TW201319741A - Colored curable composition, color filter and method of producing the same, display apparatus, and solid-state imaging device - Google Patents

Abstract

This invention provides a colored curable composition for forming a colored film for maintaining good pattern formation and excellent hue for a long period of time even in a high-temperature treatment. The colored curable composition contains a dye (A), a binder resin (B), and an organic solvent (C), wherein the binder resin (B) contains at least one structural unit (b-1) represented by the formula (1) and formula (2), and a structural unit (b-2) having an acid group, and the acid value of the binder resin (B) is in a range of 150 to 300 mgKOH/g. In formula (1), R11 represents hydrogen atom or methyl group, R12 and R13 represent hydrogen atom or a carbonyl group having carbon number 3 to 20 and containing unsaturated double bond as a partial structure, and a condition that R12 and R13 are both hydrogen atoms is excluded. In formula (2), R20 represents hydrogen atom or methyl group, and R21 to R25 represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group.

Description

Colored curable composition, color filter, method for producing the same, display element, and solid-state imaging element

The present invention relates to a coloring curable composition, a color filter using the colored curable composition, a method for producing the same, and a display element and a solid-state imaging device including the color filter.

The pigment dispersion method is widely used as a display element such as a liquid crystal display element, an organic electroluminescence (EL) display element, or a color filter used in a solid-state imaging device or the like. As the pigment dispersion method, there is a method of producing a color filter by photolithography using a colored radiation-sensitive composition obtained by dispersing a pigment in various photosensitive compositions. In this method, since the colored radiation-sensitive composition contains a pigment, it is stable to light or heat, and since it is patterned by photolithography, positional accuracy can be sufficiently ensured, and it is considered to be suitable for production. A method of using a color filter or the like for a color display.

The coloring compounds used in the production of color filters are not only pigmented, but also pigment compounds other than pigments such as dyes have been extensively studied. Among them, dyes are known to have various dye precursors such as pyrromethene dyes, pyrimidine azo dyes, pyrazole azo dyes, xanthene dyes, and the like, and by using various dyes, For example, a technique in which a pyrromethene dye is used together with a dye having a phthalocyanine structure to obtain high color purity is known (for example, refer to Japanese Laid-Open Patent Publication No. 2008-292970).

It is considered that when a dye is used as the coloring compound, the hue or brightness of the image to be displayed when the image is displayed can be improved by the color purity of the dye itself or the vividness of the hue, which is useful. However, the current state of the art is that in color filters using dyes, dyes as colorants generally have lower storage stability than pigments, and are still stable in hue stability in high temperature treatment such as durability and post-baking steps. There is room for improvement.

As described above, when a color filter is produced using a dye as a coloring agent, there is a problem that sufficient contrast, hue durability, and high-temperature treatment property cannot be obtained.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a color-curable composition which can maintain excellent pattern formability and which can be excellent for a long period of time even when subjected to high-temperature treatment or the like. The color film of the hue. Further, a further object of the present invention is to provide a color filter which is excellent in hue and excellent in durability, and which is suitable for use in a display element or a solid-state imaging element, and a display method thereof, and a display image. A display element having excellent color tone and excellent display characteristics or a solid-state imaging element excellent in color separation.

Specific forms of the invention are as follows.

<1> A colored curable composition comprising: (A) a dye; (B) a binder resin comprising a structural unit represented by the following formula (1) and a formula (2) At least one structural unit (b-1) of the structural unit represented, and the structural unit (b-2) having an acidic group, and having an acid value in the range of 150 mgKOH/g to 300 mgKOH/g; and (C) Organic solvents;

In the above formula (1), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² and R ¹³ each independently represent a hydrogen atom or a carbon group having a carbon number of 3 to 20 containing an unsaturated double bond as a partial structure, and R ¹² is absent. And R ¹³ are both hydrogen atoms; when at least one of R ¹² and R ¹³ represents a carbon group having 3 to 20 carbon atoms which contains an unsaturated double bond as a partial structure, a carboxyl group may be further included as a partial structure;

In the above formula (2), R ²⁰ represents a hydrogen atom or a methyl group, and R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group.

<2> The color hardening composition according to <1>, wherein the (A) dye contains at least one selected from the group consisting of a compound represented by the following formula (I) which is coordinated to a metal atom or a metal compound. Metal complex dye (a-1), and dye (a-2) represented by the following formula (II);

In the formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a hetero atom. Ring base

In the above formula (II), R ^a , R ^b , R ^c , R ^d , R ^e , R ^f , R ^g , R ^h , R ⁱ , R ^j , R ^k , R ^l , R ^m , R ⁿ , R ^o and R ^p each independently represent a hydrogen atom or a monovalent substituent, and R ^a , R ^b , R ^c , R ^d , R ^e , R ^f , R ^g , R ^h , R ⁱ , R ^j , R are absent. ^{When k} , R ^l , R ^m , R ⁿ , R ^o and R ^{p are} all a hydrogen atom or a halogen atom.

<3> The colored curable composition according to <1> or <2>, wherein the (B) binder resin is contained in an amount of 0.1 part by mass to 20 parts by mass based on 1 part by mass of the (A) dye.

The colored hardening composition according to any one of the above (1), wherein the (B) binder resin is selected from the group consisting of the following general formula (1) and the following general formula (2) The molar ratio of at least one structural unit (b-1) to the structural unit (b-2) having an acidic group is 1:0.1 to 1:3.

The colored hardening composition according to any one of <1> to <4> wherein the (B) binder resin further comprises the structural unit (b-1) and the structural unit having an acidic group. (b-2) Structural units with different structures.

The colored hardening composition according to any one of the above-mentioned (a-1), wherein the (a-1) metal complex dye is a compound represented by the following formula (I-2) :[化5]

In the above formula (I-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent hydrogen. An atom or a monovalent substituent; R ⁷ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group; and Ma represents a metal atom or a metal compound.

The colored hardening composition according to any one of <1> to <6> further comprising a polymerizable compound different from the (B) binder resin structure.

<8> A color filter comprising: a support; and a colored region formed by using the colored curable composition according to any one of <1> to <7>.

<9> A method of producing a color filter, comprising the step of applying a color hardening composition according to any one of <1> to <7> on a support to form a coloring layer; The formed colored layer is exposed to a pattern and developed to form a colored region.

<10> A display element comprising the color filter of <8> or a color filter manufactured by the method of <9>.

<11> A solid-state photographic element comprising the color filter of <8> or a color filter manufactured by the method of <9>.

Although the effects of the present invention are not clear, they are considered as follows.

In the color hardening composition of the present invention, since the binder resin having a high acid value and having a specific acidic group and a crosslinkable group is contained, it is between the acid group of the binder resin and the dye such as the metal complex dye. A good interaction is formed to improve the storage stability of the dye. When the dye which is uniformly fixed to the binder by the interaction imparts energy to the colored curable composition and hardens the composition, it is stably contained in the hardening by the function of the crosslinkable group in the binder. In the film, for example, even when a high-temperature treatment such as a post-baking step is performed, it is possible to effectively suppress a hue change or a decrease in brightness due to decomposition of a dye or the like. Further, it is considered that since the acid value of the binder resin is high, the uncured region is excellent in removability, and excellent pattern formability can be exhibited.

According to one aspect of the present invention, it is possible to provide a color-curable composition capable of maintaining good pattern formability and maintaining excellent hue for a long period of time even when high-temperature treatment or the like is performed. Color film.

Further, according to another aspect of the present invention, it is possible to provide a color filter which is excellent in hue and excellent in durability, and which is suitable for use in a display element or a solid-state imaging element, and a manufacturer thereof, using the above-described colored curable composition of the present invention. The method and the display element having excellent color tone and excellent display characteristics, or a solid-state imaging element excellent in color separation property.

Hereinafter, the color hardening composition of the present invention will be described in detail, and a color filter, a method for producing the same, and a liquid crystal display device which also use the colored curable composition will be described in detail.

Colored hardening composition

The color hardening composition of the present invention contains: (A) a dye; (B) a binder resin (hereinafter, suitably referred to as (B) a specific binder), which is selected from the group consisting of the following formula (1) a structural unit (b-1) having at least one of a structural unit and a structural unit represented by the following formula (2) having a crosslinkable group, and a structural unit (b-2) having an acidic group, and having an acid value of 150 mg KOH / g ~ 300 mg KOH / g; and (C) organic solvent.

The colored curable composition of the present invention may further contain a photopolymerization initiator, a polymerizable compound different in structure from the component (B), and various additives as needed.

Hereinafter, each component constituting the colored curable composition of the present invention will be described in detail. In the following, the colored curable composition of the present invention may be simply referred to as "the colored composition of the present invention" or "colored composition".

In addition, in this specification, the numerical range represented by "~" is a range in which the numerical value described before and after "~" is included as a lower limit and an upper limit.

In the present specification, "alkyl group" is a generic term for "linear, branched, and cyclic" alkyl groups.

Further, the substituent (atomic group) in the present specification includes an unsubstituted group and a more substituted group. That is, in the present specification, the "alkyl group" includes an unsubstituted alkyl group and a substituted alkyl group, and the other substituents are also the same.

Hereinafter, each component constituting the colored curable composition of the present invention will be described in detail.

(A) dye

The colored curable composition of the present invention contains at least one dye.

In the present invention, the term "dye" is used to dissolve 1% by mass or more of a coloring agent in an organic solvent selected from the group consisting of an alkylene glycol ether solvent, an ester solvent, and a ketone solvent. The "dye" in the invention is distinguished from the pigment as an organic solvent-insoluble colorant. The dye used in the present invention is not particularly limited as long as it satisfies the above physical properties, and a metal complex dye can be preferably used from the viewpoint of the interaction formation property of the specific binder (B) to be described later.

In addition, the metal complex dye in the present invention is a dye-missing compound having a metal as a central element, and is a dye-miscible compound which is dissolved in the above-mentioned organic solvent in an amount of 1% by mass or more, and is characterized by spectroscopic characteristics and heat resistance. Excellent sex. By providing the (A) dye, preferably a metal complex dye, and the (B) binder resin described below, a color-curable composition capable of forming a colored cured film excellent in hue and heat resistance can be obtained.

The metal complex dye in the present invention may be a complex compound in which the dye compound is coordinated centering on a metal atom or a metal compound, and specifically, a dipyrromethene compound (dipyrromethene) may be mentioned. Metal complex compounds), phthalocyanine metal complex compounds, and the like.

Dipyrromethene metal complex compound

The preferred dye which can be contained in the colored photosensitive composition of the present invention is represented by the following general formula (I) from the viewpoint of the brightness of the color filter produced by coloring the photosensitive composition. The structure is a compound which is coordinated to a metal atom or a metal compound (hereinafter, referred to as "dipyrromethene metal compound" as appropriate).

In the formula (I), R ¹ to R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group.

Hereinafter, a metal-substituted compound (dipyrromethene metal-substituted compound) in which a structure represented by the formula (I) is bonded to a metal atom or a metal compound will be described in detail.

The monovalent substituent in the formula (I) represents a halogen atom (for example, a fluorine atom, a chlorine atom or a bromine atom), an alkyl group (preferably having a carbon number of 1 to 48, more preferably a carbon number of 1). The linear, branched or cyclic alkyl group of 24 may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group. 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl or 1-adamantyl), alkenyl (preferably carbon number 2~) 48. More preferably, the alkenyl group having 2 to 18 carbon atoms may, for example, be a vinyl group, an allyl group or a 3-buten-1-yl group, or an aryl group (preferably having a carbon number of 6 to 48, more preferably Examples of the aryl group having 6 to 24 carbon atoms include a phenyl group or a naphthyl group, and a heterocyclic group (preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms), and examples thereof include: 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl or benzotriazole-1- a decyl group (preferably a decyl group having a carbon number of 3 to 38, more preferably a carbon number of 3 to 18, and examples thereof include a trimethyl decyl group and a triethyl decyl group; Tributyl decyl, tert-butyldimethyl decyl or trihexyl dimethyl decyl), hydroxy, cyano, nitro, alkoxy (preferably from 1 to 48, more preferably Examples of the alkoxy group having 1 to 24 carbon atoms include a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, an isopropoxy group, a third butoxy group, and a dodecyloxy group. Or a cycloalkoxy group such as a cyclopentyloxy group or a cyclohexyloxy group, or an aryloxy group (preferably an aryloxy group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms), and examples thereof include a phenoxy group. Or 1-naphthyloxy), a heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms), for example, 1-phenyltetrazole-5-oxygen a base or a 2-tetrahydropyranyloxy group, a decyloxy group (preferably a decyloxy group having a carbon number of 1 to 32, more preferably a carbon number of 1 to 18, for example) Examples thereof include a trimethyldecyloxy group, a tert-butyldimethylsilyloxy group or a diphenylmethyldecyloxy group, and a decyloxy group (preferably having a carbon number of 2 to 48, more preferably a carbon number). Examples of the nonyloxy group of 2 to 24 include an ethoxycarbonyl group, a pivaloyloxy group, a benzhydryloxy group or a dodecyloxy group, and an alkoxycarbonyloxy group. The alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, may, for example, be an ethoxycarbonyloxy group, a third butoxycarbonyloxy group or a cyclohexyloxycarbonyloxy group. a cycloalkyloxycarbonyloxy group, an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms), for example, phenoxycarbonyl Oxyl), carbamoyloxy group (preferably a carbamethoxy group having a carbon number of 1 to 48, more preferably 1 to 24 carbon atoms, for example, N,N-dimethylamine Methoxyoxy, N-butylamine methyl methoxy, N-phenylamine methyl methoxy or N-ethyl-N-phenylamine methyl methoxy, sulfonyloxy (preferably The sulfonyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N,N-diethylaminesulfonyloxy or N-propylaminesulfonyloxy), an alkane The sulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, for example, a methylsulfonyloxy group or a hexadecylsulfonyloxy group; Or a cyclohexylsulfonyloxy group, an arylsulfonyloxy group (preferably an arylsulfonyloxy group having a carbon number of 6 to 32, more preferably a carbon number of 6 to 24, and examples thereof include a phenylsulfonyloxy group; Base group, sulfhydryl group (preferably a sulfhydryl group having a carbon number of 1 to 48, more preferably a carbon number of 1 to 24, and examples thereof include a methyl group, an ethyl group, a pivaloyl group, and a benzene group. An alkoxycarbonyl group having a carbon number of 2 to 48, more preferably a carbon number of 2 to 24, and a methoxy group, for example, a methoxy group (for example, a fluorenyl group, a tetradecylmercapto group or a cyclohexyl group). Carbonyl, ethoxycarbonyl, eighteen Alkoxycarbonyl, cyclohexyloxycarbonyl or 2,6-di-t-butyl-4-methylcyclohexyloxycarbonyl), aryloxycarbonyl (preferably having a carbon number of 7 to 32, more preferably Examples of the aryloxycarbonyl group having 7 to 24 carbon atoms include a phenoxycarbonyl group and an amine carbenyl group (preferably a carbohydrin group having a carbon number of 1 to 48, more preferably a carbon number of 1 to 24, for example, There may be mentioned: an aminomethyl group, N,N-diethylamine, a N-ethyl-N-octylamine, a N,N-dibutylamine, a N-propyl group, an N-propyl group. Aminomethyl sulfhydryl, N-phenylamine methyl hydrazino, N-methyl-N-phenylamine methyl hydrazino or N,N-dicyclohexylamine fluorenyl), an amine group (preferably having a carbon number of less than An amine group equal to 32, more preferably a carbon number of 24 or less, and examples thereof include an amine group, a methylamino group, an N,N-dibutylamino group, a tetradecylamino group, and a 2-ethylhexylamine. Or a cyclohexylamino group, an anilino group (preferably an anthranyl group having 6 to 32 carbon atoms, more preferably 6 to 24, for example, an anilino group or an N-methylanilino group) or a heterocyclic amino group ( Preferably, the heterocyclic amino group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, 4-pyridylamino group, and the carbenamine group (preferably having a carbon number of 2 to 48, more preferably 2~24 methionine, for example For example, an acetamino group, a benzylamino group, a tetradecyl guanylamino group, a pentyl guanidino group or a cyclohexylamino group, a urea group (preferably a carbon number of 1 to 32, more) Examples of the urea group having a carbon number of 1 to 24 include, for example, a urea group or an N,N-dimethylureido group, an N-phenylureido group, and a quinone imine group (preferably having a carbon number of 36 or less). More preferably, the quinone imine group having a carbon number of 24 or less may, for example, be an N-succinimide group or an N-phthalimido group or an alkoxycarbonylamine. The base (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, a methoxycarbonylamino group, an ethoxycarbonylamino group, a third butoxy group; a carbonylamino group, an octadecyloxycarbonylamino group or a cyclohexyloxycarbonylamino group), An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, for example, a phenoxycarbonylamino group) or a sulfonylamino group (more preferably The sulfonamide group having a carbon number of 1 to 48, more preferably 1 to 24 carbon atoms, for example, may be exemplified by: methanesulfonylamino, butylsulfonylamino, benzenesulfonylamino, hexadecanesulfonamide Or a sulfonylamino group, an aminesulfonylamino group (preferably a sulfonylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N, N -dipropylaminesulfonylamino, or N-ethyl-N-dodecylamaminesulfonylamino), azo (preferably having a carbon number of from 1 to 32, more preferably a carbon number of 1) Examples of the azo group of ~24 include a phenylazo group or a 3-pyrazolylazo group, and an alkylthio group (preferably a carbon number of 1 to 48, more preferably an alkyl group having 1 to 24 carbon atoms). Examples of the sulfur group include a methylthio group, an ethylthio group, an octylthio group or a cyclohexylthio group, and an arylthio group (preferably, an arylthio group having a carbon number of 6 to 48, more preferably a carbon number of 6 to 24). Examples thereof include a phenylthio group and a heterocyclic thio group (preferably a heterocyclic thio group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms), and examples thereof include a 2-benzothiazolylthio group. 2-pyridylthio or 1 -Phenyltetrazolylthio), alkylsulfinyl (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, dodecyl group a sulfinyl group, an arylsulfinyl group (preferably, an arylsulfinyl group having a carbon number of 6 to 32, more preferably a carbon number of 6 to 24, for example, a phenylsulfinyl group) The alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl) , butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl or cyclohexylsulfonyl), arylsulfonyl (preferably carbon number 6 to 48, more preferably carbon number Examples of the arylsulfonyl group of 6 to 24 include a phenylsulfonyl group or a 1-naphthylsulfonyl group, and an aminesulfonyl group (preferably having a carbon number of 32 or less, more preferably a carbon number of less than or equal to The amidoxime group of 24 may, for example, be an amine sulfonyl group, N,N-dipropylamine sulfonyl group, N-ethyl-N-dodecylamine sulfonyl group, N-ethyl-N. - phenylamine sulfonyl group or N-cyclohexylamine sulfonyl group), sulfo group, phosphinium group (preferably a phosphinium group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms), for example, : phenoxyphosphonium fluorenyl, octyloxyphosphonium or phenylphosphonium fluorenyl), phosphinylamino group (preferably a phosphinylamine having a carbon number of 1 to 32, more preferably a carbon number of 1 to 24) The base may, for example, be diethoxyphosphinylamino or dioctyloxyphosphonylamino).

When the above monovalent substituent is a group which may be further substituted, it may be further substituted by any of the above groups. Further, when there are two or more further substituents, the substituents may be the same or different.

In the general formula (I), R ¹ and R ² may be bonded to each other to form a ring of 5 members, 6 members or 7 members, and R ² and R ³ may be bonded to each other to form 5 members, 6 members or 7 members. Rings, R ⁴ and R ⁵ may be bonded to each other to form a ring of 5 members, 6 members or 7 members, and R ⁵ and R ⁶ may be bonded to each other to form a ring of 5 members, 6 members or 7 members. Further, as the ring to be formed, either a saturated ring or an unsaturated ring may be used. Examples of the saturated or unsaturated ring of the 5-member, the 6-membered member or the 7-membered member include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, and a pyrrole. The pyridine ring, the piperidine ring, the cyclopentene ring, the cyclohexene ring, the benzene ring, the pyridine ring, the pyrazine ring, and the pyridazine ring are preferably a benzene ring or a pyridine ring.

In addition, when the formed 5, 6 and 7 members of the ring can be further When the group to be substituted is substituted with any one of the groups exemplified as the monovalent substituent in the above formula (I), in the case of being substituted by two or more substituents, These substituents may be the same or different.

Further, in the formula (I), R ⁷ represents a halogen atom, an alkyl group, an aryl group or a heterocyclic group. The halogen atom, alkyl group, aryl group or heterocyclic group represented by R ⁷ has the same meaning as the halogen atom, alkyl group, aryl group or heterocyclic group of the above R ¹ to R ⁶ in the formula (I), and is preferably. The range is also the same as the preferred range of the halogen atom, the alkyl group, the aryl group or the heterocyclic group as the above R ¹ to R ⁶ .

In the general formula (I), as R ¹ and R ⁶ , among the above, an alkylamino group, an arylamine group, a formamidine group, a ureido group, a guanidino group, an alkoxycarbonyl group is preferred. Or a sulfonamide group, more preferably a formamidine, a ureido group, an alkoxycarbonylamino group or a sulfonylamino group, and more preferably a formamidine group, a ureido group, an alkoxycarbonylamino group or a sulfonium group. An amine group, particularly preferably a formamidine or a urea group.

In the general formula (I), as R ² and R ⁵ , among the above, preferred are alkoxycarbonyl, aryloxycarbonyl, aminecarbenyl, alkylsulfonyl, arylsulfonyl, nitrile. , anthracenylene or an amine-mercaptosulfonyl group, more preferably an alkoxycarbonyl group, an aryloxycarbonyl group, an amine carbaryl group, an alkylsulfonyl group, a nitrile group, a quinone imine group or an amine mercapto group Sulfhydryl, more preferably alkoxycarbonyl, aryloxycarbonyl, aminemethanyl, nitrile, oxime imine or amine carbaryl sulfonyl, particularly preferably alkoxycarbonyl, aryloxy Carbonyl or amine carbenyl.

In the formula (I), as R ³ and R ⁴ , among them, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic ring is preferred. More preferably, it is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group.

In the formula (I), the alkyl group when R ³ and R ⁴ represent an alkyl group is preferably a linear, branched or cyclic substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. More specifically, for example, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, and ring may be mentioned. Hexyl and benzyl. The alkyl group is more preferably a branched or cyclic substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, and more specifically, for example, isopropyl group, cyclopropyl group, isobutyl group, and the like. Tributyl, cyclobutyl, cyclopentyl, cyclohexyl, more preferably a secondary or tertiary substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, more specifically, for example, Propyl, cyclopropyl, isobutyl, tert-butyl, cyclobutyl, cyclohexyl.

In the formula (I), as the aryl group when R ³ and R ⁴ represent an aryl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group is preferable, and more preferably A substituted or unsubstituted phenyl group.

In the general formula (I), as the heterocyclic group in the case where R ³ and R ⁴ represent a heterocyclic group, a substituted or unsubstituted 2-thienyl group, a substituted or unsubstituted 4- is preferable. Pyridyl, substituted or unsubstituted 3-pyridyl, substituted or unsubstituted 2-pyridyl, substituted or unsubstituted 2-furyl, substituted or unsubstituted 2-pyrimidinyl , substituted or unsubstituted 2-benzothiazolyl, substituted or unsubstituted 1-imidazolyl, substituted or unsubstituted 1-pyrazolyl, substituted or unsubstituted benzotrien The azole-1-yl group is more preferably a substituted or unsubstituted 2-thienyl group, a substituted or unsubstituted 4-pyridyl group, a substituted or unsubstituted 2-furyl group, substituted or not Substituted 2-pyrimidinyl, substituted or unsubstituted 1-pyridyl.

Next, a metal atom or a metal compound which forms a dipyrromethene metal complex compound will be described.

As the metal or metal compound, any metal atom or metal compound which can form a complex compound may be used, including a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide or a divalent metal chloride. Compound. For example, in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., also includes AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ a metal chloride such as GeCl ₂ , a metal oxide such as TiO or VO, or a metal hydroxide such as Si(OH) ₂ .

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

A preferred form of the dipyrromethene metal-doped compound in which the structure represented by the formula (I) is coordinated to a metal atom or a metal compound is shown below.

That is, a preferred form of the dipyrromethene metal compound is exemplified by the following formula: In the formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, an alkyl group, an alkenyl group or an aromatic group. Base, heterocyclic group, decyl group, hydroxy group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, fluorenyl group, alkoxycarbonyl group, amine carbaryl group, amine group, anilino group, heterocyclic amino group , mercaptoamine, ureido, oximine, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, azo, alkylthio, arylthio, heterocyclic thio, Alkylsulfonyl, arylsulfonyl or phosphinylamino; R ² and R ⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a cyanyl group Base, nitro, alkoxy, aryloxy, heterocyclooxy, decyl, alkoxycarbonyl, aryloxycarbonyl, aminecarboxamido, oximeimido, alkoxycarbonylamino, sulfonium sulfonate Amino, azo, alkylthio, arylthio, heterocyclothio, alkylsulfonyl, arylsulfonyl or aminesulfonyl; R ³ and R ⁴ are each independently a hydrogen atom; Halogen atom, alkyl group, alkenyl group, aryl group Heterocyclyl, decyl, hydroxy, cyano, alkoxy, aryloxy, heterocyclooxy, decyl, alkoxycarbonyl, amidyl, anilino, carbamide, ureido, hydrazine Imino, alkoxycarbonylamino, sulfonylamino, azo, alkylthio, arylthio, heterocyclic thio, alkylsulfonyl, arylsulfonyl, amine sulfonyl or A phosphinylamino group; R ⁷ is represented by a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group; a metal atom or a metal compound is Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni , Co, TiO, B or VO.

A more preferred form of the dipyrromethene metal complex compound is shown below.

That is, a more preferable form of the dipyrromethene metal-doped compound may be exemplified by the following formula: In the formula (I), R ¹ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, and an aromatic group. Base, heterocyclic group, cyano group, fluorenyl group, alkoxycarbonyl group, amine carbenyl group, amine group, heterocyclic amine group, formamidine group, ureido group, quinone imine group, alkoxycarbonylamino group, Aryloxycarbonylamino, sulfonylamino, azo, alkylsulfonyl, arylsulfonyl or phosphinylamino; R ² and R ⁵ are each independently alkyl, alkenyl, Aryl, heterocyclic, cyano, nitro, fluorenyl, alkoxycarbonyl, aryloxycarbonyl, aminemethantyl, quinone imine, alkylsulfonyl, arylsulfonyl or amine sulfonate The fluorenyl group; R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a decyl group, an alkoxycarbonyl group, an amine carbaryl group, a formamidine group, Urea, sulfhydrido, alkoxycarbonylamino, sulfonylamino, alkylthio, arylthio, heterocyclic thio, alkylsulfonyl, arylsulfonyl or sulfonyl ; R ^{7 is} a hydrogen atom, a halogen atom, an alkyl group, an aryl group or The heterocyclic group is represented by a metal atom or a metal compound represented by Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B or VO.

The preferred form of the dipyrromethene metal-doped compound in which the structure represented by the formula (I) is coordinated to a metal atom or a metal compound is exemplified by the following formula (I-1) and formula (I). -2) and a compound represented by the formula (I-3).

[Chemistry 7]

In the formula (I-1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. Ma represents a metal atom or a metal compound, X ¹ represents a group bondable to Ma, and X ² represents a group required to neutralize the charge of Ma. Further, X ¹ and X ² may be bonded to each other to form a ring of 5 members, 6 members or 7 members together with Ma.

R ¹ to R ⁶ in the formula (I-1) are synonymous with R ¹ to R ⁶ in the formula (I), respectively, and the preferred forms are also the same.

The metal in the formula (I-1) represents a metal atom or a metal compound, and the metal atom or metal compound in the above "the compound represented by the formula (I) is complexed with a metal atom or a metal compound". Synonymous, the preferred range is also the same.

R ⁷ of formula (I-1) in general formula (I) in the same meaning as R ^7, preferred are also the same type.

X ¹ in the formula (I-1) may be any group which may be bonded to Ma, and may be derived from water, an alcohol (for example, methanol, ethanol, propanol) or the like. Metal Chelate" [1] Sakaguchi Takeshi, Ueno Jingping (1995 Nanjiang Hall), "Metal Chelate" [2] (1996), "Metal Chelate" [3] (1997), etc. A group of the compounds described. Among them, in terms of production, water, a carboxylic acid compound, an alcohol, an amine compound, and a guanamine compound are preferable, and water, a carboxylic acid compound, and a guanamine compound are more preferable.

X ² in the formula (I-1) represents a group required for neutralizing the charge of Ma, and represents, for example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxyl group, and an aliphatic quinone imine. (For example, succinimide, maleimide, glutarimide or diethylamine may be mentioned, and amber or imine or cis is preferred. a monovalent group of butenyleneimine) derived from an aromatic quinone imine group or a heterocyclic quinone imide (for example, phthalimide, naphthyl imine, 4-bromo neighbor) Benzoquinone imine, 4-methylphthalimide, 4-nitrophthalimide, naphthoquinone imine or tetrabromophthalimide, preferably The monovalent group of o-xylylene imine, 4-bromophthalimide or 4-methylphthalimide is derived from an aromatic carboxylic acid (for example, Benzoic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid, 4-methoxybenzoic acid, 4-chlorobenzoic acid, 2-naphthoic acid, salicylic acid, 3,4,5-trimethoxy Benzoic acid, 4-heptyloxybenzoic acid or 4-tert-butylbenzoic acid, etc. The monovalent group of benzoic acid, 4-methoxybenzoic acid, or salicylic acid may be mentioned, and it may be derived from an aliphatic carboxylic acid (for example, formic acid, acetic acid, acrylic acid, methacrylic acid, acetic acid) (ethanoic acid), propionic acid, lactic acid, trimethylacetic acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, neodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, isohard Fatty acid, 2-hexadecyl octadecanoic acid, 2-hexyl decanoic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, 5-norbornene-2-carboxylic acid or 1-adamantanecarboxylic acid, etc. A monovalent group of acetic acid, methacrylic acid, lactic acid, trimethylacetic acid, 2-ethylhexanoic acid or stearic acid, etc., derived from dithiocarbamic acid (for example, dimethyl group is exemplified) A monovalent group of dithiocarbamic acid, diethyldithiocarbamic acid or dibenzyldithiocarbamic acid derived from a sulfonamide (for example, benzenesulfonamide, 4-chloro Phenylsulfonamide, 4-methoxybenzenesulfonamide, 4-methylbenzenesulfonamide, 2-methylbenzenesulfonamide or methanesulfonamide, preferably benzenesulfonamide or methanesulfonate Monovalent group of guanamine, derived from hydroxamic acid (eg There may be mentioned a monovalent group of an oxonium hydroxamic acid, a octyl hydroxamic acid or a phenyl hydroxamic acid, which is derived from a nitrogen-containing cyclic compound (for example, carbendazim, 1-benzyl-5-ethoxyl) Urethane, 1-allyl carbendazim, 5,5-diphenylethylene carbazide, 5,5-dimethyl-2,4-oxazolidinedione, barbituric acid , imidazole, pyrazole, 4,5-dicyanoimidazole, 4,5-dimethylimidazole, benzimidazole or diethyl 1H-imidazole-4,5-dicarboxylate, etc., preferably exemplified by 1- Benzyl-5-ethoxyethyl carbazide, 5,5-dimethyl-2,4-oxazolidinedione, 4,5-dicyanoimidazole or 1H-imidazole-4,5-dicarboxylic acid Monovalent group of diethyl ester).

Among them, in terms of production, X ^{2 is} preferably a halogen atom, an aliphatic carboxylic acid group, an aromatic carboxylic acid group, an aliphatic quinone imine group, an aromatic fluorenylene group, a sulfonic acid group, or a nitrogen-containing ring compound. More preferably, it is a hydroxyl group, an aliphatic carboxylic acid group, an aromatic quinone imine group, and a nitrogen-containing ring compound.

X ¹ and X ² in the formula (I-1) may be bonded to each other to form a ring of 5 members, 6 members or 7 members together with Ma. The formed ring of 5 members, 6 members and 7 members may be a saturated ring or an unsaturated ring. Further, the ring of 5 members, 6 members, and 7 members may be composed only of a carbon atom and a hydrogen atom, or may be a hetero ring having at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom.

In the formula (I-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent hydrogen. Atom or a monovalent substituent. R ⁷ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. Ma represents a metal atom or a metal compound.

R ¹ to R ⁶ in the formula (I-2) have the same meanings as R ¹ to R ⁶ in the formula (I), and the preferred forms are also the same.

The monovalent substituent represented by R ⁸ to R ¹³ in the formula (I-2) is synonymous with the monovalent substituent represented by R ¹ to R ⁶ of the compound represented by the formula (I), and is preferably a group. The type is also the same. When the monovalent substituent represented by R ⁸ to R ¹³ of the compound represented by the formula (I-2) is a group which may be further substituted, it may be used as a monovalent substituent in the above formula (I). Whereas any of the exemplified groups are substituted, when substituted by two or more substituents, the substituents may be the same or different.

General formula R (I-2) ⁷ with formula (I) in the same meaning as R ^7, preferred are also the same type.

R ¹⁴ in the formula (I-2) represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group, and a preferred range of R ¹⁴ is the same as the above preferred range of R ⁷ . When R ¹⁴ is a group which may be further substituted, it may be substituted by any one of the groups exemplified as the monovalent substituent in the above formula (I), when substituted by two or more When the group is substituted, the substituents may be the same or different.

In the formula (I-2), Ma represents a metal or a metal compound, and is synonymous with a metal atom or a metal compound in the above "the compound represented by the formula (I) is a complex of a metal atom or a metal compound". And the preferred range is also the same.

R ⁸ and R ⁹ in the formula (I-2) may be bonded to each other to form a saturated or unsaturated ring of 5, 6 or 7 members, and R ⁹ and R ¹⁰ may be bonded to each other to form 5 members. 6 or 7 members of the saturated or unsaturated ring, R ¹¹ and R ¹² may be bonded to each other to form a saturated or unsaturated ring of 5, 6 or 7 members, and R ¹² and R ¹³ may be bonded to each other. Form a saturated or unsaturated ring of 5, 6 or 7 members. As the saturated or unsaturated ring formed, it is synonymous with a saturated ring or an unsaturated ring formed by R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ or R ⁵ and R ⁶ , and preferred examples The same is true.

In the formula (I-3), R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic ring. base. R ⁸ and R ⁹ each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group or a heterocyclic amino group. Ma represents a metal atom or a metal compound. X ³ and X ⁴ each independently represent NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group or an arylsulfonyl group), an oxygen atom or a sulfur atom. . Y ¹ and Y ² each independently represent NRb (Rb represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group or an arylsulfonyl group), an oxygen atom or a sulfur atom. Or a carbon atom. X ⁵ represents a group bondable to Ma, and a represents 0, 1, or 2. R ⁸ and Y ¹ may be bonded to each other to form a ring of 5 members, 6 members or 7 members, and R ⁹ and Y ² may be bonded to each other to form a ring of 5 members, 6 members or 7 members.

R ² to R ⁵ and R ⁷ in the formula (I-3) have the same meanings as R ² to R ⁵ and R ⁷ in the formula (I), and the preferred forms are also the same.

In the general formula (I-3), Ma represents a metal or a metal compound, and is synonymous with a metal atom or a metal compound in which a compound represented by the above formula (I) is coordinated to a metal atom or a metal compound, and The preferred range is also the same.

In the formula (I-3), R ⁸ and R ⁹ each independently represent an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, for example, There may be mentioned methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, and ring. A hexyl group or a 1-adamantyl group, an alkenyl group (preferably an alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12), and examples thereof include a vinyl group, an allyl group or a 3-buten-1-yl group. And an aryl group (preferably, an aryl group having 6 to 36 carbon atoms, more preferably 6 to 18, for example, a phenyl group or a naphthyl group) or a heterocyclic group (preferably having a carbon number of 1 to 24, more preferably) Examples of the heterocyclic group of 1 to 12 include a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, a 2-pyrimidinyl group, a 1-pyridyl group, a 2-benzothiazolyl group, and a 1-imidazolyl group. 1-pyrazolyl or benzotriazol-1-yl), alkoxy (preferably an alkoxy group having 1 to 36 carbon atoms, more preferably 1 to 18), and examples thereof include a methoxy group and an ethoxy group. a group, a propoxy group, a butoxy group, a hexyloxy group, a 2-ethylhexyloxy group, a dodecyloxy group or a cyclohexyloxy group), an aryloxy group (preferably having a carbon number of 6 to 24, more preferably 6 to 18 aryloxy groups, for example Examples thereof include a phenoxy group or a naphthyloxy group, and an alkylamino group (preferably an alkylamino group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms, and examples thereof include a methylamino group, an ethylamine group, and a propylamine group. , butylamino, hexylamino, 2-ethylhexylamino, isopropylamino, tert-butylamino, trioctylamino, cyclohexylamino, N,N-diethylamino, N, N-dipropylamino, N,N-dibutylamino or N-methyl-N-ethylamino), arylamine (preferably aryl having 6 to 36, more preferably 6 to 18) The amine group may, for example, be a phenylamino group, a naphthylamino group, an N,N-diphenylamino group or an N-ethyl-N-phenylamino group or a heterocyclic amino group (preferably a carbon number). The heterocyclic amino group of 1 to 24, more preferably 1 to 12, may, for example, be a 2-aminopyrrolyl group, a 3-aminopyrazolyl group, a 2-aminopyridyl group or a 3-aminopyridyl group.

In the formula (I-3), an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group or a heterocyclic ring represented by R ⁸ and R ⁹ . When the amine group is a group which may be further substituted, it may be substituted by any one of the above groups represented by the above R ⁸ or R ⁹ , and when substituted by two or more substituents, The substituents may be the same or different.

In the formula (I-3), X ³ and X ⁴ each independently represent NRa, an oxygen atom or a sulfur atom. Ra represents a hydrogen atom or an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group and a different alkyl group. Propyl, butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl or 1-adamantyl), alkenyl (comparative The alkenyl group having preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, for example, a vinyl group, an allyl group or a 3-buten-1-yl group, or an aryl group (preferably having a carbon number of 6 to 36) More preferably, the aryl group of 6 to 18 is a phenyl group or a naphthyl group, or a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms), and examples thereof include: 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl or benzotriazole-1- Base group, sulfhydryl group (preferably a fluorenyl group having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, for example, an ethyl fluorenyl group, a pentylene group, a 2-ethylhexyl group, a benzamidine group or a ring Alkylsulfonyl group, preferably an alkylsulfonyl group having 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, for example, a methylsulfonyl group, an ethylsulfonyl group, an isopropyl group Sulfonyl or Cyclohexylsulfonyl), arylsulfonyl (preferably an arylsulfonyl group having a carbon number of 6 to 24, more preferably 6 to 18, for example, a phenylsulfonyl group or a naphthylsulfonyl group; ). Further, when Ra may be substituted, it may be further substituted by each of the above groups, and when substituted by a plurality of substituents, the substituents may be the same or different.

X ³ and X ⁴ are each preferably an oxygen atom or a sulfur atom, and X ³ and X ⁴ are each preferably an oxygen atom.

In the formula (I-3), Y ¹ and Y ² each independently represent NRb, a sulfur atom or a carbon atom, and Rb has the same meaning as Ra in the above X ³ .

Y ¹ and Y ² are each independently NRb (wherein Rb may be a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), and Y ¹ and Y ^{2 are} particularly preferably NH.

In the formula (I-3), R ⁸ and Y ¹ may be bonded to each other to form a 5-membered ring (for example, cyclopentane, pyrrolidine or tetrahydrofuran, together with R ⁸ , Y ¹ , and together with the adjacent carbon atoms. Dioxolane, tetrahydrothiophene, pyrrole, furan, thiophene, anthracene, benzofuran or benzothiophene), 6-membered ring (eg cyclohexane, piperidine, piperazine, morphine, tetrahydropyran) , dioxane, pentamethylene sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline or quinazoline) or 7-membered ring (eg cycloheptane or hexamethylene) Imine).

In the formula (I-3), R ⁹ and Y ² may be bonded to each other to form a ring of 5 members, 6 members or 7 members together with R ⁹ and Y ² together with the adjacent carbon atoms. Examples of the ring of the five members, the six members, and the seven members formed include a ring in which one of the rings formed by the above R ⁸ and Y ¹ and a carbon atom is a double bond.

In the general formula (I-3), when a ring of 5 members, 6 members, and 7 members formed by bonding R ⁸ and Y ¹ or R ⁹ and Y ^{2 is} a ring which can be further substituted, it can be used as the above. The group substituted by any one of the groups exemplified in the monovalent substituent in the formula (I) may be the same when substituted by two or more substituents. different.

In the formula (I-3), X ⁵ represents a group bondable to Ma, and examples thereof include the same groups as those of X ² in the above formula (I-1). a represents 0, 1, or 2.

A preferred form of the compound represented by the formula (I-3) is shown below.

That is, a preferred form of the compound represented by the formula (I-3) is a form in which R ² to R ⁵ , R ⁷ , and Ma respectively contain a structure represented by the formula (I) and a metal atom or The complex form of the metal compound (dipyrromethene metal compound) is the same, and X ³ and X ⁴ are each independently NRa (Ra may be exemplified by a hydrogen atom, an alkyl group or a heterocyclic group) or The oxygen atom, Y ¹ and Y ² are each independently NRb (Rb may be a hydrogen atom or an alkyl group), a nitrogen atom or a carbon atom, and X ⁵ is a group bonded via an oxygen atom or a nitrogen atom, R ⁸ and R ⁹ Each independently represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group or an alkylamino group, or R ⁸ and Y ¹ are bonded to each other to form a 5- or 6-membered ring, and R ⁹ and Y ² are bonded to each other. A 5-member, 6-member ring is formed, and a is represented by 0 or 1.

A more preferred form of the compound represented by the formula (I-3) is shown below.

That is, the compound represented by the formula (I-3) is more preferably in the form of R ² to R ⁵ , R ⁷ , and Ma, respectively, and a structure comprising a metal atom or a metal compound represented by the formula (I). The preferred form of the complex (dipyrromethene metal complex compound) is the same; X ³ and X ⁴ are oxygen atoms; Y ¹ is NH; Y ² is a nitrogen atom; X ⁵ is an oxygen atom or via nitrogen An atom-bonded group; R ⁸ and R ⁹ each independently represent an alkyl group, an aryl group, a heterocyclic group, an alkoxy group or an alkylamino group, or R ⁸ and Y ¹ are bonded to each other to form a 5 member or 6 Member ring, R ⁹ and Y ² are bonded to each other to form a 5-member, 6-member ring, and a is represented by 0 or 1.

The preferred form of the dipyrromethene metal complex compound in which the structure represented by the formula (I) is coordinated to a metal atom or a metal compound is the above formula (I-1) and formula (I-2). Among the mismatched compounds represented by the formula (I-3), a particularly preferred form is a compound represented by the above formula (I-3).

Hereinafter, specific examples of the metal-substituted compound (dipyrromethene metal-cobalt compound) in which the compound represented by the above formula (I) used in the present invention is bonded to a metal atom or a metal compound is shown. However, the invention is not limited to the specific examples.

First, the exemplified compound (1) to the exemplified compound (30) are shown.

The exemplified compounds (1) to (30) are compounds represented by the following formula (I-4), and R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , X ¹⁰¹ and M ¹ in the formula (I-4) are as follows The combined compounds shown.

[化10]

Examples of the compound represented by the formula (I-4) include the following examples. The compound (31) to the exemplified compound (45) and the like are shown.

[化15]

[Chemistry 16]

In the exemplified compounds in which the structure represented by the general formula (I) is coordinated to a metal atom or a metal compound (dipyrromethene metal complex compound), the compound (40) to the exemplified compound are exemplified ( 44) is also an exemplified compound of the formula (I-1), and the exemplified compound (45) is also an exemplified compound of the formula (I-2), and the exemplified compound (1) to the exemplified compound (39) are also a formula (I). -3) exemplified compounds.

Examples of the dipyrromethene metal complex compound include the exemplified compound (Ia-3) to the exemplified compound (Ia-83) described in JP-A-2008-292970. ,example The compound (Ia-1) to the exemplified compound (IIa-20), the exemplified compound (I-1) to the exemplified compound (I-36), the exemplified compound (II-1) to the exemplified compound (II-11), and the exemplified Illustrative compounds (III-1) to exemplified compounds (III-103), and exemplified by the exemplified compounds (I-1) to exemplified compounds (I-35) and Japanese Patent No. 3279035 The exemplified compound (2-1) to the exemplified compound (2-32) and the exemplified compound (3-1) described in JP-A-11-256057, the compound (I-1) to the exemplified compound (I-13) ~ exemplified compound (3-32), exemplified compound (4-1) - exemplified compound (4-26), and exemplified compound (5-1) - exemplified compound (5-26), Japanese Patent Laid-Open No. 2005-77953 Illustrative compounds (I-1) to exemplified compounds (I-6), and exemplified compounds (VII-1) to exemplified compounds (VII-8) and Japanese Patent Application Laid-Open No. Hei 11-352686 The compound (1-1) to the exemplified compound (1-45), the exemplified compound (1-1) to the exemplified compound (1-50) described in JP-A-2000-19729, and the Japanese Patent Laid-Open No. 11- The exemplified combination described in 352685 Compound (1-1) to exemplified compound (1-45).

Indigo green metal compound

The phthalocyanine metal-substituted compound is preferably a compound represented by the following formula (II).

[化17]

In the above formula (II), R ^a , R ^b , R ^c , R ^d , R ^e , R ^f , R ^g , R ^h , R ⁱ , R ^j , R ^k , R ^l , R ^m , R ⁿ , R ^o and R ^p each independently represent a hydrogen atom, a halogen atom or a monovalent substituent, R ^a , R ^b , R ^c , R ^d , R ^e , R ^f , R ^g , R ^h , R ⁱ , R ^j , At least one of R ^k , R ^l , R ^m , R ⁿ , R ^o and R ^p represents a monovalent substituent.

In the above formula (II), M represents a metal or a metal compound.

The metal or metal compound may be any of a metal or a metal compound which can form a complex compound, and includes a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide or a divalent metal chloride. Compound.

M in the general formula (II) includes, for example, Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, and Fe, and the like, and AlCl, InCl, FeCl, TiCl ₂ , SnCl. ₂ , metal chlorides such as SiCl ₂ and GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si(OH) ₂ .

In terms of improving color purity, in the present invention The maximum absorption wavelength λ _{max of the} metal complex is preferably from 580 nm to 700 nm, more preferably from 600 nm to 680 nm. Further, the maximum absorption wavelength is measured in the same manner as the dipyrromethene metal complex compound in the present invention.

In the formula (II), a monovalent substituent in the case where R ^a to R ^p represents a monovalent substituent is synonymous with an example of a substituent represented by R ¹ to R ⁶ in the above formula (I), and a preferred form thereof The state is also the same. Further, all of the 16 substituents R ^a to R ^{p present are} not a hydrogen atom or a halogen atom, and at least one of them is required to be a hydrogen atom and a monovalent substituent other than a halogen atom.

When the monovalent substituent represented by R ^a to R ^p of the compound represented by the general formula (II) is ^a group which may be further substituted, it may be substituted by the substituent described in the above R ¹ to R ⁶ When substituted by two or more substituents, the substituents may be the same or different.

Hereinafter, examples (T-1 to T141) of a halogen atom and a monovalent substituent which may be employed in R ^a to R ^p in the general formula (II) are shown. However, the present invention is not limited to these examples.

[化18]

[Chemistry 19]

[Chemistry 20]

Hereinafter, a preferred range of the phthalocyanine dye represented by the general formula (II) will be described.

Here, the above monovalent substituent in the case where R ^a to R ^p represents a monovalent substituent is preferably a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a decyl group, a hydroxyl group, a carboxyl group or a cyano group. , nitro, alkoxy, aryloxy, heterocyclooxy, nonyloxy, decyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, amine methyloxy, amine sulfonium oxide Sulfamoyloxy), alkylsulfonyloxy, arylsulfonyloxy, fluorenyl, alkoxycarbonyl, aryloxycarbonyl, aminemethanyl, amine, anilino, formamide, ureido,醯imino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, aminesulfonylamino, azo, alkylthio, arylthio, heterocyclic thio, alkyl A sulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an aminesulfonyl group, a sulfo group, a phosphonium group or a phosphonylamino group; more preferably an alkyl group, Alkenyl, aryl, heterocyclic, alkoxy, aryloxy, heterocyclooxy, decyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, aminemethyloxy, sulfonamide Oxyl, alkylsulfonyloxy, arylsulfonyloxy, Mercapto, alkoxycarbonyl, aryloxycarbonyl, aminemethionyl, formamidine, ureido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfonamide Base, alkylthio, arylthio, heterocyclic thio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, aminesulfonyl, sulfo, phosphine Mercapto or phosphinium amino group; particularly preferred are: heterocyclic group, alkoxy group, aryloxy group, heterocyclic oxy group, decyloxy group, amine methyl methoxy group, amine sulfonyloxy group, alkyl sulfonate a decyloxy group, an arylsulfonyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amine carbenyl group, a formamidine group, a urea group, a sulfonylamino group, an aminesulfonylamino group, an alkylthio group, An arylthio group, a heterocyclic thio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group or an aminesulfonyl group. Examples of M include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, TiO, VO, and the like; more preferably, Cu, Zn, Co, TiO, VO, Mg; particularly preferred are: Cu, Zn, Co, TiO, VO.

Specific examples of the phthalocyanine dye represented by the formula (II) are shown below. However, Benedict It is not limited to these specific examples.

[Chem. 21]

[Chem. 24]

The phthalocyanine dye represented by the above formula (II) can be synthesized by referring to the descriptions of paragraphs [0192] to [0199] in JP-A-2008-292970.

Other dyes

In addition to the above preferred dyes, the (A) dye in the present invention may be, for example, a xanthene dye, an anthraquinone dye, a porphyrin dye, or a cyanine dye. (cyanine dye) and methine dye (methine dye).

The colored curable composition of the present invention may contain only one kind of (A) dye, and may be used in combination of two or more kinds according to the purpose. Usually two or more types are used simultaneously in order to achieve a desired hue. Further, the pigment may be used in combination depending on the purpose.

The content of the (A) dye in the colored curable composition of the present invention is preferably from 1% by mass to 50% by mass, and more preferably from 5% by mass to 40% by mass, based on the solid content of the composition. When the content of the metal complex dye is 1% by mass or more, good spectral characteristics and heat resistance can be obtained, and if it is 50% by mass or less, it is advantageous in terms of hue.

In addition, the "solid content" as used herein means the total amount of all the components except the solvent in the coloring curable composition.

(B) at least one structural unit (b-1) selected from the structural unit represented by the following general formula (1) and the structural unit represented by the following general formula (2), and a structural unit having an acidic group (b-2), and an adhesive resin having an acid value in the range of 150 mgKOH/g to 300 mgKOH/g

Hereinafter, the important component (B) of the present invention is bonded to a specific adhesive. Line description. (B) The specific binder must contain a crosslinkable group and an acidic group of a specific structure in the molecule, and the acid value is in the range of 150 mgKOH/g to 300 mgKOH/g.

The (B) specific binder of the present invention is at least one structural unit (b-1) containing a monomer represented by the following formula (1) and a monomer represented by the following formula (2). Copolymer. Further, as indicated by the following structure, the structural unit (b-1) is a monomer having a crosslinkable group, and (B) the specific binder has a crosslinkage derived from the structural unit (b-1) in the molecule. Sexual basis.

In the above formula (1), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² and R ¹³ each independently represent a hydrogen atom or a carbon group having a carbon number of 3 to 20 containing an unsaturated double bond as a partial structure, and R ¹² is absent. Both R and R ¹³ are hydrogen atoms.

Here, R ¹¹ represents a hydrogen atom or a methyl group, preferably a methyl group.

R ¹² and R ¹³ each independently represent a hydrogen atom or a carbonyl group having a carbon number of 3 to 20 which contains an unsaturated double bond as a partial structure, and when R ¹² and R ¹³ represent the carbonyl group, a carboxyl group may be contained as a partial structure, preferably It represents an α,β unsaturated carbonyl group having a carbon number of 3 to 4.

Specific examples of the structural unit represented by the general formula (1) are shown below, but the present invention is not limited to these specific examples.

[化32]

In the above formula (2), R ²⁰ represents a hydrogen atom or a methyl group, and R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group.

Here, R ²⁰ represents a hydrogen atom or a methyl group, preferably a methyl group.

Specific examples of the halogen atom in the case where R ²¹ to R ²⁵ represent a halogen atom include, for example, Cl, Br, and I.

The alkyl group in the case where R ²¹ to R ²⁵ represent an alkyl group may be any of a straight chain, a branched chain, and a cyclic group, and specific examples thereof include a methyl group, a n-propyl group, an isopropyl group and a Tributyl or the like is preferably an alkyl group having 1 to 7 carbon atoms.

The aryl group in the case where R ²¹ to R ²⁵ represent an aryl group may, for example, be a phenyl group, a furyl group or a naphthyl group.

R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are each preferably a hydrogen atom, more preferably all hydrogen atoms.

Specific examples of the structural unit (b-2) include the following structures, but the present invention is not limited to these structures.

[化33]

The (B) specific binder of the present invention is a copolymer further comprising a structural unit derived from the monomer (b-2) having an acidic group.

The acidic group in the monomer having an acidic group used in the present invention may, for example, be a carboxyl group, an anthranylene group or the like.

Further, examples of such a monomer having an acidic group include acrylic acid, methacrylic acid, sulfonic acid, phosphoric acid, and the like. Among them, acrylic acid and methacrylic acid are preferable.

(B) a monomer (b-1) having at least one selected from the group consisting of the monomer represented by the formula (1) and the monomer represented by the formula (2) in the specific binder; The structural unit (structural unit: b-1) and the structural unit derived from the monomer (b-2) having an acidic group (structural unit: b-2) preferably contain a molar ratio of 1:0.3 to 1: In the range of 2, it is more preferably in the range of 1:0.3 to 1:1.

Further, the (B) specific binder may further comprise other structural units different from the structural unit: (b-1) and the structural unit: (b-2).

Examples of the monomer which can provide other structural units which can be used for (B) a specific binder include benzyl methacrylate, cyclohexyl methacrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, and A. Isobutyl acrylate, styrene, and the like.

Further, (B) when the specific binder contains other structural units, the content of the other structural units is preferably from 0 mol% to 40 mol%, and the content is more preferably 30 mol% or less.

Specific examples of the (B) specific binder which can be preferably used in the present invention together with the monomer constituting the binder, the weight average molecular weight and the acid value measured by GPC gel permeation chromatography are listed below, but The invention is not limited to this.

The following monomer abbreviations represent the following compounds.

GMA-MAA: glycidyl methacrylate / methacrylic acid

Allyl-MA: allyl methacrylate

MAA: Methacrylic acid

AA: Acrylic

BzMA: benzyl methacrylate

CHMA: cyclohexyl methacrylate

The (B) specific binder used in the present invention can be synthesized by a usual method. Hereinafter, a synthesis example of the exemplified compounds 1 and 6 is shown. Other exemplary compounds can also be synthesized by analogous methods.

Exemplary synthesis of compound 1

Methyl acrylate (55 parts by weight), cyclohexyl methacrylate (61 parts by weight), 1-methoxy-2-propanol (175 parts by weight), V-601 (trade name: manufactured by Wako Pure Chemical Industries, Ltd.) , polymerization initiator (dimethyl azobisisobutyrate) A mixed solution of (Dimethyl 2,2'-azobis(2-methylpropionate))) (6.8 parts by weight) was polymerized under a nitrogen gas stream at 90 ° C for 4 hours. Thereafter, glycidyl methacrylate (37 parts by weight), tetraethylammonium bromide (0.6 parts by weight), and methyl ethyl ketone (40 parts by weight) were added to the reaction mixture solution, and the mixture was reacted at 100 ° C for 4 hours. Thus, Compound 1 was exemplified by the synthesis.

The weight average molecular weight (GPC, polystyrene conversion) of the obtained polymer was 30,000.

Synthesis of exemplified compound 6

Allyl methacrylate (79 parts by weight), methacrylic acid (32 parts by weight), 1-methoxy-2-propanol (140 parts by weight), V-65 (trade name: Wako Pure Chemical Industries, Ltd.) A mixed solution of a polymerization initiator (2,2'-azobis(2,4-dimethyl)valeronitrile): 0.6 part by weight) was polymerized under a nitrogen gas stream at 70 ° C for 8 hours. After cooling the reaction solution to room temperature, water (200 parts by weight) was added to carry out a reprecipitation treatment. The condensed polymer was filtered, washed with water, and dried to synthesize the exemplified compound 6.

The weight average molecular weight (GPC method, polystyrene conversion) of the obtained polymer was 33,000.

The content of the (B) specific binder in the colored curable composition of the present invention is preferably in the range of 0.1 part by mass to 20 parts by mass based on 1 part by mass of the above (A) dye.

(C) organic solvent

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

The organic solvent is basically not particularly limited as long as it satisfies the solubility of the respective components or the coatability when the color-curable composition is formed. It is selected in consideration of solubility, coating property, and safety of a solid component.

Examples of the organic solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, and butyl. Ethyl acetate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (for example, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, etc., more specifically Examples thereof include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and the like, and 3-oxypropionic acid alkane. Base esters, alkyl 2-oxypropionates, methyl 2-oxy-2-methylpropanoate, ethyl 2-oxy-2-methylpropionate, methyl pyruvate, pyruvic acid Ethyl ester, propyl pyruvate, methyl acetate methyl acetate, ethyl acetate ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

Further, examples of the ether which can be used as the organic solvent include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl acetate sulphate, and ethyl celecoxib acetate. , diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, dipropylene glycol Ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol methyl n-propyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like.

Examples of the ketone which can be used as the organic solvent include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.

The aromatic hydrocarbon which can be used as the organic solvent is preferably, for example, toluene, xylene or the like.

From the viewpoints of the solubility of each of the above components and the solubility of the (A) dye or (B) specific binder and the state of the coated surface, it is preferred to mix the organic solvents in two or more kinds. . In this case, it is particularly preferable to contain a mixed solution of two or more selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl celecoxib acetate. Ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, diethylene glycol methyl ether Dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, butyl carbitol acetate, propylene glycol methyl ether and propylene glycol methyl ether acetate.

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

In the colored curable composition of the present invention, in addition to the above (A) dye, (B) specific binder, and (C) organic solvent, various compounds may be contained depending on the purpose within a range that does not impair the effects of the present invention. .

Polymeric compound

The color hardening composition of the present invention may further contain at least one polymerizable compound different from the (B) specific binder structure. By containing a polymerizable compound, the hardenability of the coloring curable composition can be improved.

The polymerizable compound is exemplified by a photopolymerizable compound. The photopolymerizable compound is preferably a compound having a boiling point of 100 ° C or more at normal pressure and having at least one ethylenically unsaturated group capable of undergoing addition polymerization. Examples of the photopolymerizable compound include polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate. Monofunctional acrylate or methacrylate; polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, Pentaerythritol tri(meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexane diol (meth) acrylate , trimethylolpropane tris(propylene methoxypropyl) ether, tris(propylene decyloxyethyl)isocyanurate, addition of epoxy to polyfunctional alcohols such as glycerol or trimethylolethane The compound obtained by (meth)acrylation after ethane or propylene oxide is disclosed in Japanese Patent Publication No. Sho 48-41708, Japanese Patent Publication No. Sho-50-6034, and Japanese Patent Laid-Open No. Sho 51-37193. The urethane acrylates described in the Japanese Patent Publication No. Sho 48-64183, Japanese Patent Publication No. Sho 49-43191, and Japanese Patent Publication No. Sho 52-30490, etc. The reaction product of esters, epoxy resins and (meth)acrylic acid, ie epoxy acrylate Polyfunctional acrylate or methacrylate and a mixture of these.

Further, in addition to the photopolymerizable compound, a thermally polymerizable compound may be contained as the polymerizable compound. Examples of the thermopolymerizable compound include an epoxy compound, an oxetane compound, and a 1,2-halo alcohol compound. More specifically, Japanese Patent No. 3599866, Japanese Patent No. 4,459,651, and Japanese Patent No. 3,850,756 The compound described in Japanese Patent No. 4185245 or the like.

Further, examples of the polymerizable compound include an alkali-soluble resin having a polymerizable group. Examples of the alkali-soluble resin having a polymerizable group include an alkali-soluble resin containing a (meth)acryl fluorenyl group and a glycidyl group, and specific examples thereof include Japan. The resin described in JP-A-2007-233184, JP-A-2005-326507, and the like. Further, it may be an alkali-soluble resin having a polymerizable group in a side chain, and a polymer having a side chain having an allyl group, a (meth)acrylic group or an allyloxyalkyl group, or the like may also be used. Examples of the polymerizable group-containing polymer include KS Resist-106 (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (trade name, manufactured by Daicel Chemical Industries Co., Ltd.), and the like. .

Further, a compound which is described as a photocurable monomer and an oligomer in JP-A-0, No. 7, P.300-P.308, may be mentioned.

When the polymerizable compound is used, the content of the polymerizable compound in the colored curable composition is preferably from 0.1% by mass to 90% by mass, more preferably from 1.0% by mass to 80% by mass based on the solid content of the colored curable composition. %, particularly preferably from 2.0% by mass to 70% by mass.

Photopolymerization initiator

The colored curable composition of the present invention preferably contains at least one radiation-sensitive initiator. The photopolymerization initiator is a compound which generates a radical, generates an acid or generates a chemical reaction under ultraviolet (UV) light of 400 nm or less, and can (B) a specific binder or a polymerization property as needed. The compound is insolubilized by a reaction such as crosslinking or polymerization, or polymerization of a polymerizable monomer or oligomer coexisting in the coating film, crosslinking of a crosslinking agent, etc., thereby insolubilizing the coating film with respect to the alkali developing solution.

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

The photopolymerization initiator may, for example, be at least one active halogen compound selected from the group consisting of a halomethyl oxadiazole compound and a halomethyl s-triazine compound, a 3-aryl-substituted coumarin compound, and a porphin dimer ( Dimer lophine), benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, and lanthanoid compounds.

Specific examples of the photopolymerization initiators include the examples described in paragraphs [0261] to [0266] of JP-A-2008-292970. Among them, a quinone compound is preferred from the viewpoint of a rapid polymerization reaction and the like.

The ruthenium-based compound (hereinafter also referred to as an oxime-based photopolymerization initiator) is not particularly limited, and examples thereof include, for example, JP-A-2000-80068, WO02/100903A1, and JP-A-2001-233842. The lanthanide compound described in the above.

Specific examples of the above lanthanoid compound include 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-butanedione and 2-(O-benzene). Methyl hydrazide)-1-[4-(phenylthio)phenyl]-1,2-pentanedione, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio) Phenyl]-1,2-hexanedione, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-heptanedione, 2-(O -benzylidene hydrazide)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 2-(O-benzylidene fluorenyl)-1-[4-(methyl Phenylthio)phenyl]-1,2-butanedione, 2-(O-benzylidene fluorenyl)-1-[4-(ethylphenylthio)phenyl]-1,2-butane Ketone, 2-(O-benzylidene fluorenyl)-1-[4-(butylphenylthio)phenyl]-1,2-butanedione, 1-(O-ethylindenyl)-1 -[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-methyl -6-(2-methylbenzimidyl)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9- -6-(2-methylbenzimidyl)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-ethyl-6-(2- Ethyl benzhydryl)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-ethyl-6-(2-butylbenzylidene) )-9H-carbazol-3-yl]ethanone. However, it is not limited to these specific examples.

Among these, from the viewpoint of forming a pattern with a smaller amount of exposure, it is particularly preferable that it is 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]- 1,2-octanedione, 1-(O-ethylindenyl)-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]B Specific examples of the oxime-O-fluorenyl compound such as a ketone include CGI-124, CGI-242, and Irgacure OXE01 (the above are trade names, manufactured by Ciba Japan Co., Ltd.).

In the present invention, the oxime compound is more preferably a compound represented by the following formula (3) or formula (4) from the viewpoint of sensitivity and stability over time.

In the above formula (3) and formula (4), 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 from 0 to 5. When n is an integer of 2 to 5, a plurality of Xs may be the same or different from each other.

From the viewpoints of high sensitivity in the general formula (3) and the general formula (4), a mercapto group is preferred, and specifically, an ethyl fluorenyl group, a propyl fluorenyl group, and a benzamidine group are preferred. Or tolylmethyl group.

The A in the general formula (3) and the general formula (4) is preferably an unsubstituted alkylene group or an alkyl group (for example, a viewpoint of improving sensitivity and suppressing coloring caused by heating over time. Alkyl, ethyl, tert-butyl or dodecyl) substituted alkyl, alkyl substituted by alkenyl (eg vinyl or allyl), aryl (eg phenyl, p-tolyl) An alkylene group substituted with xylyl, cumyl, naphthyl, anthracenyl, phenanthryl or styryl).

The Ar in the general formula (3) and the general formula (4) is preferably a substituted or unsubstituted phenyl group from the viewpoint of improving sensitivity and suppressing coloring caused by heating over time. When it is 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.

The X in the general formula (3) and the general formula (4) is preferably an alkyl group which may have a substituent and an aromatic group which may have a substituent from the viewpoint of improving solvent solubility and absorption efficiency in a long wavelength region. An alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, may have a substitution An arylthio group, an amine group which may have a substituent.

Further, n in the general formula (3) and the general formula (4) is preferably 01 to 2 Integer.

Specific examples of the compound represented by the formula (1) are shown below, but the present invention is not limited to these specific examples.

[化36]

In the color hardening composition of the present invention, in addition to the above photopolymerization initiator Other known photopolymerization initiators described in paragraph [0079] of JP-A-2004-295116 may be used.

The radiation-sensitive compound (particularly, a photopolymerization initiator) may be contained alone or in combination of two or more.

When the photopolymerization initiator is used, the content of the photopolymerization initiator in the coloring curable composition (in the case of two or more kinds, the total content) is preferably 0.01 mass based on the total solid content of the polymerizable compound. %~50% by mass, more preferably 1% by mass to 30% by mass, particularly preferably 1% by mass to 20% by mass. When the content is within the above range, the polymerization proceeds well and the film strength is excellent.

A sensitizer or a light stabilizer may be used together with the above photopolymerization initiator.

Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-fluorenone, 2-bromo-9. -fluorenone, 2-ethyl-9-fluorenone, 9,10-fluorene, 2-ethyl-9,10-fluorene, 2-tert-butyl-9,10-fluorene, 2,6 -Dichloro-9,10-oxime, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-ethoxyox Anthrone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzalacetone, pair (Dimethylamino)phenylstyrene ketone, p-(dimethylamino)phenyl-p-methylstyrene ketone, benzophenone, p-(dimethylamino)benzophenone (or Or a benzothiazole compound described in Japanese Patent Publication No. Sho 51-48516, or TINUVIN 1130, TINUVIN 400, or a benzothiazole compound such as (p-ethylamino) benzophenone or benzofluorenone. Wait.

Further, it is preferred to further add a thermal polymerization inhibitor in addition to the above, and for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, and t-butyl are useful. Catechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-third Butyl phenol), 2-mercaptobenzimidazole, and the like.

(Other binder resins)

The colored curable composition of the present invention may further contain a binder (referred to as another binder) having no crosslinkable group different from the structure of (B) a specific binder. The binder can be selected from an alkali-soluble binder. In this case, it is not particularly limited as long as it has alkali solubility, and it is preferably selected from the viewpoints of heat resistance, developability, and availability.

The alkali-soluble binder is preferably a linear organic high molecular polymer which is soluble in an organic solvent and which can be developed by a weakly alkaline aqueous solution. Examples of such a linear organic polymer include a polymer having a carboxylic acid in a side chain. For example, Japanese Patent Laid-Open No. Sho 59-44615, Japanese Patent Publication No. Sho 54-34327, Japanese Patent Publication No. Sho 58-12577, Japan A methacrylic copolymer, an acrylic copolymer, an itaconic acid copolymer, and the like, which are described in Japanese Patent Laid-Open Publication No. Sho 59-53836, and Japanese Patent Laid-Open Publication No. SHO 59-71048, Butenoic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, and the like. Among the alkali-soluble binders, particularly acidic cellulose derivatives having a carboxylic acid in a side chain are useful. In addition to the above, a substance obtained by adding an acid anhydride to a polymer having a hydroxyl group, or a polyhydroxystyrene resin, a polyoxyalkylene resin, or a poly(methyl)propyl group. Ethyl 2-hydroxyethyl acrylate, polyvinyl pyrrolidone or polyethylene oxide, polyvinyl alcohol and the like are also useful.

Further, a monomer having a hydrophilic group may be copolymerized, and examples thereof include alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, and glyceryl (meth)acrylate. (Meth) acrylamide, N-methylol acrylamide, secondary and tertiary alkyl acrylamide, dialkylaminoalkyl (meth) acrylate, morpholinyl (meth) acrylate , N-vinylpyrrolidone, N-vinyl caprolactam, vinyl imidazole, vinyl triazole, methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylic acid branch Or an amyl propyl ester, a (meth)acrylic acid branched or linear butyl ester, phenoxy hydroxypropyl (meth) acrylate or the like.

In addition, as the monomer having a hydrophilic group, a tetrahydroindenyl group, a phosphoric acid moiety, a phosphate moiety, a quaternary ammonium salt moiety, an extended ethoxylated chain, a propoxylated chain, a sulfonic acid, and a salt thereof are contained. A monomer such as a moiety or a morpholinylethyl group is also useful.

Further, in order to increase the strength of the cured film, alcohol-soluble nylon or a polyether of 2,2-bis(4-hydroxyphenyl)propane and epichlorohydrin or the like is also useful.

From the viewpoint of heat resistance, the other binder is preferably a polyhydroxystyrene resin, a polyoxyalkylene resin, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin. Further, from the viewpoint of controlling developability, the other binder is preferably an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin. The acrylic resin preferably contains a component selected from the group consisting of benzyl (meth)acrylate, (meth)acrylic acid, and (meth)acrylic acid. A copolymer of a monomer such as hydroxyethyl enoate or (meth) acrylamide or the like.

The other binder is preferably a polymer having a mass average molecular weight (polystyrene equivalent value measured by a GPC method) of 1000 to 2 × 10 ⁵ , more preferably a polymer having a mass average molecular weight of 2,000 to 1 × 10 ⁵ , Particularly preferred are polymers having a mass average molecular weight of from 5,000 to 5 x 10 ⁴ .

When other binders are used, the content of the other binder in the colored curable composition is preferably from 10% by mass to 90% by mass, more preferably from 20% by mass to 80% by mass, based on the total solid content of the composition. It is 30% by mass to 70% by mass.

Various additives

Various additives such as a filler, a polymer compound other than the above, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-coagulant, and the like can be prepared as needed in the colored curable composition of the present invention.

The various additives mentioned above are the additives described in Paragraph Nos. [0275] to [0276] of JP-A-2008-292970.

Coloring ingredients

In addition to the above (A) dye, a pigment or the like may be further contained as a coloring component in a range that does not impair the effects of the present invention. The hue and color purity of the target can be achieved by combining various pigments.

The color hardening composition of the present invention can be preferably used for a liquid crystal display (LCD) or a solid-state imaging device (for example, a charge coupled device (CCD), a complementary metal oxide semiconductor (Complementary Metal Oxide). The use of color filters such as color filters used in semiconductors, CMOS, etc., and the use of printing inks, inkjet inks, and paints. In the present invention, in particular, it is preferably used for a color filter for a liquid crystal display element.

Color filter and manufacturing method thereof

The color filter of the present invention comprises a colored cured film which is obtained by using the above (A) dye, (B) specific binder, and (C) organic solvent, and may contain other components as needed. The color filter of the present invention is formed by providing a support and a colored region (colored cured film) formed on the support using the colored curable composition of the present invention. ) constitutes.

Since the color filter of the present invention contains the above (B) specific binder in the present invention together with the above (A) dye, the stability of the dye (A) is improved even when exposed to a high temperature environment such as a post-baking step. It is also possible to suppress discoloration or fading caused by (A) dye decomposition, and it is possible to maintain an excellent hue for a long period of time. Therefore, an image with good color tone can be displayed for a long time.

The color filter of the present invention can be formed by any method as long as it is a method of forming a colored film (colored pattern) which is cured by using the colored curable composition of the present invention.

The color filter of the present invention can be preferably produced by a method comprising the steps of: applying the colored curable composition of the present invention to a support to form a colored layer; and forming the above-mentioned The colored layer is exposed to a pattern and is developed to form a colored region.

Specifically, the colored hardenable composition of the present invention is coated by spin coating A coating method such as cloth, cast coating, or roll coating is applied onto a support to form a radiation-sensitive composition layer, and then the layer is exposed to a predetermined pattern through, for example, a mask pattern, and a developer is used. Development is carried out, whereby a colored pattern constituting the color filter, that is, a desired colored region can be formed. These operations are repeated in accordance with the desired number of colors, whereby a color filter containing a desired number of hue can be obtained.

The light source used for the exposure is preferably a light source having a wavelength of 400 nm or less. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, and the like, and a paragraph number of the Japanese Patent Laid-Open Publication No. 2008-292970 [0278] The light source described in . From the viewpoint of cost and exposure energy, it is preferably ultraviolet light, more preferably i-line.

For the pattern formed by exposure and development, a curing step of performing heat and/or exposure to further harden the pattern may be further provided as needed. The light or radiation at this time is preferably a radiation such as an i-line.

Examples of the support include a soda glass used in a liquid crystal display element, a Pyrex (registered trademark) glass, a quartz glass, and a support in which a transparent conductive film is attached to the glass; or a photoelectric conversion used for a photographic element or the like. The element substrate, for example, a germanium substrate or the like, or a complementary metal oxide film semiconductor (CMOS) or the like. These supports also have a black stripe in which each pixel is isolated. Further, from the viewpoint of improving adhesion to a layer provided on the support as needed, preventing diffusion of a substance, or flattening the surface of the support, an undercoat layer may be provided on the support.

The developer to be used for development does not contain a region (unhardened portion) in which the coloring curable composition is to be developed and removed, and does not dissolve the other regions (hardened portions). Special restrictions. Specifically, the developer may use a combination of various organic solvents or an alkaline aqueous solution. The above organic solvent may, for example, be the above solvent used in the preparation of the composition. In addition, the alkaline aqueous solution can be obtained by dissolving the basic aqueous solution so that the concentration thereof is 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass. Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, and hydroxide. Tetraethylammonium, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7-undecene, and the like.

In the case of using an aqueous alkaline solution, it is usually washed with water after development.

The color filter of the present invention can be used for an organic EL display device, a liquid crystal display device or a solid-state imaging device, and is particularly suitable for use in a liquid crystal display device. When it is used for a liquid crystal display device, the dye containing (A) excellent in spectral characteristics and heat resistance, preferably a metal complex dye, is used as a colorant, so that the change in hue due to heat treatment or the like is small, and the color tone of the displayed image is good. And the display characteristics are excellent.

Display device

The color filter of the present invention is particularly suitable as a color filter for a display device such as an organic EL display device or a liquid crystal display device because it has a color pixel excellent in hue and excellent in light resistance. Contains this color filter The display image of the light-emitting display device has a good color tone, and can display a high-quality image excellent in display characteristics for a long period of time.

In other words, the display device of the present invention includes a color filter obtained by using the colored curable composition of the present invention or a color filter obtained by the method for producing a color filter of the present invention.

The definition of the display device or the details of each display device is, for example, "Electronic display device (sasaki Sasaki, Industrial Research Association, Inc., 1990)", "Display device (Ibuki Shunzhang, Industrial Book Co., Ltd.) It was published in 1989). In addition, the liquid crystal display device is described in, for example, "Next-generation liquid crystal display technology (edited by Uchida Ryuo, Industrial Investigations Co., Ltd., 1994)". The liquid crystal display device to which the present invention is applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the "Next Generation Liquid Crystal Display Technology".

Among them, the color filter of the present invention is particularly effective for a liquid crystal display device of a Thin Film Transistor (TFT) type. A liquid crystal display of a color TFT type is described, for example, in "Color TFT liquid crystal display (issued by Kyoritsu Publishing Co., Ltd., 1996)". Furthermore, the present invention can also be applied to a liquid crystal display device having a wide viewing angle such as a horizontal electric field driving method such as In-plane Switching (IPS) or a pixel division method such as Multi-domain Vertical Alignment (MVA). Or Super Twisted Nematic (STN), Twisted Nematic (TN), Vertical Alignment (VA), Optical Compensation Diffusion (Optically Compensated Splay, OCS), Fringe Field Switching (FFS), and Reflective Optically Compensated Bend (R-OCB).

In addition, the color filter of the present invention is also available in a bright and highly accurate color-filter on Array (COA) method. In the COA liquid crystal display device, in addition to the usual required characteristics as described above, the required characteristics of the color filter layer may require the required characteristics of the interlayer insulating film, that is, the low dielectric constant and the peeling liquid resistance. Sex. The color filter of the present invention is a color filter obtained by curing a curable composition containing the (B) specific binder together with the above (A) dye, and it is considered that (A) the thermal stability of the dye The stability over time is dramatically improved, and the deterioration of display characteristics is eliminated. Thereby, since the color purity and the like are excellent and the color tone is excellent, it is possible to provide a COA liquid crystal display device having high resolution and excellent long-term durability. Further, in order to satisfy the required characteristics, a resin film may be provided on the color filter layer.

Further, in the coloring layer formed by the COA method, in order to electrically connect the indium tin oxide (ITO) electrode disposed on the colored layer and the terminal of the driving substrate below the colored layer, it is necessary to form one side length. a rectangular through hole or "1 μm~15 μm" It is preferable that the size of the guide passage (that is, the length of one side) is 5 μm or less, and the guide passage for forming 5 μm or less is also used by using the guide passage of the U-shaped concave portion. may. These image display methods are described, for example, in "EL, PDP, LCD Display Technology and Market Trends - (Toray Research Center, Research and Development, 2001)", page 43 and the like.

In addition to the color filter of the present invention, the display device of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle securing film. The color filter of the present invention can be applied to a liquid crystal display element including such well-known members. These components are described, for example, in '94 Markets for Liquid Crystal Display Peripherals and Chemicals (Shima Kotaro, CMC Co., Ltd., issued in 1994), and "2003 Liquid Crystal Related Market Status and Future Outlook (Volume 2)" "Bian Liangji, Fuji Chimera Research Institute Co., Ltd., issued in 2003)".

The backlight is described in SID meeting Digest 1380 (2005) (A. Konno et. al) or "Monthly Display, December 18, 2005, pages 18 to 24 (Island Kang Yu), December 2005, No. 25 Page ~ 30 pages (Yamamu Longming)" and so on.

By using the color filter of the present invention in a liquid crystal display element, high contrast can be achieved when combined with a three-wavelength tube of a previously known cold cathode tube, and the red, green, and blue LED light source (RGB-LED) can be realized. A backlight is provided to provide a liquid crystal display device having high luminance, high color purity, and good color reproducibility.

Solid photographic element

The solid-state imaging device of the present invention comprises the above-described color filter of the present invention.

The solid-state imaging element of the present invention is constituted as long as it contains the present invention. The color filter is not particularly limited as long as it can function as a solid-state imaging element, and examples thereof include the following configurations.

In the support, a plurality of photodiodes constituting a light receiving region of a solid-state imaging device (a CCD image sensor, a CMOS image sensor, or the like) and a transfer electrode including a polysilicon or the like are provided on the support, and the photodiode is provided. And a light-shielding film containing tungsten or the like in which the light-receiving portion of only the photodiode is opened, and the light-shielding film includes a tantalum nitride or the like which is formed to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode. The device protective film has the color filter for a solid-state imaging device of the present invention on the device protective film.

Furthermore, it is also possible to have a configuration of a light collecting means (for example, a microlens or the like, which is the same below) on the device protective layer and below the color filter (near the support side), or to have a light collecting on the color filter. The composition of the organization, etc.

[Example]

Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to the following examples as long as the gist of the invention is not exceeded. In addition, “parts” are quality standards unless otherwise stated.

Synthesis Example 1: Synthesis of Compound 1

Methyl acrylate (55 parts by weight), cyclohexyl methacrylate (61 parts by weight), 1-methoxy-2-propanol (175 parts by weight), V-601 (trade name: manufactured by Wako Pure Chemical Industries, Ltd.) The mixed solution of 6.8 parts by weight was subjected to polymerization at 90 ° C for 4 hours under a nitrogen stream. Further, glycidyl methacrylate (37 parts by weight), tetraethylammonium bromide (0.6 parts by weight), and methyl ethyl ketone were added to the reaction mixture solution. (40 parts by weight), and reacted at 100 ° C for 4 hours, thereby synthesizing the exemplified compound 1.

The weight average molecular weight (GPC method, polystyrene conversion) of the obtained polymer was 30,000.

Synthesis Example 2: Synthesis of exemplified compound 6

Allyl methacrylate (79 parts by weight), methacrylic acid (32 parts by weight), 1-methoxy-2-propanol (140 parts by weight), V-65 (polymerization initiator, trade name: The mixed solution of Wako Pure Chemical Industries, Ltd.: 0.6 parts by weight) was polymerized at 70 ° C for 8 hours under a nitrogen stream. After cooling the reaction solution to room temperature, water (200 parts by weight) was added to carry out a reprecipitation treatment. The condensed polymer was filtered, washed with water, and dried to synthesize the exemplified compound 6.

The weight average molecular weight (GPC method, polystyrene conversion) of the obtained polymer was 33,000.

Example 1 Preparation of coloring photosensitive composition

Each component described in the following composition 1 was mixed and dissolved to prepare a colored photosensitive composition.

(composition 1)

Preparation of blue pigment dispersion

The blue pigment dispersion 1 was prepared in the following manner.

12.8 parts of CI Pigment Blue 15:6, 7.2 parts of a dispersant (trade name: Solsperse 5500, manufactured by Lubrizol Co., Ltd., Japan), and 80.0 parts of propylene glycol monomethyl ether acetate were mixed, and the pigment was sufficiently dispersed using a bead mill to prepare blue. Pigment dispersion.

Preparation of dye solution 1

The dye solution 1 was prepared by mixing and dissolving each of the following components.

Preparation of dye solution 2

The dye solution 2 was prepared by mixing and dissolving each of the following components.

Hereinafter, the dye (A-1) used in the preparation of the coloring photosensitive composition of Example 1 is an exemplary compound (11) of a pyrromethene metal complex dye. The dye (B-1) is an anthracene compound (a compound having a fluorene-9,10-dione skeleton) having the following structure.

Photosensitive film formation

Next, the photosensitive colored curable composition prepared above was applied onto glass (#1737, manufactured by Corning) by a spin coating method, and then heated at 100 ° C for 80 seconds to volatilize volatile components. Photosensitive colored film. After cooling, the photosensitive colored film was irradiated with an i-line (wavelength: 365 nm) and cured. The light source of the i line uses an ultrahigh pressure mercury lamp, and at this time, the amount of irradiation light is set to 40 mJ/cm ² . Then, after developing for 40 seconds in a 0.05% KOH solution at 25 ° C, the developer was washed away by a rinse treatment using pure water.

Next, this colored film was post-baked at 230 ° C for 60 minutes to obtain a colored film having a film thickness of 2 μm.

Evaluation (1) Spectroscopic characteristics

The transmission spectrum of the coloring film obtained above was measured using a microscopic spectrophotometer MCPD-3000 (trade name) manufactured by Otsuka Electronics Co., Ltd. From the obtained transmission spectrum, the color coordinate x value, y value, and Y value in the CIE 1931 color system were obtained.

Regarding the spectral characteristics, when the Y value at (x, y) = (0.141, 0.090) is a high value, it is considered to have excellent spectral characteristics.

(2) Heat resistance (luminance reduction rate)

With respect to the coloring film obtained above, the chromaticity was measured before and after the post-baking step (heating at 230 ° C for 60 minutes) using a microscopic spectrophotometer MCPD-3000 (trade name). The Y value drop amount was obtained from the Y value difference at y=0.090, and was set to the ΔY value. The results are shown in Table 1 below. In addition, When the ΔY value was 0.4, it was judged to have excellent heat resistance.

(3) Chemical resistance (poor color)

The colored film after the post-baking step obtained above was immersed in N-methylpyrrolidone (NMP) at 25 ° C, and the chromaticity before and after immersion was measured to calculate the index of color change ΔE ^* Ab. The results are shown in Table 1 below. Further, when ΔE ^* ab is less than or equal to 3, it is judged that the hue change is small and the stability is excellent.

Example 2~Example 9

A photosensitive colored curable composition was prepared in the same manner as in Example 1 except that the specific adhesive (B) in Example 1 was changed to the adhesive shown in Table 1, and a colored film was formed and evaluated. The evaluation results are shown in Table 1 below.

Comparative Example 1 to Comparative Example 3

A photosensitive colored curable composition was prepared in the same manner as in Example 1 except that the comparative adhesive shown in Table 1 (Comparative Compounds 1-3) was used instead of (B) a specific adhesive in Example 1, and a colored film was formed. And evaluate. The evaluation results are shown in Table 1 below.

As shown in the above Table 1, it was found that a structural unit (b-1) containing a crosslinkable group and a structural unit (b-2) derived from (meth)acrylic acid were used, and the acid value was 150 mgKOH. (g) a colored cured film obtained by (B) a color-curable composition made of a specific binder resin, which exhibits the effects of the present invention, has a good hue, and has a small decrease in luminance during baking, and is excellent Heat resistance.

On the other hand, Comparative Example 1 of the comparative compound 1 having an acid value other than the range of the present invention, and the use only includes the structural unit (b-1) and the structure, using a structural unit containing the monomer derived from the present invention. In either of the comparative compound 2 of the unit (b-2), the comparative example 2 of the comparative compound 3, and the comparative example 3, neither of the luminance reduction in the post-baking step was suppressed, and the hue of the displayed image was poor, and The display characteristics are poor.

The entire disclosure of Japanese Patent Application No. 2011-218597 is incorporated herein by reference.

All the documents, Japanese patent application, and technical standards described in the present specification are incorporated by reference to the same extent as the respective disclosures of To this manual.

Claims (14)

A colored hardening composition comprising: (A) a dye; (B) a binder resin comprising a structural unit represented by the following general formula (1) and a structure represented by the following general formula (2) At least one structural unit (b-1) in the unit, and a structural unit (b-2) having an acidic group, and having an acid value in the range of 150 mgKOH/g to 300 mgKOH/g; and (C) an organic solvent; In the above formula (1), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² and R ¹³ each independently represent a hydrogen atom or a carbon group having a carbon number of 3 to 20 containing an unsaturated double bond as a partial structure, and R ¹² is absent. And R ¹³ are both hydrogen atoms; when at least one of R ¹² and R ¹³ represents a carbon group having 3 to 20 carbon atoms which contains an unsaturated double bond as a partial structure, a carboxyl group may be further included as a partial structure; [Chemical 2] In the above formula (2), R ²⁰ represents a hydrogen atom or a methyl group, and R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group. The colored hardening composition according to Item 1, wherein the dye (A) contains at least one selected from the group consisting of a compound represented by the following formula (I) which is coordinated to a metal atom or a metal compound. Metal complex dye (a-1), and dye (a-2) represented by the following formula (II); In the formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group. Or a heterocyclic group; In the above formula (II), R ^a , R ^b , R ^c , R ^d , R ^e , R ^f , R ^g , R ^h , R ⁱ , R ^j , R ^k , R ^l , R ^m , R ⁿ , R ^o and R ^p each independently represent a hydrogen atom or a monovalent substituent, and R ^a , R ^b , R ^c , R ^d , R ^e , R ^f , R ^g , R ^h , R ⁱ , R ^j , R are absent. ^{When k} , R ^l , R ^m , R ⁿ , R ^o and R ^{p are} all a hydrogen atom or a halogen atom. The colored hardening composition according to the first aspect of the invention, wherein the (B) binder resin is contained in an amount of 0.1 part by mass to 20 parts by mass based on 1 part by mass of the (A) dye. The colored hardening composition according to the above aspect of the invention, wherein the (B) binder resin is at least one structural unit selected from the group consisting of the following general formula (1) and the following general formula (2) ( The molar ratio of b-1) to the structural unit (b-2) having an acidic group is 1:0.1 to 1:3. The color hardening composition according to Item 1, wherein the (B) binder resin further comprises a structure different from the structural unit (b-1) and the structural unit (b-2) having an acidic group. Structural units. The colored hardening composition according to Item 2, wherein the (a-1) metal complex dye is a compound represented by the following formula (I-2): In the above formula (I-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent hydrogen. An atom or a monovalent substituent; R ⁷ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group; and Ma represents a metal atom or a metal compound. The colored hardening composition according to Item 2, wherein the (a-1) metal complex dye is a compound represented by the following formula (I-2): In the above formula (I-3), R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic ring. R ⁸ and R ⁹ each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group or a heterocyclic amine group; Ma represents a metal An atom or a metal compound; X ³ and X ⁴ each independently represent NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group or an arylsulfonyl group), An oxygen atom or a sulfur atom; Y ¹ and Y ² each independently represent NRb (Rb represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group or an arylsulfonyl group) , an oxygen atom, a sulfur atom or a carbon atom; X ⁵ represents a group bondable to Ma; a represents 0, 1 or 2; R ⁸ and Y ¹ may be bonded to each other to form a 5-, 6- or 7-membered Rings, R ⁹ and Y ² may be bonded to each other to form a ring of 5, 6 or 7 members. The color hardening composition as described in item 1 of the patent application scope Further, it further contains a polymerizable compound and a photopolymerization initiator different from the above (B) binder resin structure. A color filter comprising: a support; and a colored region formed on the support and using the colored curable composition according to any one of claims 1 to 8. A method of producing a color filter, comprising: applying a color-curable composition according to any one of claims 1 to 8 to a support to form a colored layer; The formed colored layer is exposed to a pattern and developed to form a colored region. A display element comprising the color filter of claim 9 of the patent application. A display element comprising a color filter manufactured by the method of claim 10 of the patent application. A solid-state photographic element comprising the color filter of claim 9 of the patent application. A solid-state photographic element comprising a color filter manufactured by the method of claim 10 of the patent application.