structure different from the specific metal complex compound

In the coloring composition of the present invention, a dye having another structure different from the specific metal complex compound may be used. The dyes having other structures are not particularly limited, and known dyes can be used. For example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, JP-A-2592207, U.S. Patent No. 4,808,501, U.S. Patent No. 5,667,920, U.S. Patent No. 5,059,500, U.S. Patent No. 5,333,207, U.S. Patent No. 6,351,303, and U.S. Patent No. 6-51115 Japanese Patent Application Laid-Open No. 6-194828, Japanese Patent Application Laid-Open Nos. 8-211599, 4-249549, 10-123316, 11-302283 Japanese Patent Application Laid-Open Nos. 7-286107, 2001-4823, 8-15522, 8-29771, 8-146215, Japanese Patent Application Laid-Open No. 11-343437, Japanese Patent Application Laid-Open No. 8-62416, Japanese Patent Application Laid-Open No. 2002-14220, Japanese Patent Application Laid-Open No. 2002-14221, 222, 2002-14223, 8-302224, 8-73758, 8-179120, 8-151531 And Japanese Patent Application Laid-Open No. 6-230210.

Examples of the dyes having other structures include pyrazole azo compounds, anilino azo compounds, triphenylmethane compounds, anthraquinone compounds, anthrapyridone compounds, benzylidene compounds, oxolin compounds, pyrazolotriazole compounds, pyridazo compounds, Dyes having a chemical structure such as thiazine, pyrrolopyrazolamomethine, xanthene, squarylium, phthalocyanine, benzopyran, indigo, and the like. Among them, anthraquinone, azanthene and squarylium dyes are preferable in terms of hue and anthraquinone dyes are particularly preferable.

The coloring composition of the present invention may contain one kind of dye having another structure or two or more kinds of dyes.

The total content of the specific metal complex compound and the dye having another structure in the coloring composition of the present invention is preferably from 0.1% by mass to 70% by mass, more preferably from 1% by mass to 50% by mass relative to the total solid content of the coloring composition, Is more preferable. When the total content of the dyes is 0.1 mass% or more, a better color density (for example, a color density suitable for liquid crystal display) is obtained. When the total content of the dyes is 70 mass% or less, Which is advantageous in that the patterning of the mask pattern is improved.

Anthraquinone compound

An anthraquinone compound (anthraquinone dye) which is suitable as a dye having another structure will be described.

The coloring composition of the present invention may contain an anthraquinone compound.

By containing the anthraquinone compound, the contrast of the color filter obtained using the coloring composition of the present invention can be effectively increased.

One of the favorable aspects of the coloring composition of the present invention is that the pigment and the anthraquinone compound described later are used together with the specific metal complex compound. By using the coloring composition of the present invention, a color filter excellent in color and contrast and excellent in fastness can be produced.

The anthraquinone compound in the present invention is a compound having an absorption maximum at 400 nm to 700 nm, and in the present invention preferably has an absorption maximum at 500 nm to 700 nm, particularly preferably 550 nm to 700 Is an anthraquinone compound having an absorption maximum in nm. An anthraquinone compound having such an absorption maximum is not particularly limited in structure. When the coloring composition of the present invention containing such anthraquinone compound is applied to a color filter, the effect of improving the contrast is excellent.

Among the anthraquinone compounds in the present invention, the diamino anthraquinone compound represented by the following general formula (II) is preferable.

Among the compounds represented by the general formula (II), from the viewpoint of the absorption characteristics, the compound represented by the following general formula (III) is more preferable and the compound represented by the following general formula (IV) (V) or the following general formula (VI) is particularly preferable from the viewpoint of compatibility between the absorption property and the thermal stability.

First, the compound represented by the following general formula (II) will be described.

In formula (II), R ^11a and R ^12a each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. However, R ^11a and R ^12a do not represent a hydrogen atom at the same time.

The alkyl group represented by R ^11a or 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, such as methyl group, ethyl group, iso- Propyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group and cyclohexyl group.

The aryl group represented by R ^11a or R ^12a is preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as phenyl group, o- Methylphenyl group, p-methylphenyl group, 2,6-dimethylphenyl group, 2,6-diethylphenylbiphenyl group, 2,6-dibromophenyl group, naphthyl group, anthranyl group and phenanthryl group.

The heterocyclic group represented by R ^11a or R ^12a is preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom and a sulfur atom . Examples of the heterocyclic group include an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a thienyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a naphthothiazolyl group, A carbazolyl group, an azepinyl group, and the like.

The alkyl group, aryl group or heterocyclic group represented by R ^11a or R ^12a may further have a substituent. Examples of the substituent include an alkyl group (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, such as a methyl group, an ethyl group, , an alkenyl group (preferably having a carbon number of from 2 to 30, more preferably from 2 to 30, more preferably from 1 to 30, and still more preferably from 1 to 30), an alkoxy group , More preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms, such as a vinyl group, an allyl group, a 2-butenyl group and a 3-pentenyl group), an alkynyl group (Preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as propargyl group and 3-pentynyl group), aryl Group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably That include an aryl group of 6 to 12 decimal, for example, phenyl, p- methylphenyl group, a biphenyl group, a naphthyl group, anthranyl group, phenanthryl group and the like),

An amino group (preferably an amino group having from 0 to 30 carbon atoms, more preferably from 0 to 20 carbon atoms, particularly preferably from 0 to 10 carbon atoms, and includes an alkylamino group, an arylamino group or a heterocyclic amino group, An alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 20 carbon atoms), an amino group Is an alkoxy group having 1 to 10 carbon atoms such as methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc.), an aryloxy group (preferably having 6 to 30 carbon atoms, Preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenyloxy group, a 1-naphthyloxy group and a 2-naphthyloxy group), an aromatic hetero Hwang Oxy (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, such as a pyridyloxy group, a pyrazinoxy group, A quinolyloxy group, etc.),

An 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, such as an acetyl group, a benzoyl group, a formyl group, , An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group Etc.), 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, for example, phenyloxycarbonyl Etc.), an acyloxy group (preferably an acyloxy group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as an acetoxy group, Benzoyloxy group etc. And an acylamino group (preferably an acylamino group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms, for example, acetylamino group, benzoylamino group, etc.) , An alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 12 carbon atoms, such as a methoxycarbonylamino group and the like) , &Lt; / RTI &gt;

An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino group, etc.) A 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, A sulfonyl group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably a sulfamoyl group having 0 to 12 carbon atoms, for example, sulfamoyl group, A methylsulfamoyl group, a dimethylsulfamoyl group, a phenylsulfamoyl group and the like).

A 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, such as a carbamoyl group, a methylcarbamoyl group, a diethyl (Preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms), an alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms, (Preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably arylthio having 6 to 12 carbon atoms), an arylthio group And examples thereof include phenylthio and the like),

An aromatic heterocyclic thio group (preferably an aromatic heterocyclic thio group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as pyridylthio group, Imidazolylthio group, 2-benzoxazolylthio group and 2-benzthiazolylthio group), a sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably A sulfinyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably a sulfonyl group having 1 to 12 carbon atoms, for example, a mesyl group or a tosyl group) (Preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably a sulfinyl group having 1 to 12 carbon atoms, for example, methanesulfinyl group, benzenesulfinyl group and the like) Is a ureido group having 1 to 12 carbon atoms, for example, taurine (Preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, is a phosphoric acid amide group, , For example, diethylphosphoric acid amide group, phenylphosphoric acid amide group and the like)

A halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group , A heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom and a sulfur atom. A thienyl group, a piperidyl group, a morpholino group, a benzoxazolyl group, a benzimidazolyl group, a benzthiazolyl group, a carbazolyl group, an azinyl group, etc. And a silyl group (preferably a silyl group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms, such as trimethylsilyl group, triphenyl Silyl group and the like) It can be given. These substituents may be further substituted.

In the formula (Ⅱ), n11 is an integer from 1 to 4, and when n11 is an integer from 2 to 4, a plurality of NR ^11a R ^12a may be the same or different and is.

Next, the compound represented by the general formula (III) will be described.

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

The alkyl group represented by R ^21a or 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, such as methyl group, ethyl group, iso- Propyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group and cyclohexyl group.

The aryl group represented by R ^21a or R ^22a is preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Examples of the aryl group include a phenyl group, an o- Methylphenyl group, p-methylphenyl group, 2,6-dimethylphenyl group, 2,6-diethylphenylbiphenyl group, 2,6-dibromophenyl group, naphthyl group, anthranyl group and phenanthryl group.

The alkyl group or aryl group represented by R ^21a or R ^22a may further have a substituent. Examples of such substituents include those described as substituents for the alkyl group, aryl group or heterocyclic group represented by R ^11a or R ^12a in the general formula (II). Among them, examples of the substituent are preferably an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, a sulfonylamino group, , A sulfonyl group, an ureido group, a hydroxy group, a halogen atom, a sulfo group, a carboxyl group and the like. Details and preferred embodiments thereof are the same as those described above.

Next, the compound represented by the general formula (IV) will be explained.

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

The alkyl group represented by R ^31a , R ^32a , R ^33a , or R ^34a is preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, particularly preferably 1 to 2 carbon atoms, , Methyl group, ethyl group, isopropyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group and cyclohexyl group.

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

In the general formula (IV), R ^35a and R ^36a each independently represent an alkyl group, an alkoxy group, an aryloxy group, a sulfo group or a salt thereof, an aminosulfonyl group, an alkoxysulfonyl group or a phenoxysulfonyl group.

The alkyl group represented by R ^35a or R ^36a is the same as the alkyl group represented by R ^31a , R ^32a , R ^33a , or R ^34a , and preferred embodiments thereof are also the same.

The alkoxy group represented by R ^35a or 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, such as methoxy, Ethoxy, butoxy, 2-ethylhexyloxy and the like.

The aryloxy group represented by R ^35a or 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, 1-naphthyloxy group, 2-naphthyloxy group, and the like.

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

The aminosulfonyl group represented by R ^35a or R ^36a is preferably an aminosulfonyl group having 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 15 carbon atoms, and specific examples include ethylamino A sulfonyl group, a sulfonyl group, a propylaminosulfonyl group, an isopropylaminosulfonyl group, a butylaminosulfonyl group, an isobutylaminosulfonyl group, a sec-butylaminosulfonyl group, a pentylaminosulfonyl group, an isopentylaminosulfonyl group, a hexylaminosulfonyl group, An aminosulfonyl group, a 2-ethylhexylaminosulfonyl group, a decylaminosulfonyl group, a dodecylaminosulfonyl group, and a phenylaminosulfonyl group. Specific examples of the aminosulfonyl group represented by R ^35a or R ^36a include a dimethylaminosulfonyl group, a diethylaminosulfonyl group, a dipropylaminosulfonyl group, a diisopropylaminosulfonyl group, a dibutylaminosulfonyl group, di-sec-butyl A dialkylaminosulfonyl group such as an aminosulfonyl group, a di-sec-aminosulfonyl group, a dihexylaminosulfonyl group, a methylethylaminosulfonyl group, a methylbutylaminosulfonyl group, an ethylbutylaminosulfonyl group and a phenylmethylaminosulfonyl group . Of these, a dialkylaminosulfonyl group having 4 to 15 carbon atoms in the alkyl moiety is particularly preferable.

The alkoxysulfonyl group represented by R ^35a or R ^36a is preferably an alkoxysulfonyl group having 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 carbon atoms. Specific examples thereof include a butylsulfonyl group, a hexanesulfonyl group, a decylsulfonyl group, and a dodecylsulfonyl group.

The phenoxyprotophenyl group represented by R ^35a or R ^36a is preferably a phenoxy group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 15 carbon atoms. As a specific example, A tolyl sulfonyl group, and the like.

R ^35a and R ^36a may further have a substituent, and examples of the substituent include the examples described as the substituent of the alkyl group, aryl group or heterocyclic group represented by R ^11a or R ^12a in formula (II) have.

In the formula (Ⅳ), n31 and n32 each independently represents an integer of 0 to 2, when n31 and n32 is 2, a plurality of R ^35a and R ^36a may be the same or different, respectively.

Among the diamino anthraquinone compounds described above, compounds selected from compounds represented by the following general formula (V) or the following general formula (VI) are preferable.

The compound represented by the general formula (V)

In the general formula (V), R ^41a , R ^42a , R ^43a and R ^44a each independently represents an alkyl group or a halogen atom, and the alkyl group and the halogen atom are the same as R ^31a , R &^lt; ^32a &gt;, R &^lt; ^33a &gt;, or R &lt; ^34a &gt;, respectively, and preferred embodiments are also the same.

R ^45a , R ^46a , R ^47a and R ^48a in the general formula (V) each independently represent an alkyl group, a sulfo group or a salt thereof, or an aminosulfonyl group. Either one of R ^45a and R ^47a and either R ^46a or R ^48a represents a sulfo group or a salt thereof or an aminosulfonyl group. The alkyl group, the sulfo group or the salt thereof, and the aminosulfonyl group represented by R ^45a , R ^46a , R ^47a or R ^48a are an alkyl group, a sulfo group or a salt thereof represented by R ^35a or R ^36a in the general formula (IV) , And an aminosulfonyl group, respectively, and preferred embodiments are also the same.

The compound represented by the general formula (VI)

In the general formula (VI), R ^51a , R ^52a , R ^53a and R ^54a each independently represents an alkyl group or a halogen atom, and the alkyl group and the halogen atom are the same as R ^31a , R &^lt; ^32a &gt;, R &^lt; ^33a &gt;, or R &lt; ^34a &gt;, respectively, and preferred embodiments are also the same.

In the general formula (VI), R ^55a and R ^56a each independently represents a hydrogen atom or an alkyl group, and the alkyl group is an alkyl group of R ^31a , R ^32a , R ^33a or R ^34a in the general formula (IV) Alkyl group, and the preferred embodiment is also the same.

Each of R ^57a and R ^58a independently represents 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, Methyl group.

In formula (VI), L ^51a and L ^52a each independently represents a divalent linking group, and includes an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, -O-, -S-, -NR -, -SO ₂ -, -CO-, or a divalent linking group formed by combining a plurality of these groups. More preferably, L ^51a and L ^52a are an alkylene group having 1 to 10 carbon atoms, a phenylene group having 6 to 12 carbon atoms, a sulfonylamino group, or a divalent linking group formed by combining a plurality of these groups, An alkylene group having 1 to 10 carbon atoms, a sulfonylamino group, or a bivalent linking group formed by combining a plurality of these groups.

In the general formula (VI), an alkylene group having 1 to 10 carbon atoms represented by L ^51a or L ^52a , or a divalent linking group formed by combining this with -O-, etc. may be unsubstituted or may have a substituent, A propylene aminosulfonyl group, a butylene aminosulfonyl group, a pentylene aminosulfonyl group, a 1-methylethylenesulfonyl group and the like may be used as the alkylene group, . Among them, an alkylenaminosulfonyl group having 2 to 10 carbon atoms (e.g., an ethyleneaminosulfonyl group, a propylene aminosulfonyl group, a butyleneaminosulfonyl group, a pentyleneaminosulfonyl group) is preferable.

In the general formula (VI), an arylene group having 6 to 20 carbon atoms represented by L ^51a or L ^52a or a divalent linking group formed by combining this with -O- may be unsubstituted or may have a substituent, Include a phenylene group, a biphenylene group, and a phenyleneaminosulfonyl group. Among them, an arylene aminosulfonyl group having 6 to 12 carbon atoms (e.g., phenyleneaminosulfonyl group and the like) is preferable.

In the formula (VI), R in -NR- represented by L ^51a or L ^52a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isobutyl group, a butyl group, an isobutyl group, a sec-butyl group and a 2-ethylhexyl group.

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

Among the above, preferred anthraquinone compounds in the present invention are compounds selected from the compounds represented by the general formula (V) or the general formula (VI). As the compound represented by the general formula (V) or the general formula (VI), the following cases are particularly preferable.

In the general formula (V), 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 each independently represent a C 2-15 , And R ^47a and R ^48a are preferably methyl groups.

In the general formula (VI), 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 each independently represent a hydrogen atom Or a methyl group, R ^57a and R ^58a are each independently a hydrogen atom or a methyl group, L ^51a and L ^52a each independently represent an alkylene aminosulfonyl group having 1 to 10 carbon atoms, an aralkylene group having 7 to 12 carbon atoms An aminosulfonyl group or an alkyleneoxy group having 2 to 10 carbon atoms, and L ^53a and L ^54a are preferably oxygen atoms.

Specific examples of the anthraquinone compound in the present invention are shown below. However, the present invention is not limited thereto.

The coloring composition of the present invention may contain an anthraquinone compound singly or two or more.

When the coloring composition of the present invention contains an anthraquinone compound, the ratio of the anthraquinone compound to the total amount of the total dye compound containing the specific metal complex compound is preferably 50 mass% or less, more preferably 2 mass% By mass to 100% by mass, and more preferably 10% by mass to 50% by mass. When the proportion of the anthraquinone compound is 50% by mass or less based on the total amount of the total dye compound, when the coloring composition is used for the production of a color filter, the color of the colored image is good while the fastness is maintained, .

[Pigment]

In the coloring composition of the present invention, the above-described dye and pigment may be used in combination.

As the pigment, a pigment having an average primary particle diameter of 10 nm or more and 30 nm or less is preferable.

In the above-described aspect, a coloring composition capable of producing a color filter excellent in hue and contrast can be obtained.

As the pigment, conventionally known various inorganic pigments or organic pigments can be used, but from the viewpoint of reliability, it is preferable to use an organic pigment. As the organic pigment in the present invention, for example, the organic pigment described in paragraph 0093 of Japanese Patent Application Laid-Open No. 2009-256572 can be mentioned.

In particular,

C.I. Pigment Red 177, 209, 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, 15: 3, 60,

C. I. Pigment Violet 23

But it is not limited to these in the present invention.

These organic pigments can be used singly or in various combinations in order to increase color purity.

When a pigment is used, the content in the coloring composition of the present invention is preferably 1% by mass to 55% by mass, more preferably 5% by mass to 45% by mass, relative to the total solid content of the composition. When the content of the pigment is within the above range, it is effective in securing excellent color characteristics.

[Pigment dispersant]

The coloring composition of the present invention, when containing a pigment together with a specific metal complex compound, may contain a pigment dispersant.

Examples of the pigment dispersant that can be used in the present invention include polymer dispersants (for example, polyamide amines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, (Meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate), and surfactants such as polyoxyethylene alkylphosphoric ester, polyoxyethylene alkylamine, and alkanolamine, and pigment derivatives.

The polymer dispersant can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer in its structure. It is preferable that all of the end-modified polymer, graft-type polymer, and block-type polymer have an anchor sites (an acid group, a basic group, a partial skeleton of an organic dye, or a heterocycle) on the surface of a pigment.

Examples of the terminal-modified polymer having an anchor site on the surface of the pigment include a polymer having a phosphoric acid group at the terminals described in JP-A-3-112992 and JP-A-2003-533455, A polymer having a sulfonic acid group at the terminal thereof described in JP-A-273191, a polymer having a partial skeleton of an organic dye described in Japanese Patent Application Laid-Open No. 9-77994, etc., and a polymer having a heterocyclic ring. Also, a polymer having two or more anchor sites on the surface of the polymer introduced into the polymer terminal described in Japanese Patent Application Laid-Open No. 2007-277514 is preferable because of its excellent dispersion stability.

Examples of the graft-type polymer having an anchor portion on the surface of the pigment include a polyester-based dispersant and the like, and specific examples thereof include those disclosed in JP-A-54-37082, JP-A-8-507960 , Reaction products of poly (lower alkyleneimine) and polyester described in JP-A-2009-258668 and the like, reaction products of polyallylamine and polyester described in JP-A-9-169821 and the like, A copolymer of a macromonomer and a nitrogen atom monomer described in JP-A-10-339949, JP-A-2004-37986, etc., JP-A-2003-238837, JP-A-2008-9426, A graft polymer having a partial skeleton of an organic dye or a heterocycle described in JP-A No. 81732/1995, etc., a copolymer of a macromonomer and an acid group-containing monomer described in JP-A-2010-106268 Can. Particularly, a positive dispersion resin having a basic group and an acidic group described in Japanese Patent Application Laid-Open No. 2009-203462 is preferable from the viewpoints of the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the coloring composition using the pigment dispersion.

As a macromonomer used for producing a graft polymer having an anchor site on the surface of a pigment by radical polymerization, a known macromonomer can be used, and a macromonomer AA-6 (a macromonomer having a terminal group of methacryl AS-6 (polystyrene having a terminal group of methacryloyl group), AN-6S (copolymer of styrene and acrylonitrile having a terminal group of methacryloyl group), AB-6 (terminal group of polymethyl methacrylate) Butyl acrylate), DECEL available from Gakugei Co., Ltd., Fraxel FM5 (5 mol equivalent of? -Caprolactone in 2-hydroxyethyl methacrylate), FA10L (acrylic acid 2-hydroxy 10 mole equivalent of epsilon -caprolactone of ethyl), and polyester-based macromonomers described in Japanese Patent Application Laid-Open No. 2-272009. Among them, polyester-based macromonomers having particularly good flexibility and good solventability are preferable from the viewpoints of dispersibility of the pigment dispersion, dispersion stability, and developability exhibited by the coloring composition using the pigment dispersion. In addition, Based macromonomer represented by the polyester-based macromonomer described in JP-A No. 272,009, and most preferably a polyester-based macromonomer represented by the polyester-

As block type polymers having anchor sites on the surface of the pigment, block type polymers described in JP-A-2003-49110 and JP-A-2009-52010 are preferable.

DA-7301 "manufactured by Kusunoki Seiki Co., Ltd.," Disperbyk-101 "(polyamide amine phosphate) manufactured by BYK Chemie, 107 (Copolymer of ethylene oxide and propylene oxide), 110 (a copolymer containing an acid group), 130 (polyamide), 161,162,163,164,165,166,170 (polymeric copolymer), BYK-P104, P105 Unsaturated polycarboxylic acid), EFKA4047, 4050 to 4010 to 4165 (polyurethane), EFKA4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyester amide), 5765 (Azobisisobutyronitrile), 6220 (fatty acid polyesters), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative), Ajinomoto Fine Technosaccharide AJI Super PB821, PB822, PB880, PB881, Rolen TG-710 (urethane oligomer) &quot;, &quot; Polyflow No. &quot; 50E, No. 873, 874, # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705 , "DA-725", Kaosha "DEMOR RN, N (naphthalene sulfonic acid formalin polycondensate)", MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "," Homogenol L- "Acetamin 86 (stearylamine acetate)" manufactured by Nippon Lubricants Co., Ltd., "Sol Spurs 5000" (phthalocyanine derivative (trade name) manufactured by Nippon Lubrizol Corporation), "Emulsion 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ), 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 17000, 27000 (polymer having function at the terminal portion), 24000, 28000, 32000, 38500 (graft type polymer), Nikko Chemical Co., (Polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Kawaken Fine Chemicals Co., Ltd., Pinot Noir W001: cationic surfactant ", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene stearyl ether, polyoxyethylene stearyl ether, polyoxyethylene stearyl ether, polyoxyethylene stearyl ether, Nonionic surface active agents such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; "W004, W005, W017 47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 "manufactured by Morishita Sangyo Co., Ltd., anionic surfactants such as" Disperse AID 6, Disperse 8, Disperse A 15, Disperse A 9100 ", Adeka Fluoronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121 and P-123 "manufactured by Sanyo Chemical Industries, Ltd. and" Ionet (trade name) S-20 "manufactured by Sanyo Chemical Industries, Ltd. and the like.

These pigment dispersants may be used alone or in combination of two or more.

In the present invention, it is preferable to use, as a pigment dispersant, a combination of a pigment derivative and a polymer dispersant.

As the pigment dispersant in the present invention, an alkali-soluble resin may be used in combination with an end-modified polymer, graft-type polymer, or block-type polymer having an anchor site on the surface of the pigment. Examples of the alkali-soluble resin include (meth) acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, etc. and acidic cellulose derivatives having a carboxylic acid in the side chain, (Meth) acrylic acid copolymer is particularly preferable. The N-substituted maleimide monomer copolymer disclosed in Japanese Patent Application Laid-Open No. 10-300922, the ether dimer copolymer disclosed in Japanese Patent Application Laid-Open No. 2004-300204, the polymerizable compound described in JP-A No. 7-319161 Is also preferable.

The content of the pigment dispersant in the coloring composition of the present invention is preferably 1 to 80 parts by mass, more preferably 5 to 70 parts by mass, and more preferably 10 to 60 parts by mass relative to 100 parts by mass of the pigment desirable.

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

When the pigment derivative is used in combination, the amount of the pigment derivative to be used is preferably in the range of 1 to 30 parts by mass, more preferably in the range of 3 to 20 parts by mass, and more preferably 5 parts by mass To 15 parts by mass.

[Other Ingredients]

The coloring composition of the present invention may further contain other components described below insofar as the effect of the present invention is not impaired.

[Polymerizable compound]

The coloring composition of the present invention preferably contains at least one kind of polymerizable compound.

As the polymerizable compound, for example, a polymerizable compound having at least one ethylenic unsaturated double bond can be mentioned. The polymerizable compound may be selected from the components contained as a polymerizable compound in a known composition, and examples thereof include the components described in paragraphs [0010] to [0020] of Japanese Patent Application Laid-Open No. 2006-23696, and And the components described in paragraphs [0027] to [0053] of Japanese Patent Application Laid-Open No. 2006-64921.

As the polymerizable compound, an urethane addition polymerizable compound produced by the addition reaction of an isocyanate and a hydroxyl group is also favorable. For example, Japanese Unexamined Patent Application Publication No. 51-37193, Japanese Unexamined Patent Publication No. 2-32293 , Urethane acrylates as disclosed in Japanese Patent Application Laid-Open No. Hei 2-16765, and Japanese Patent Application Laid-Open No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417 And the urethane compounds having an ethylene oxide skeleton described in JP-A-62-39418 are preferred.

Other examples of the polymerizable compound include polyester acrylates such as those described in JP-A-48-64183, JP-A-49-43191, JP-A-52-30490 Polyfunctional acrylates or methacrylates such as epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid. Also, Japan Adhesion Society vol. 20, No. 7, pages 300 to 308 (1984), which are incorporated herein by reference, as photo-curable monomers and oligomers.

Specific examples of the polymerizable compound include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (metha) (Meth) acryloyloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate alkylene oxide-modified product, and dipentaerythritol hexa (meth) acrylate alkylene oxide-modified product NK Oligo UA-32P, NK Oligo UA-7200 (manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.), Aronix M-3M, and NK Oligo UA- 305, Aronix M-306, Aronix M-309, Aronix M-450, Aronix M-402 and TO-1382 (manufactured by Toa Kosase Co., Ltd.), V # 802 (Osaka Yuki Kagaku Kogyo D-320, GAYALAD D-310, GAYALAD DPHA (above) There may be mentioned horn Kayaku Co. agent) or the like as a preferable example.

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

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

Alkali soluble binder

The coloring composition of the present invention preferably contains an alkali-soluble binder.

The alkali-soluble binder is not particularly limited, except that it has alkali solubility, and can be preferably selected from the viewpoints of heat resistance, developability, availability and the like.

The alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent, and capable of being developed with a weakly alkaline aqueous solution. Examples of such linear organic polymer polymers include polymers having a carboxylic acid in the side chain, such as those disclosed in Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Laid- Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, and acrylic acid copolymers as described in the respective publications of Japanese Patent Application Laid-Open No. 25957, Japanese Patent Application Laid-open No. 59-53836, Maleic acid copolymers, partially esterified maleic acid copolymers and the like, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

Examples of the alkali-soluble binder in the present invention include those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate ), Polyvinyl pyrrolidone and polyethylene oxide, and polyvinyl alcohol are also useful. The linear organic polymer may be a copolymer of a monomer having hydrophilicity. Examples of the monomer having hydrophilicity include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, (Meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, (Meth) acrylate, branched or linear propyl (meth) acrylate, branched or straight chain butyl (meth) acrylate, and phenoxy hydroxypropyl (meth) acrylate. Examples of the hydrophilic monomer include monomers containing a tetrahydrofurfuryl group, monomers containing a phosphoric acid group, monomers containing a phosphate ester group, monomers containing a quaternary ammonium salt group, monomers containing an ethyleneoxy group, , Monomers containing a group derived from a sulfonic acid group or a salt thereof, and monomers containing a morpholinoethyl group are also useful.

The alkali-soluble binder may have a polymerizable group in the side chain in order to improve the crosslinking efficiency. For example, a polymer containing an allyl group, a (meth) acrylic group, an allyloxyalkyl group or the like in its side chain is also useful. Examples of the above-mentioned polymer containing a polymerizable group include commercially available dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Photomer 6173 (COOH group-containing polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co. Ltd); Viscot R-264 and KS Resist 106 (all manufactured by Osaka Kikugaku Kogyo Co., Ltd.); Cyclomer P series, and Fraxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.); Ebecryl 3800 (manufactured by Daicel-Cotech Co., Ltd.) and the like. Alcohol-soluble nylon and polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful for increasing the strength of the cured coating.

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

Examples of the acrylic resin include copolymers composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, and (meth) acrylamide, and commercially available dianal NR series (Mitsubishi Rayon (Manufactured by Daicel Chemical Industries, Ltd.), KS Resist-106 (manufactured by Osaka Yuki Kagaku Kogyo K.K.), Cyclomer P series, and Fraxel CF200 series (manufactured by Daicel Chemical Industries, Ltd.).

The alkali-soluble binder is, developability, from the viewpoint of solution viscosity, and a weight average molecular weight (GPC method in terms of polystyrene measured by a) preferably is a 1000~2 × 10 ⁵ polymer, is a polymer 2000~1 × 10 ⁵ More preferred is a polymer having a weight of 5000 to 5 x 10 &lt; ⁴ &gt;

The alkali-soluble binder may be used alone or in combination of two or more.

The content of the alkali-soluble binder in the coloring composition of the present invention is preferably from 1 to 80% by mass, more preferably from 5 to 70% by mass, and still more preferably from 10 to 60% by mass, based on the total solid content of the coloring composition Do.

[Photopolymerization initiator]

The coloring composition of the present invention preferably contains at least one photopolymerization initiator.

The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, and cost.

The photopolymerization initiator is a compound that initiates and accelerates polymerization of a polymerizable compound by being sensitized by exposure light. A compound capable of initiating and promoting polymerization of a polymerizable compound in response to an actinic ray having a wavelength of 300 nm or more is preferable. In addition, it can be preferably used in combination with a photopolymerization initiator or sensitizer that does not directly react with an actinic ray having a wavelength of 300 nm or more.

Specific examples of the photopolymerization initiator include oxime ester compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxides, azo compounds, coumarin compounds, A nitrile compound, a metallocene compound, a hexaarylbimidazole compound, an organic boric acid compound, a disulfonic acid compound, an onium salt compound, an acylphosphine (oxide), a benzophenone compound, an acetophenone compound and a derivative thereof.

Of these, oxime ester compounds and hexaarylbimidazole compounds are preferable in terms of sensitivity.

Examples of the oxime ester compounds include compounds described in JP 2000-80068 A, JP 2001-233842 A, JP 2004-534797 A, WO 2005/080337 A, WO 2006/018973 A pamphlet, The compounds described in Japanese Patent Application Laid-Open Nos. 2007-210991, 2007-231000, 2007-269779, 2009-191061 and 2009/131189 pamphlets can be used have.

Specific examples thereof include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- ] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) - (phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- ) -1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) (O-acetyloxime) -1- [9-ethyl-6- (2- (4-fluorophenyl) (9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] 1- (9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) - [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- ) -9H- 2- (acetoxyimino) -4- (4-chlorophenyl) -1- [4- (phenylthio) Thio) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1-butanone. However, the present invention is not limited to these.

Further, in the present invention, as the oxime compound, the compound represented by the following formula (E1) is also favorable from the viewpoints of sensitivity, stability with time (time stability) and coloration upon post heating.

In the general formula (E1), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 0 to 5;

Among the general formula (E1), R is preferably an acyl group in view of high sensitivity, and specifically, an acetyl group, a propionyl group, a benzoyl group or a toluyl group is preferable.

Among the general formula (E1), A is preferably an unsubstituted alkylene group, an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group or a dodecyl group) in view of increasing the sensitivity and inhibiting coloration with heating An alkylene group substituted with a substituted alkylene group, an alkenyl group (e.g., a vinyl group or an allyl group), an aryl group (e.g., a phenyl group, a p-tolyl group, a xylyl group, a cumenyl group, a naphthyl group, , Phenanthryl group, styryl group) is preferable.

Among the general formula (E1), Ar is preferably a substituted or unsubstituted phenyl group in view of increasing the sensitivity and suppressing coloring with heating. In the case of a substituted phenyl group, the substituent is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

In the general formula (E1), X is preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, a substituent , An alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, or an amino group which may have a substituent.

In the general formula (E1), n is preferably an integer of 1 to 2.

Examples of the organic halogenated compound include, specifically, those described in Wakabayashi et al., &Quot; Bull Chem. Soc. Japan, 42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Examined Patent Application Publication No. 46-4605, Japanese Examined Patent Application Publication No. 48-36281, Japanese Examined Patent Application Publication No. 55-32070, 60-239736, 61-169835, 61-169837, 62-58241, 62-212401, Japanese Patent Application Laid-Open No. 62-212401, Japanese Patent Application Laid- Compounds described in MP Hutt "Journal of Heterocyclic Chemistry" 1 (No. 3), (1970) and the like can be mentioned, and in particular, oxirane substituted with a trihalomethyl group Sol, and s-triazine compounds.

Examples of the hexaaryl biimidazole compound include various compounds described in each specification such as Japanese Patent Publication No. Hei 6-29285, U.S. Patent Nos. 3,479,185, 4,311,783, 4,622,286, and the like, specifically, , 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis , 5'-tetraphenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- Chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4' Bis (o-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4 , 4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-trifluorophenyl) -4,4', 5,5'-tetraphenylbiimidazole and the like .

The photopolymerization initiator may be used alone or in combination of two or more. When an initiator that does not absorb light at the exposure wavelength is used, it is necessary to use a sensitizer.

The total content of the photopolymerization initiator is preferably 0.5% by mass to 30% by mass, more preferably 2% by mass to 20% by mass, and still more preferably 5% by mass to 18% by mass relative to the total solid content in the coloring composition of the present invention. Is more preferable. When the total content of the photopolymerization initiator is within this range, the sensitivity at the time of exposure is higher and the color characteristic is also better.

[Increase / decrease]

The coloring composition of the present invention may contain a sensitizer.

Typical sensitizers that can be used in the present invention include those described in J. V. Crivello, Adv. in Polymer Sci, 62, 1 (1984), and specific examples thereof include pyrene, perylene, acridine, thioxanthone, 2-chlorothioxanthone, benzofurabin, N- , 9,10-dibutoxyanthracene, anthraquinone, benzophenone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives and the like.

The sensitizer is preferably contained in a proportion of from 50 mass% to 200 mass% with respect to the photopolymerization initiator.

[Chain transfer agent]

The coloring composition of the present invention may contain a chain transfer agent.

Examples of the chain transfer agent usable in the present invention include N, N-dialkylamino benzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzooxa Sol, 2-mercaptobenzoimidazole, N-phenylmercaptobenzoimidazole, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine- (1H, 3H, 5H) -tione and the like, and a mercapto compound having a heterocyclic ring such as pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane And aliphatic polyfunctional mercapto compounds such as aliphatic polyfunctional mercapto compounds.

The chain transfer agent may be used alone, or two or more kinds may be used in combination.

The content of the chain transfer agent is preferably from 0.01% by mass to 15% by mass, based on the total solid content of the coloring composition of the present invention, from the viewpoint of reducing the sensitivity unevenness, more preferably from 0.1% by mass to 10% And particularly preferably 0.5% by mass to 5% by mass.

[Polymerization inhibitor]

The coloring composition of the present invention may contain a polymerization inhibitor.

The term "polymerization inhibitor" refers to an agent capable of hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation (or the like) to a polymerization initiator (polymerization initiation species) such as a radical generated in a colored photosensitive resin composition by light or heat , Electron donating), and the like, and deactivating the polymerization initiator to inhibit the polymerization from being initiated unintentionally. For example, the polymerization inhibitor described in paragraphs 0154 to 0173 of Japanese Patent Application Laid-Open No. 2007-334322 or the like can be used.

Of these, p-methoxyphenol is preferably used as the polymerization inhibitor.

The content of the polymerization inhibitor in the coloring composition of the present invention is preferably from 0.0001 mass% to 5 mass%, more preferably from 0.001 mass% to 5 mass%, and still more preferably from 0.001 mass% to 5 mass%, based on the total mass of the polymerizable compound. By mass to 1% by mass.

[Organic solvents]

The coloring composition of the present invention preferably contains an organic solvent.

The organic solvent is not particularly limited insofar as it can satisfy the solubility of the coexisting components and the coating property when it is used as a colored composition, and is preferably selected in consideration of solubility, coatability, and safety of the solid content Do.

Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyl butyrate, Methyl lactate, ethyl lactate, and oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specifically, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl ethoxyacetate, and the like), 3-oxypropionic acid alkyl esters, 2-oxypropionic acid alkyl esters, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy- Methyl, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate and ethyl 2-oxobutanoate.

Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl 3-ethoxypropionate, 3 Ethyl ethoxypropionate, and the like.

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

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

These organic solvents preferably contain two or more kinds of these organic solvents in view of the solubility of the respective components and the solubility thereof in the case of containing an alkali-soluble binder, and the improvement on the coated surface. In this case, particularly preferable examples thereof include methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, Is a mixed solution containing at least two kinds selected from the group consisting of onium, cyclohexanone, ethylcarbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

The content of the organic solvent in the coloring composition of the present invention is preferably such that the total solid content concentration in the coloring composition is 5 mass% to 80 mass%, more preferably 5 mass% to 60 mass% And particularly preferably from 10% by mass to 60% by mass.

[Surfactants]

The coloring composition of the present invention may contain a surfactant.

As the surfactant, any of anionic, cationic, nonionic or amphoteric surfactants may be used, but a preferred surfactant is a nonionic surfactant. Specific examples include the nonionic surfactants described in paragraph 0058 of Japanese Patent Application Laid-Open No. 2009-098616, and among them, fluorinated surfactants are preferred.

Examples of other surfactants that can be used in the present invention include commercially available products such as Megapac F142D, F172, F173, F176, F177, F183, F479, F482, F554, F780, FC-135C, FC-170C, FC-170C, FC-170C, FC-170C, FC- S-112, S-113, S-131, and S-131 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG7105, 7000, 950, 7600, FC-431, Novec FC-4430 S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105 and SC-106 (manufactured by Asahi Sosho (Available from Mitsubishi Materials Denshi Kasei Co., Ltd.) and Fotogen 250 (manufactured by Neos Co., Ltd.), and the like.

Further, as the surfactant, the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography using a tetrahydrofuran as a solvent and containing the constituent unit A and the constituent unit B represented by the following formula (S1) A preferred example is a copolymer having a number of from 1,000 to 10,000.

In the general formula (S1), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a straight chain alkylene group having 1 to 4 carbon atoms and R ⁴ represents a hydrogen atom or a C1- P represents an alkylene group having 3 to 6 carbon atoms, p and q each represent a weight percentage representing a polymerization ratio, p represents a value of 10 mass% or more and 80 mass% or less, q represents an amount of 20 mass% Or more and 90 mass% or less, r is an integer of 1 or more and 18 or less, and n is an integer of 1 or more and 10 or less.

In the structural unit B, L is preferably a branched alkylene group represented by the following general formula (S2). R ⁵ in the general formula (S2) represents an alkyl group having 1 to 4 carbon atoms and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to a surface to be coated, An alkyl group is more preferred. It is preferable that the sum (p + q) of p and q is p + q = 100, that is, 100 mass%.

The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

These surfactants may be used singly or in combination of two or more.

The content of the surfactant in the coloring composition of the present invention is preferably 0.01% by mass to 2.0% by mass, particularly preferably 0.02% by mass to 1.0% by mass, based on the solid content of the coloring composition. Within this range, the coating property and the uniformity of the cured film become better.

[Adhesion improver]

The coloring composition of the present invention may contain an adhesion improver.

The adhesion improver is preferably used as a material for improving adhesiveness between an inorganic material as a substrate such as glass, silicon, silicon oxide, silicon compound such as silicon nitride, gold, copper, aluminum and the like and a cured film formed by using a coloring composition . Specific examples thereof include silane coupling agents and thiol compounds. The silane coupling agent as the adhesion improver is for the purpose of modifying the interface and is not particularly limited and a known silane coupling agent can be used.

As the silane coupling agent, a silane coupling agent described in paragraph 0048 of Japanese Patent Application Laid-Open No. 2009-98616 is preferable, and among these,? -Glycidoxypropyltrialkoxysilane and? -Methacryloxypropyltrialkoxysilane are more preferable Do. These may be used alone or in combination of two or more.

The content of the adhesion improver in the coloring composition of the present invention is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 5% by mass, based on the total solid content of the coloring composition.

[Crosslinking agent]

By using a crosslinking agent in a complementary manner to the coloring composition of the present invention, it is possible to further increase the hardness of the colored cured film obtained by curing the coloring composition.

The cross-linking agent is not particularly limited as long as it can perform film curing by a cross-linking reaction, and examples thereof include (a) an epoxy resin, (b) at least one substituent selected from methylol group, alkoxymethyl group, and acyloxymethyl group A phenol compound, a naphthol compound or a hydride compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, which is substituted with a hydroxyl group, a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, And a hydroxyanthracene compound. Among them, a polyfunctional epoxy resin is preferable.

Specific examples of crosslinking agents and the like can be found in the paragraphs [0134] to [0147] of Japanese Patent Application Laid-Open No. 2004-295116.

[Development promoter]

In order to promote the alkali solubility of the non-exposed region and to further improve the developability of the coloring composition of the present invention, a development accelerator may be added. The development accelerator is preferably a low molecular weight organic carboxylic acid compound having a molecular weight of 1000 or less or a low molecular weight phenol 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, diethylacetic acid, enantic acid and caprylic acid; There may be mentioned oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, And aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarballyl acid, aconitic acid, and camphoronic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemellitic acid, and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melotropic acid, and pyromellitic acid; And examples thereof include phenylacetic acid, hydro atropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, cumaric acid, .

[Other additives]

In the coloring composition of the present invention, various other additives such as a filler, a polymer compound other than the above, an ultraviolet absorber, an antioxidant, an anti-aggregation agent and the like may be added as necessary. Examples of such additives include those described in paragraphs [0155] to [0156] of Japanese Patent Application Laid-Open No. 2004-295116.

The coloring composition of the present invention may contain the light stabilizer described in paragraph [0078] of Japanese Patent Application Laid-Open No. 2004-295116, and the thermal polymerization inhibitor described in paragraph [0081] of the same publication.

[Preparation of coloring composition]

The preparation method of the coloring composition of the present invention is not particularly limited, but can be prepared by mixing the above-mentioned respective components such as a specific metal complex compound, a polymerizable compound and a photopolymerization initiator, and optional components as required.

In the preparation of the coloring composition, the respective components contained in the coloring composition may be blended at one time, or each component may be dissolved and dispersed in a solvent and then blended in succession. Further, the order of introduction and the working conditions at the time of compounding are not particularly limited. For example, the composition may be prepared by dissolving and dispersing all the components in a solvent at the same time in a solvent. If necessary, each component may be used as two or more enemy solutions and / or dispersions, May be mixed and prepared as a composition.

In the preparation of the coloring composition of the present invention, for the purpose of eliminating foreign matters or reducing defects, it is preferable that the components are mixed and then filtered by a filter. The filter used conventionally is not particularly limited, and is used in filtration applications. Specific examples thereof include fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon-6 and nylon-6,6, polyolefin resins such as polyethylene and polypropylene (PP) , Ultra high molecular weight), and the like. Of these filter materials, polyamide resins such as nylon-6 and nylon-6,6, and polypropylene (including high-density polypropylene) are preferable.

The pore diameter of the filter is suitably about 0.01 to 7.0 mu m, preferably about 0.01 to 2.5 mu m, and more preferably about 0.01 to 2.0 mu m. Within this range, it is possible to reliably remove fine foreign matter which inhibits the preparation of a uniform coloring composition in a subsequent step, and to form a uniform and smooth colored composition.

When using a filter, other filters may be combined. At this time, the filtering using the first filter may be performed only once or two or more times. The first filtering may be performed by combining the first filter with a plurality of filters by combining the filters of different pore sizes within the above-mentioned range. The pore referred to here can refer to the nominal value of the filter maker. As commercially available filters, there may be mentioned, for example, filters manufactured by Nippon Polyurethane Industry Co., Ltd., Advantech Yoga Co., Ltd., Nippon Ince Grease Co., Ltd. (formerly Nippon Microlis Co., Ltd.) It is possible to select among various types of filters to be provided.

The second filter may be formed of the same material as that of the first filter described above.

Further, for example, the filtering in the first filter may be performed only on the pigment dispersion, and the second filtering may be performed after mixing the pigment dispersion with other components to obtain a coloring composition.

The coloring composition of the present invention can be applied to various applications such as color filters for image display devices such as color filters for solid-state imaging devices, liquid crystal displays, organic EL devices, printing inks, inkjet inks and the like.

Particularly, since the colored cured film obtained by curing the coloring composition of the present invention is a homogeneous cured film having a high color purity, a thin layer, a high extinction coefficient, an excellent fastness (particularly light resistance) A color filter for a display device, and a color filter for a solid-state image pickup device. In addition, when the colored cured film is applied to a liquid crystal display device, a voltage maintaining ratio excellent when a voltage is applied can be obtained.

Color filter and manufacturing method thereof

The color filter of the present invention has, on an arbitrary support, a colored region (colored cured film) formed by the colored composition of the present invention.

The colored regions on the support are composed of coloring films such as red (R), green (G), and blue (B), for example, which make up each pixel of the color filter.

The color filter of the present invention may be formed by any method as long as it can form a colored region (colored hardened film) in a cured pattern containing a specific metal complex compound. The color filter of the present invention is preferably manufactured using the method of manufacturing a color filter of the present invention described later.

The method of manufacturing a color filter of the present invention is a method of manufacturing a color filter, comprising the steps of providing a coloring composition of the present invention on a support to form a coloring composition layer (hereinafter also referred to as step (A)), (Hereinafter also referred to as a step (B)) of forming a coloring region (colored cured film) on the pattern by exposing the resist film to a pattern-like pattern)

By coloring these processes a plurality of times, a coloring pattern composed of pixels of each color (three colors or four colors) is formed, and a color filter can be obtained.

In the method of manufacturing a color filter according to the present invention, in particular, there may be a step of irradiating ultraviolet light to a colored region on a pattern formed in the step (B) (hereinafter also referred to as a step (C)), (Hereinafter also referred to as &quot; step (D) &quot;) for performing a heat treatment on the colored region.

By using the manufacturing method of a color filter of the present invention, an image display apparatus such as a liquid crystal display apparatus and a color filter used for a solid-state image pickup device can be manufactured with low difficulty in process quality, and at low cost.

Hereinafter, a method of manufacturing a color filter of the present invention will be described in more detail.

Step (A)

In the method for producing a color filter of the present invention, first, the colored composition of the present invention described above is applied directly or via another layer by a desired method to form a coating film (coloring composition layer) comprising the coloring composition do. Thereafter, if necessary, pre-curing (pre-baking) is performed to dry the colored composition layer.

Examples of the support include a non-alkali glass, a soda glass, a Pyrex (registered trademark) glass, a quartz glass and a transparent conductive film adhered thereto, and a photoelectric conversion element used for a solid- A substrate (for example, a silicon substrate and a plastic substrate), and the like. A black matrix for isolating each pixel may be formed on the support, or a transparent resin layer may be provided for promoting adhesion or the like. In addition, an undercoat layer may be provided on the support, if necessary, in order to improve adhesion with the upper layer, prevent diffusion of the material, or planarize the surface.

It is preferable that the plastic substrate has at least one layer selected from the gas barrier layer and the solvent-resistant layer on the surface thereof.

(Hereinafter referred to as &quot; TFT type liquid crystal driving substrate &quot;) having a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display disposed thereon is used as the supporting substrate, A coloring pattern formed by using the coloring composition of the present invention can be formed to form a color filter.

Examples of the substrate in the TFT type liquid crystal driving substrate include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may optionally be pretreated by a chemical pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition, or the like. For example, a substrate on which a passivation film such as a silicon nitride film is formed on the surface of a TFT type liquid crystal driving substrate can be used.

Examples of the method of applying the coloring composition of the present invention on a support include spin coating, slit coating, casting, roll coating, bar coating, inkjet and the like.

In the step (A), the method of imparting the coloring composition of the present invention on a support is not particularly limited, but a method using a slit nozzle such as a slit-and-spin coating method or a spinless coating method (hereinafter referred to as a slit nozzle coating method ).

In the slit nozzle spin coating method, the slit-and-spine coating method and the spin-less coating method have different conditions depending on the size of the application substrate. For example, a fifth-generation glass substrate (1100 mm x 1250 mm ) Is applied, the discharge amount of the colored composition from the slit nozzle is usually 500 to 1000 microliters / second, preferably 800 to 1500 microliters / second, and the coating rate Is usually 50 mm / sec to 300 mm / sec, and preferably 100 mm / sec to 200 mm / sec.

The solid content of the coloring composition used in the step (A) is usually 10% by mass to 20% by mass, preferably 13% by mass to 18% by mass.

In the step (A), it is usually preferable to perform the prebaking treatment after the formation of the colored composition layer. If necessary, a vacuum treatment may be performed before prebaking. Vacuum drying is usually carried out at a vacuum degree of about 13.33 Pa (0.1 Torr) to 133.32 Pa (1.0 Torr), preferably about 26.66 Pa (0.2 Torr) to about 66.66 Pa (0.5 Torr).

The conditions for prebaking include a condition of heating at 70 to 130 캜 for 0.5 to 15 minutes using a hot plate or an oven.

The thickness of the coloring composition layer formed by the coloring composition is appropriately selected depending on the purpose. In the case of a color filter for a liquid crystal display, the thickness is preferably in the range of 0.2 탆 to 5.0 탆, more preferably in the range of 1.0 탆 to 4.0 탆, and most preferably in the range of 1.5 탆 to 3.5 탆. In the case of a color filter for a solid-state image sensor, the range is preferably in the range of 0.2 탆 to 5.0 탆, more preferably in the range of 0.3 탆 to 2.5 탆, and most preferably in the range of 0.3 탆 to 1.5 탆.

The thickness of the colored composition layer is the film thickness after pre-baking.

Step (B)

Subsequently, in the method of manufacturing a color filter of the present invention, a coating film (coloring composition layer) formed of the coloring composition formed as described above is exposed on a support via, for example, a photomask. As the light or radiation usable for exposure, g line, h line, i line, j line, KrF light, ArF light are preferable, and i line is particularly preferable. When i-line is used as irradiation light, it is preferable to irradiate with an exposure amount of 100 mJ / cm 2 to 10000 mJ / cm 2.

As other exposure light beams, various visible and non-visible laser light sources such as ultrahigh pressure, high pressure, medium pressure and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps and metal halides, fluorescent lamps, tungsten lamps, .

Exposure process using laser light source

In the exposure method using a laser light source, it is preferable to use an ultraviolet laser as the light source.

The irradiation light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 300 nm, more preferably an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm, . Concretely, the third harmonic (355 nm) of a Nd: YAG laser of a solid-state laser having a large output and a relatively low output, and XeCl (308 nm) and XeF (353 nm) of an excimer laser can be used suitably.

The exposed amount of the pinhole (pattern) is in the range of 1 mJ / cm 2 to 100 mJ / cm 2, and more preferably in the range of 1 mJ / cm 2 to 50 mJ / cm 2. When the exposure dose is within this range, it is preferable from the viewpoint of productivity of pattern formation.

Examples of the exposure apparatus include, but are not limited to, commercially available products such as Callisto (manufactured by V-Technology Corporation), EGIS (manufactured by V-Technology Corporation) and DF2200G (manufactured by Dainippon Screen Corporation) Do. Other devices than the above are also used for convenience.

When a color filter for a liquid crystal display device is manufactured, exposure using h-line or i-line is preferably used by a proximity photolithography machine or a mirror projection exposure machine. When manufacturing a color filter for a solid-state imaging device, i-line is preferably used as a stepper exposure device. When a color filter is manufactured using a TFT type liquid crystal driving substrate, the photomask used is provided with a pattern for forming a through hole or a rectangular groove in addition to a pattern for forming a pixel (coloring pattern) Is used.

The exposed coloring composition layer as described above can be heated.

The exposure can be performed while flowing nitrogen gas into the chamber in order to suppress oxidation and discoloration of the coloring material in the colored composition layer.

Subsequently, the developed coloring composition layer is developed with a developing solution. Thus, a negative type coloring pattern (resist pattern) can be formed. In the development step, the uncured portions of the coated film after exposure are dissolved in the developer so that only the hardened portions remain on the support.

Any developer may be used as far as it dissolves the coating film (colored composition layer) of the colored composition in the uncured portion and does not dissolve the cured portion. For example, a combination of various organic solvents or an alkaline aqueous solution can be used.

As the organic solvent to be used in the development, there may be mentioned the solvents which can be used in preparing the coloring composition of the present invention.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, An alkaline compound such as ammonium hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo- [5,4,0] -7-undecene at a concentration of 0.001% by mass to 10% And preferably 0.01% by mass to 1% by mass. When the developer is an alkaline aqueous solution, the alkali concentration is preferably adjusted to a pH of 11 to 13, more preferably a pH of 11.5 to 12.5.

To the alkaline aqueous solution, for example, a water-soluble organic solvent such as methanol or ethanol, and / or a surfactant may be added in an appropriate amount.

The developing temperature is usually 20 占 폚 to 30 占 폚, and the developing time is preferably 20 seconds to 90 seconds.

The phenomenon may be a dipping method, a showering method, a spraying method, or the like, and a swing method, a spin method, an ultrasonic method, or the like may be combined with the phenomenon. It is also possible to wet the surface to be developed with water or the like before coming into contact with the developing solution to prevent development unevenness. Further, the substrate may be inclined and developed.

When manufacturing a color filter for a solid-state imaging device, a paddle phenomenon may be used.

After the development process, the development process is carried out after the rinsing process for cleaning and removing the developing solution of the fingernail (s), followed by drying, and then heat treatment (post-baking) is performed to complete the curing.

The rinse treatment is usually carried out with pure water, but pure water is used in the final rinse for the fresh juice (liquid saving), pure water after the rinse is used at the beginning of the rinse, or the substrate is tilted, Or a method of using them in combination may be used.

After the rinse treatment, the water removal and the drying are carried out, the heat treatment is usually carried out preferably at about 200 to 250 캜. In this heating treatment (post baking), the coated film after development is continuously or batch-wise subjected to the above-described conditions by using a heating means such as a hot plate or a convection oven (hot air circulation type drier) or a high frequency heater .

By repeating the above steps sequentially for each color in accordance with the desired number of colors, it is possible to produce a color filter in which a cured film (colored pattern) colored with a plurality of colors is formed.

Step (C)

In the method of manufacturing a color filter of the present invention, it is also possible to perform post-exposure by ultraviolet irradiation on a colored region (colored pixel) formed on a pattern formed by using a colored composition.

Step (D)

It is preferable to further heat the colored regions in the pattern on which the post exposure is performed by the ultraviolet irradiation as described above. By heating the formed colored region (so-called post-baking treatment), the colored region can be further cured. This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, and the like.

The temperature during the heat treatment is preferably 100 占 폚 to 300 占 폚, and more preferably 150 占 폚 to 250 占 폚. The heating time is preferably about 10 minutes to 120 minutes.

The patterned color region thus obtained constitutes a pixel in the color filter. In the production of a color filter having pixels of a plurality of colors, the above-mentioned step (A), step (B) and, if necessary, step (C) and / or step (D) may be repeated according to the desired number of colors.

At least one step selected in the above-mentioned step (C) and step (D) may be carried out every time the formation of the monochromatic coloring composition layer, the exposure and the development are completed (per one color) After the formation of the coloring composition layer, the exposure and the development are completed, at least one step selected in the above-mentioned step (C) and step (D) may be carried out collectively.

Since the color filter of the present invention (color filter of the present invention) obtained by the method of producing a color filter of the present invention uses the coloring composition of the present invention, the coloring of the image display is clear, the contrast is high, And light resistance) and excellent voltage retention.

The color filter of the present invention can be used for a liquid crystal display element or a solid-state image pickup element, and is particularly suitable for use in liquid crystal display devices. When used in a liquid crystal display device, images can be displayed with excellent spectral characteristics and contrast while achieving good hues by using a dye as a colorant, and further, the voltage holding ratio is also excellent.

[Image display device]

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

Examples of the image display device include a liquid crystal display device and an organic EL display device, and the color filter of the present invention is particularly preferably used for a liquid crystal display device.

When the color filter of the present invention is used in a liquid crystal display device, the voltage holding ratio when a voltage is applied is not lowered, while the metal complex compound having excellent spectroscopic characteristics and light resistance is contained as a coloring agent, The alignment defect of the liquid crystal molecules is small and the display image has good color tone and excellent display characteristics.

Therefore, the liquid crystal display device provided with the color filter of the present invention can display a high-quality image having a good color tone of the display image and excellent display characteristics.

The definition of the display device and the details of each display device are described in detail in, for example, "Electronic Display Device (Sasaki Akio Kogyo Co., Ltd., Sakai, 1990 Issued)", "Display Device (Ibukisumi Akira, Note) published in the first year of Heisei). The liquid crystal display device is described in, for example, &quot; Next Generation Liquid Crystal Display Technology (edited by Uchida Tatsuo, published by Sakai High School Co., Ltd. in 1994) &quot;. The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, the present invention can be applied to various types of liquid crystal display devices described in the &quot; next generation liquid crystal display technology &quot;.

The color filter in the present invention may be used in a color TFT type liquid crystal display device. The color TFT type liquid crystal display device is described in, for example, &quot; Color TFT liquid crystal display (published by K. Hazard Co., Ltd., 1996) &quot;. The present invention can also be applied to a liquid crystal display device such as a transverse electric field driving system such as IPS, a pixel division system such as MVA and the like, and a STN, TN, VA, OCS, FFS and R-OCB .

In addition, the color filter in the present invention can be provided in a color-filter on array (COA) method which is bright and high definition. In the COA type liquid crystal display device, the required characteristics for the color filter layer may require the characteristics required for the interlayer insulating film, that is, the low dielectric constant and the peel liquid resistance, in addition to the usual required characteristics as described above. The color filter of the present invention is excellent in color purity and light transmittance and excellent in color tone of a colored pattern (pixel) in that a dye compound having excellent color is used. Therefore, the color filter of the COA type having high resolution and excellent in long- A display device can be provided. In order to satisfy the required characteristics of low dielectric constant, a resin film may be provided on the color filter layer.

These image display methods are described in, for example, page 43 of "EL, PDP, and LCD display technology and the latest trend in the market" (issued by Dora Research Center Superintendent Kenkyukubon 2001).

The liquid crystal display device provided with the color filter in the present invention has various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film in addition to the color filter in the present invention. The color filter of the present invention can be applied to a liquid crystal display device having these known members. These members are described, for example, in "Market of Liquid Crystal Display Materials and Chemicals, 1994 (published by Shimaguchi Co., Ltd., CMC 1994)", "2003 Current Status of Liquid Crystal Related Markets and Future Prospects (Published by Fuji Chimera Soken Co., Ltd., 2003).

Regarding the backlight, it is described in the SID meeting Digest 1380 (2005) (A. Konno et al), Monthly Display December 2005, pages 18-24 (Yamazaki Shimaya), 25-30 pages (Yagi Takaaki) have.

When the color filter according to the present invention is used in a liquid crystal display device, high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube. However, when an LED light source (RGB-LED) It is possible to provide a liquid crystal display device having higher luminance and higher color purity and better color reproducibility.

[Solid-state image pickup device]

The solid-state image pickup device of the present invention includes the color filter of the present invention described above.

The configuration of the solid-state imaging device of the present invention is not particularly limited as long as the configuration includes the color filter of the present invention and functions as a solid-state imaging device. For example, the following configuration can be given.

That is, a plurality of photodiodes constituting a light receiving area of a solid-state image pickup device (a CCD image sensor, a CMOS image sensor, or the like) and a transfer electrode made of polysilicon or the like are formed on a support, Shielding film made of tungsten or the like having only the light receiving portion of the photodiode opened and having a device protective film made of silicon nitride or the like formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light receiving portion, .

The structure of the solid-state image pickup device of the present invention may be a structure having a condensing means (for example, a microlens or the like) on the device protective layer and below the color filter Or a structure having a light condensing means.

[Example]

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples unless it is beyond the ordinary knowledge. Unless otherwise noted, "parts" and "%" are on a mass basis.

[Example 1: synthesis of specific metal complex compound]

[Synthesis Examples of Exemplary Compounds P-1, P-7, P-16, and P-26]

Exemplary compounds P-1, P-7, P-16, and P-26 were synthesized according to Reaction Scheme A below as specific examples of specific metal complex compounds.

[Synthesis of Intermediate 1]

Intermediate 1 was synthesized by the method described in JP-A-2012-140586.

Intermediates 2 to 7, Exemplified Compounds P-1, P-7, P-16, and P-26 were synthesized as shown below.

[Synthesis of intermediate 2]

16 ml of toluene and 0.37 g (5 mmol) of dimethylformamide were added to 11.4 g (50 mmol) of 2-phenoxymethylbenzoic acid, and the mixture was stirred at room temperature. To this solution, 6 g (50 mmol) of thionyl chloride was added dropwise and stirred at 50 DEG C for 1 hour to obtain a reaction solution A. Subsequently, 20.3 ml of toluene and 9.3 g (10 mmol) of Intermediate 1 were added to 43.2 g (0.27 mol) of 25% sodium hydroxide aqueous solution, and the mixture was stirred at room temperature. To this solution was added dropwise the reaction solution A prepared above, and the mixture was stirred at room temperature for 7 hours. After completion of the reaction, the water layer was removed, and the reaction solution was washed three times with 50 ml of a 5% aqueous solution of sodium hydroxide and then once with 50 g of a 15% aqueous acetic acid solution. Subsequently, 100 ml of methanol was added to this solution, and the mixture was stirred at 10 캜 for 2 hours, and then the resulting solid was filtered and dried. Thus, 10.2 g (yield: 81%) of Intermediate 2 was obtained.

[Synthesis of Exemplified Compound P-1]

6.26 g (5 mmol) of Intermediate 2 was added to 30 ml of tetrahydrofuran and stirred at room temperature, and then 1.32 g (6 mmol) of zinc acetate dihydrate was added and stirred for 2 hours. Subsequently, 100 ml of methanol was added to the solution, and the mixture was further stirred at 0 ° C for 2 hours. After completion of the reaction, the precipitated solid was filtered, and the filtrate was washed with methanol and dried. Thus, 6.4 g (yield: 93%) of the exemplified compound P-1 was obtained.

Details of ¹ H-NMR (CDCl ₃ ) were as follows:?: 11.83 (s, 2H), 7.88 (d, 2H), 7.80 2H), 5.62 (d, 4H), 1.77 (s, 3H), 6.70 (s, 18H), 0.66 (d, 6H), 0.57-0.45 (m, 2H), 0.28 (m, 2H), 1.27-1.16 To 0.19 (m, 2H).

The molar extinction coefficient (?) In the chloroform solution was measured using a spectrophotometer UV-1800PC (Shimadzu Corporation) and the absorbance (Abs) at the maximum absorption wavelength (? Max) Was normalized to 1.0 and the absorbance at 450 nm was evaluated.

The maximum absorption wavelength? Max of the exemplified compound P-1 was 563 nm and the molar extinction coefficient? Was 123000. The results of the maximum absorption wavelength? Max and the molar extinction coefficient? Are shown in Table 1 below.

[Synthesis of Intermediate 3]

25.1 g of potassium hydroxide and 100 ml of toluene were added to 30 g (223.7 mmol) of phthalide, and the mixture was refluxed for 2 hours while being dehydrated with Dean-Stark. Subsequently, 73.8 g (447.3 mmol) of hexyl bromide was added and heated and stirred for 24 hours. After the reaction, 100 ml of NMP was added and the mixture was stirred for 3 hours. After the toluene layer was concentrated, 35.8 g of 50% sodium hydroxide aqueous solution, 100 ml of ethanol and 30 ml of water were added and refluxed for 5 hours. After completion of the reaction, extraction was performed with ethyl acetate, and 20 g (yield: 38%) of Intermediate 3 was obtained by silica gel column chromatography.

[Synthesis of intermediate 4]

30 ml of tetrahydrofuran and 1 ml of dimethylformamide were added to 10 g (42.3 mmol) of Intermediate 3, and the mixture was stirred at room temperature. 5.4 g (42.3 mmol) of oxalyl chloride was added dropwise to this solution, and the mixture was stirred at room temperature for 30 minutes to obtain a reaction solution B. Next, 50 ml of NMP was added to 11.6 g (28.3 mmol) of the intermediate A synthesized by the method described in the specification of United States Patent Application Publication No. 2008/0076044, and the mixture was stirred at room temperature. To this solution was added dropwise the reaction solution B prepared above, and the mixture was stirred at room temperature for 5 hours. After completion of the reaction, 200 ml of water was added, and the mixture was stirred for 1 hour. The obtained solid was filtered, washed with methanol, and dried. Thus, 12.7 g (yield: 72%) of Intermediate 4 was obtained.

[Synthesis of Intermediate 5]

12.7 g (0.02 mol) of Intermediate 4 and 4.5 g (0.03 mol) of triethyl orthoformate were added to 25 ml of acetonitrile and the mixture was stirred at room temperature. To this solution was added 23 g of trifluoroacetic acid, and the mixture was stirred at room temperature for 5 hours. After the completion of the reaction, the reaction solution was poured into 400 ml of water and 18 g of sodium hydrogencarbonate, and 400 ml of ethyl acetate was added to the reaction solution. After the liquid separation, the ethyl acetate layer was concentrated, and further purified by silica gel column chromatography to obtain 5.1 g (40% yield) of Intermediate 5.

[Synthesis of Exemplified Compound P-7]

3.8 g (3 mmol) of Intermediate 2 was added to 20 ml of tetrahydrofuran and stirred at room temperature. Then, 0.72 g (3.3 mmol) of zinc acetate dihydrate was added and stirred for 2 hours. After completion of the reaction, the reaction solution was concentrated, and the mixture was heated and stirred in 20% acetic acid methanol solution for 2 hours. The precipitated solid was filtered and dried. Thus, 3.4 g (yield: 81%) of the exemplified compound P-7 was obtained.

Details of ¹ H-NMR (CDCl ₃ ) were as follows:?: 11.63 (s, 2H), 7.77 (d, 2H), 7.70 (d, 2H), 7.58-7.40 3H), 1.57-1.50 (m, 6H), 1.30 (s, 2H), 5.00 (s, 2H) (M, 2H), 0.28-0.19 (m, 2H), 0.65 (d, 6H), 0.50-0.46

The maximum absorption wavelength? Max and the molar extinction coefficient? Of the exemplified compound P-7 were measured in the same manner as in the case of the exemplified compound P-1. The maximum absorption wavelength? Max of the exemplified compound P-7 was 561 nm, (?) was 125,000.

[Synthesis of intermediate 6]

20 ml of toluene and 0.5 ml of dimethylformamide were added to 10 g (41 mmol) of 2-thiophenoxymethylbenzoic acid, and the mixture was stirred at room temperature. 5.5 g (43 mmol) of oxalyl chloride was added dropwise to this solution, and the mixture was stirred at room temperature for 1 hour to obtain a reaction solution C. Subsequently, 8.8 g of sodium hydroxide was dissolved in 26.5 ml of water, 7.6 g (8.2 mmol) of 25 ml of toluene and intermediate 1 were added, and the mixture was stirred at 0 占 폚. To this solution was added dropwise the reaction solution C prepared above, and the mixture was stirred at room temperature for 5 hours and at 60 ° C for 2 hours. After completion of the reaction, the water layer was removed, and the reaction solution was washed three times with 20 ml of a 5% aqueous solution of sodium hydroxide and then once with 20 g of an aqueous 15% acetic acid solution. Subsequently, the reaction solution was concentrated, 100 ml of methanol was added, and the mixture was stirred for 1 hour. The resulting solid was filtered, further washed with acetonitrile, and dried. Thus, 9.7 g (yield 92%) of Intermediate 6 was obtained.

[Synthesis of Exemplified Compound P-16]

8.2 g (6.4 mmol) of Intermediate 2 was added to 40 ml of tetrahydrofuran, and the mixture was stirred at room temperature. Subsequently, 1.6 g (7.1 mmol) of zinc acetate dihydrate was added and stirred for 2 hours. Subsequently, 100 ml of methanol was added to the solution, and the mixture was further stirred at 0 ° C for 2 hours. After completion of the reaction, the reaction solution was concentrated, and then stirred with a methanol solution for 2 hours. The precipitated solid was filtered and dried. Thus, 6.2 g (yield: 69%) of the exemplified compound P-16 was obtained.

Details of ¹ H-NMR (CDCl ₃ ) were as follows:?: 11.56 (s, 2H), 7.72-7.69 (m, 4H), 7.35-7.00 3H), 1.26-1.16 (m, 6H), 1.00-0.96 (m, 4H), 0.84-1.40 (m, 2H), 4.89-4.85 0.78 (m, 36H), 0.66 (d, 6H), 0.57-0.41 (m, 2H), 0.31-0.20 (m, 2H).

Further, when the maximum absorption wavelength? Max and the molar absorption coefficient? Were measured in the same manner as in the case of the exemplified compound P-1, the maximum absorption wavelength? Max of the exemplified compound P-16 was 562 nm, (?) was 117,000.

[Synthesis of intermediate 7]

20 ml of toluene and 0.44 g of dimethylformamide were added to 13.6 g (60 mmol) of 2-bibenzylcarboxylic acid, and the mixture was stirred at room temperature. To this solution, 7.2 g (60 mmol) of thionyl chloride was added dropwise and stirred at 50 DEG C for 1 hour to obtain a reaction solution D. Subsequently, 30.1 ml of toluene and 11.1 g (12 mmol) of Intermediate 1 were added to 51.8 g (0.32 mol) of 25% sodium hydroxide aqueous solution and stirred at 10 占 폚. To this solution was added dropwise the reaction solution D prepared above, and the mixture was stirred at room temperature for 5 hours. After completion of the reaction, the water layer was removed, and the reaction solution was washed three times with 50 ml of a 5% aqueous solution of sodium hydroxide and then once with 50 g of a 15% aqueous acetic acid solution. Subsequently, 100 ml of methanol was added to this solution, and the mixture was stirred at 10 캜 for 2 hours, and then the resulting solid was filtered and dried. Thus, 13.6 g (yield: 91%) of Intermediate 7 was obtained.

[Synthesis of Exemplified Compound P-26]

2 g (1.6 mmol) of Intermediate 7 was added to 10 ml of tetrahydrofuran, stirred at room temperature, and then 0.26 g (1.9 mmol) of zinc chloride dissolved in 5 ml of methanol was added and stirred for 2 hours. After completion of the reaction, the reaction solution was concentrated, 20 ml of a 50% methanol aqueous solution was added, and the mixture was stirred at 60 캜 for 2 hours. The precipitated solid was filtered and dried. Thus, 2.1 g (yield 95%) of the exemplified compound P-26 was obtained.

Details of ¹ H-NMR (CDCl ₃ ) were as follows:?: 11.43 (s, 2H), 7.60 (d, 2H), 7.42-7.38 (m, 2H), 7.32-7.00 (m, 4H), 1.25-1.17 (m, 6H), 0.99-0.95 (m, 4H), 0.82 s, 18H), 0.77 (s, 18H), 0.66 (d, 6H), 0.50-0.20 (m, 4H).

Further, when the maximum absorption wavelength? Max and the molar extinction coefficient? Were measured in the same manner as in the case of the exemplified compound P-1, the maximum absorption wavelength? Max of the exemplified compound P-26 was 561 nm, (?) was 131,000.

[Evaluation of solvent solubility]

The solvent solubility of the following Exemplified Compounds P-1, P-7, P-16, and P-26 thus obtained was evaluated. The evaluation method and judgment criteria are as follows. The results are shown in Table 1.

[Evaluation Method and Criteria]

The compound to be evaluated was weighed, and a sample solution in which propylene glycol monomethyl ether acetate was added and dissolved to a concentration of 3% by mass was stirred for 30 minutes at room temperature. The presence or absence of insoluble matter in the sample solution after stirring was visually observed, and a case where no insoluble matter was observed was determined as &quot; A &quot;.

When an insoluble matter was observed in a sample solution having a concentration of 3% by mass, a sample solution having a concentration of 0.5% by mass was prepared in the same manner as a sample solution having a concentration of 3% by mass and the presence or absence of insoluble matter in the solution was observed . The case where the insoluble matter was not observed in the sample solution of 0.5 mass% concentration was judged as "B", and the case where the insoluble matter was observed was judged as "C".

[Example 2]

(Specific metal complex compounds) shown in the following Table 1 were synthesized by a similar method to the reaction scheme in Example 1, and the compounds were identified and identified in the same manner as in Example 1, Measurement of absorption wavelength? Max and molar extinction coefficient?, And evaluation of solvent solubility were carried out.

The measurement results are shown in Table 1 together with the results of the respective exemplary compounds obtained in Example 1.

[Table 1]

From the results shown in Table 1, it was found that the compound of the present invention has a high molar extinction coefficient (?), A low absorbance at 450 nm and excellent color separation, and is a compound suitable for a color filter.

[Examples of coloring composition and color filter]

Hereinafter, coloring compositions containing the specific metal complex compounds synthesized above and examples and comparative examples of color filters obtained by using the coloring compositions are shown.

[Example 3]

First, each component used for preparing each coloring composition is shown below.

(S-1): A 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: Kayalad DPHA (manufactured by Nihon Kayaku Co., Ltd.)

(Solid content: 40.0% by mass) of benzyl methacrylate / methacrylic acid (75/25 [mass ratio]) copolymer (weight average molecular weight: 12,000)

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

(V-2) Photopolymerization initiator: 2- (acetoxyimino) -4- (4-chlorophenylthio) -1- [9-ethyl-6- (2-methylbenzoyl) -9H- ] -1-butanone

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

(X-1) Solvent: Propylene glycol monomethyl ether acetate

(X-2) Solvent: ethyl 3-ethoxypropionate

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

[Preparation of coloring composition (coating liquid)] [

The components shown in Composition A below were mixed to prepare Coloring Composition 1.

Composition A

Specific metal complex compound: Exemplary compound P-1 ... 6.9 part

(Dipyrromethene metal complex compound)

Pigment dispersion: (S-1) ... 43.0 parts

Polymerizable compound: (T-1) ... 103.4 parts

Binder resin: (U-1) ... 212.2 part

(Solid value conversion value: 84.9 parts)

Photopolymerization initiator: (V-1) ... 21.2 part

Light sensitizer: (W-1) ... 3.5 parts

Organic solvent: (X-1) ... 71.9 parts

Organic solvent: (X-2) ... 3.6 part

Surfactant: (Y-1) ... 0.06 part

[Preparation of color filter using coloring composition]

The coloring composition 1 (color resist solution) was coated on a glass substrate (1737, made by Corning) having a size of 100 mm x 100 mm so as to have an x value of 0.150 which is an index of color density and dried in an oven at 90 캜 for 60 seconds (Pre-baking). Thereafter, exposure was performed at 200 mJ / cm 2 (light intensity: 20 mW / cm 2) by means of a high-pressure mercury lamp via a photomask having a mask aperture width (hole width) of 10 m to 100 m for resolution evaluation, Was covered with a 1% aqueous solution of CDK-1 (manufactured by Fuji Film Electronics Material Co., Ltd.), pure water was dispersed in a shower, and the developer was washed away. The coated film thus exposed and developed as described above was heat-treated in an oven at 220 캜 for 1 hour (post baking) to form a colored cured film on a pattern for a color filter on a glass substrate, 1).

[evaluation]

The color filter 1 obtained above was evaluated as follows. The evaluation results are shown in Table 2 below.

1. Light Resistance

The color filter 1 was irradiated with a xenon lamp at 50,000 lux for 20 hours (equivalent to one million lux · h) as a light fastness test, and the ΔE ^* ab value of color difference before and after the light fastness test was measured. The smaller ΔE ^* ab value indicates that the light resistance is good.

Criteria

5: ΔE ^* ab value <3

4: 3?? E ^* ab value <5

3: 5?? E ^* ab value <10

2: 10?? E ^* ab value <20

1: 20?? E ^* ab value

2. Brightness

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

3. Evaluation of surface irregularity

The colored composition 1 prepared above was applied on a glass substrate (EAGLE XG; manufactured by Corning) by spin coating so that the thickness of the colored film after drying was 2.5 탆, the volatile components were dried, and then heated at 100 캜 for 80 seconds To form a photosensitive coloring film (coloring composition layer).

After the photosensitive colored film obtained above was cooled, an i-line (wavelength: 365 nm) was irradiated to cure the colored film. As an i-line light source, an ultra-high pressure mercury lamp was used, and the amount of irradiation light was set to 40 mJ / cm 2 at this time. Next, the colored film after exposure was subjected to developing treatment in a 0.05% KOH aqueous solution for 40 seconds at a temperature of 25 캜, and then the developing solution was rinsed by rinsing treatment using pure water.

Next, the colored film after the development treatment was post-baked at 230 캜 for 30 minutes. The coloring film after the post-baking treatment was observed by using an optical microscope (Olympus Sha-ze MX-61L) to see whether there was unevenness in the coloring film at a magnification of 200 times. It is judged that the film is excellent in resistance to thermal stress at the time of post-baking when a uniform film is not observed due to an optical microscope.

Criteria

A: Non-uniformity observed by optical microscope

B: Slight irregularity was observed with an optical microscope

C: Significant unevenness was observed with an optical microscope

4. Development residue

Similarly to the above, the colored composition 1 was coated on a glass substrate to form a photosensitive colored film, and then the photosensitive colored film was exposed and cured. Next, as a developer, a glass substrate having a colored film after exposure was immersed in the developer for 60 seconds using a sodium bicarbonate / sodium carbonate aqueous solution adjusted to pH 12.0 at 23 占 폚, and then ion- To prepare a substrate for residue evaluation.

After development, the glass substrate having the colored film was measured with an ultraviolet visible spectrophotometer (Shimadzu Corp. UV2400-PC), and the developed residue was evaluated by the maximum absorbance at 400 nm to 700 nm. The criteria are as follows.

Criteria

A: maximum absorbance less than 0.05

B: maximum absorbance 0.05 or more

[Examples 4 to 24]

Example Compound P-1 used in preparation of Coloring Composition 1 in Example 3 was replaced with each of the compounds shown in Table 2 (all compounds exemplified as specific metal complex compound compounds) Color filters 2 to 22 were produced in the same manner as in Example 3 except that the colored compositions 2 to 22 prepared by adjusting the ratio of the compound and the pigment dispersion (S-1) were used.

Coloring compositions 2 to 22 and color filters 2 to 22 were used and evaluated in the same manner as in Example 3. The results are shown in Table 2.

[Example 25]

A color filter 23 was prepared in the same manner as in Example 3 except that the coloring composition 23 was prepared by mixing the components shown below in the composition B and the coloring composition 23 was used instead of the coloring composition 1.

The coloring composition 23, and the color filter 23 were evaluated in the same manner as in Example 3. The results are shown in Table 2.

Composition B

Specific metal complex compound: Exemplary compound P-1 ... 6.9 part

Pigment dispersion: (S-1) ... 43.0 parts

Polymerizable compound: (T-1) ... 103.4 parts

Binder resin: (U-1) ... 212.2 part

(Solid value conversion value: 84.9 parts)

Photopolymerization initiator: (V-2) ... 21.2 part

Light sensitizer: (W-1) ... 3.5 parts

Organic solvent: (X-1) ... 71.9 parts

Organic solvent: (X-2) ... 3.6 part

Surfactant: (Y-1) ... 0.06 part

[Examples 26 to 28]

Example Compound P-1 used in preparation of Coloring Composition 23 in Example 25 was replaced with each of the compounds shown in Table 2 (all compounds exemplified as specific metal complex compound compounds) Color filters 24 to 26 were obtained in the same manner as in Example 25 except that the coloring compositions 24 to 26 were prepared by controlling the ratio of the compound and the pigment dispersion (S-1).

The coloring compositions 24 to 26 and the color filters 24 to 26 were evaluated in the same manner as in Example 3. The results are shown in Table 2.

[Example 29]

A color filter 27 was obtained in the same manner as in Example 3 except that the coloring composition 27 was prepared by mixing the components shown below in the composition C and the coloring composition 27 was used instead of the coloring composition 1.

The coloring composition 27 and the color filter 27 were evaluated in the same manner as in Example 3. [ The results are shown in Table 2.

Composition C

Specific metal complex compound: Exemplary compound P-7 ... 4.7 part

Pigment dispersion: (S-1) ... 42.1 part

The following compound (5) ... 2.3 part

Polymerizable compound: (T-1) ... 103.4 parts

Binder resin: (U-1) ... 212.2 part

(Solid value conversion value: 84.9 parts)

Photopolymerization initiator (V-2) ... 21.2 part

Light sensitizer: (W-1) ... 3.5 parts

Organic solvent: (X-1) ... 71.9 parts

Organic solvent: (X-2) ... 3.6 part

Surfactant: (Y-1) ... 0.06 part

[Example 30]

Color filter 28 was obtained in the same manner as in Example 29 except that Example Compound P-7 was replaced with Exemplified Compound P-26 in preparation of Coloring Composition 27 of Example 29, to prepare Coloring Composition 28.

The coloring composition 28 and the color filter 28 were evaluated in the same manner as in Example 3. [ The results are shown in Table 2.

[Comparative Examples 1 to 4]

Example Compound P-1 was replaced with each of the comparative compounds shown in Table 2 in the preparation of Coloring Composition 1 of Example 3, and the ratio of the comparative compound to the pigment dispersion (S-1) was changed so as to match the chromaticity , And the comparative coloring compositions C1 to C4 were prepared. Color filters C1 to C4 were obtained in the same manner as in Example 3.

Coloring compositions C1 to C4 and color filters C1 to C4 were used to evaluate in the same manner as in Example 3. The results are shown in Table 2.

Details of Comparative Compounds 1 and 2 shown in Table 2 are as follows.

The solvent solubility of the comparative compounds 1 and 2 evaluated in the same manner as the specific metal complex compound such as the exemplified compound P-1 was "B" for the comparative compound 1 and "C" for the comparative compound 2.

[Comparative Example 5]

Color filter C5 was obtained in the same manner as in Example 25, except that Example Compound P-1 was used in the preparation of Coloring Composition 23 of Example 25, except that Coloring Composition C5 was prepared instead of C.I. Acid Violet 17.

The coloring composition C5, and the color filter C5. The results are shown in Table 2.

[Comparative Example 6]

Color filter C6 was obtained in the same manner as in Example 29, except that Example Compound P-7 was used in the preparation of Coloring Composition 27 of Example 29, instead of C. I. Acid Violet 49.

The coloring composition C6, and the color filter C6 were used in the same manner as in Example 3. [ The results are shown in Table 2.

[Table 2]

As shown in Table 2, the color filters of the respective Examples using specific metal complex compounds exhibited very high luminance (Y value) as compared with the color filters of Comparative Examples 1 to 2 and 5 to 6 using conventionally known compounds I have. In addition, it is clear that each of the Examples using specific metal complex compounds is superior to Comparative Examples 3 and 4 using a known dipyrromethene metal complex compound in terms of surface irregularity and development residue remediation.

Therefore, by providing the color filter of this embodiment, it is expected that an image display apparatus and a solid-state image pickup device which display color of a display image clearly and exhibit high contrast can be obtained.

From the above results, a color filter produced using a coloring composition containing a specific metal complex compound has fastness (light resistance) and good color, and also has excellent performance in surface unevenness and remnant residue improvement. The metal complex compound may be said to be a dye compound having high general-purpose properties.

The disclosure of Japanese Patent Application No. 2012-234915 is hereby incorporated by reference in its entirety.

All publications, patent applications, and technical specifications described in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, and technical specification were specifically and individually indicated to be incorporated by reference .

Claims (12)

A coloring composition comprising at least one compound selected from the group consisting of a compound represented by the following general formula (1) and a tautomer thereof.

In the general formula (I), R ¹ to R ⁸ each independently represent a hydrogen atom or a monovalent substituent. R ⁹ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Ma represents a metal or a metal compound. X represents a group capable of bonding with Ma. n1 and n2 each independently represent an integer of 1 to 8; The method according to claim 1,
Wherein, in the general formula (I), Ma represents Fe, Zn, Co, V = O, or Cu. 3. The method according to claim 1 or 2,
Further, a coloring composition containing a polymerizable compound and a photopolymerization initiator. 4. The method according to any one of claims 1 to 3,
Further, a coloring composition containing a pigment or an anthraquinone compound or containing a pigment and an anthraquinone compound together. 5. The method of claim 4,
Wherein the anthraquinone compound is a compound represented by the following general formula (II).

In the general formula (II), R ^11a and R ^12a each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. However, R ^11a and R ^12a do not represent a hydrogen atom at the same time. n11 represents an integer of 1 to 4; 6. The method according to any one of claims 1 to 5,
R ¹ and R ⁴ each independently represent an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a cyano group, an imide group or a carbamoylsulfonyl group in the above general formula (I), R ² and R ³ R ⁵ and R ⁶ each independently represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group; R ⁷ and R ⁸ each independently represent an alkyl group or an aryl group; , R ⁹ , R ¹⁰ , and R ¹¹ represent a hydrogen atom. A color filter formed by using the coloring composition according to any one of claims 1 to 6. A process for forming a coloring composition layer by applying the coloring composition according to any one of claims 1 to 6 on a support to form a coloring composition layer; Of the color filter. An image display apparatus comprising the color filter according to claim 7 or the color filter manufactured by the method for manufacturing a color filter according to claim 8. A solid-state imaging device comprising the color filter according to claim 7 or the color filter manufactured by the method for manufacturing a color filter according to claim 8. A compound represented by the following general formula (I) or a tautomer thereof.

In the general formula (I), R ¹ to R ⁸ each independently represent a hydrogen atom or a monovalent substituent. R ⁹ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Ma represents a metal or a metal compound. X represents a group capable of bonding with Ma. n1 and n2 each independently represent an integer of 1 to 8; 12. The method of claim 11,
R ¹ and R ⁴ each independently represent an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a cyano group, an imide group or a carbamoylsulfonyl group in the above general formula (I), R ² and R ³ R ⁵ and R ⁶ each independently represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group; R ⁷ and R ⁸ each independently represent an alkyl group or an aryl group; , R ⁹ , R ¹⁰ , and R ¹¹ represent a hydrogen atom, or a tautomer thereof.