TW201502700A - Coloring composition, coloring cured film, and display element - Google Patents

Abstract

An object of the present invention is to provide a coloring composition suitable for forming a coloring cured film having high contrast. The solution of the present invention is a coloring composition, which comprises (A) a colorant, (B) a bonder resin, and (C) a polymerizable compound. The colorant comprises a salt formed of cation having a xanthene skeleton or cation having a methine skeleton and anion of metal complex. The metal that forms the metal complex is at least one selected from a group consisting of iron, nickel, copper, and aluminum.

Description

Coloring composition, coloring cured film, and display element

The present invention relates to a coloring composition, a colored cured film, and a display element, and more particularly to a transparent or reflective type color liquid crystal display element, a solid-state imaging element, an organic EL display element, an electronic paper, or the like. A colored composition of a colored cured film to be used, a colored cured film formed using the colored composition, and a display element including the colored cured film.

When a color filter is produced by using a coloring-sensing radiation-linear composition, it is known to apply a pigment-dispersive coloring radiation-sensitive linear composition on a substrate and dry it, and then irradiate the dried coating film with radiation to have a desired pattern shape ( Hereinafter, it is referred to as "exposure"), and development is performed to obtain a method of each color pixel (see, for example, Patent Documents 1 and 2). Further, a method of forming a black matrix by using a photopolymerizable composition in which carbon black is dispersed is known (for example, see Patent Document 3). Furthermore, a method of obtaining a color pixel by a liquid-jet method using a pigment-dispersed colored resin composition is known (for example, see Patent Document 4).

Further, in order to achieve high luminance and high color purity of a display element, or high definition of a solid-state imaging element, it is generally known that the use of a dye as a colorant is effective; A compound (for example, refer to Patent Document 5) or a polymethine compound (for example, see Patent Document 6).

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open No. 2-144502

Patent Document 2 Japanese Patent Laid-Open No. 3-53201

Patent Document 3 Japanese Patent Laid-Open No. Hei 6-35188

Patent Document 4 Japanese Patent Laid-Open Publication No. 2000-310706

Patent Document 5 Japanese Patent Laid-Open Publication No. 2011-138094

Patent Document 6 Japanese Patent Laid-Open Publication No. 2009-235392

However, due to The compound or the multiple methyl compound is a compound which emits fluorescence, and when such a coloring agent is used, there is a problem that the contrast is lowered. So even if In the case where a dye such as a compound or a multiple methyl compound is used as a colorant, a coloring composition which can form a high contrast colored cured film is also strongly required.

Accordingly, an object of the present invention is to provide a colored composition suitable for formation of a colored cured film having high contrast. Furthermore, an object of the present invention is to provide a colored cured film formed using the colored composition and a display element provided therewith.

As a result of intensive studies, the present inventors have found that the above problems can be solved by using a coloring agent having a specific structure.

That is, the present invention provides a coloring composition comprising (A) a coloring agent, (B) an adhesive resin, and (C) a coloring composition of a polymerizable compound, wherein the coloring agent contains: The cation of the skeleton or the salt of the cation having a methine skeleton and the anion of the metal complex, the metal constituting the metal complex is at least one selected from the group consisting of iron, nickel, copper, and aluminum.

Moreover, the present invention also provides a colored cured film formed using the above colored composition, and a display element comprising the colored cured film. Here, the "coloring cured film" means a respective color pixel, a black matrix, a black spacer, or the like used for a display element or a solid-state imaging element.

When the coloring composition of the present invention is used, a colored cured film having high contrast can be formed.

Therefore, the coloring composition of the present invention is extremely suitable for use in the production of solid-state imaging elements such as color liquid crystal display elements, organic EL display elements, display elements such as electronic paper, and CMOS image sensors.

[Best Mode for Carrying Out the Invention]

Hereinafter, the present invention will be described in detail.

Coloring composition

Hereinafter, the constituent components of the colored composition of the present invention will be described in detail.

- (A) colorant -

The colored composition of the present invention is characterized by the following: a salt of a skeleton or a cation having a methine skeleton and an anion of a metal complex as (A) a colorant, and the metal constituting the metal complex is selected from the group consisting of iron, nickel, copper, and aluminum. At least one of the groups. Hereinafter, this salt is also referred to as "this coloring agent".

As having The cation of the skeleton is preferably a cation represented by the following formula (1):

In the formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, -R ⁸ or an aromatic hydrocarbon group having 6 to 10 carbon atoms; however, the hydrogen atom contained in the aromatic hydrocarbon group It may be via a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ R ⁸ , -SO ₂ NHR ⁹ or - SO ₂ NR ⁹ R ^{10 is} substituted; R ⁵ and R ⁶ independently of each other represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; and R ⁷ represents -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ R ⁸ , -SO ₂ NHR ⁹ or -SO ₂ NR ⁹ R ¹⁰ ; r represents an integer of 0 to 5, and if r is an integer of 2 or more, plural R ⁷ may be the same or different; R ⁸ represents a saturated hydrocarbon group having a carbon number of 1 to 20; but, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, and in the CC bond between the hydrocarbon group may have a saturated oxygen atom, a carbonyl group, or -NR ⁸ -; R ⁹ And R ¹⁰ independently of each other represent a chain alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms or -Z, or a carbon number of 2 to 10 in which R ⁹ and R ¹⁰ are bonded to each other. a substituted or unsubstituted heterocyclic group; However, the hydrogen atoms contained in the alkyl and the cycloalkyl group may be a hydroxyl group, a halogen atom, -Z, -CH = CH ₂ or -CH = CHR ⁸ substituents, In CC bond between the alkyl group and the cycloalkyl group may have an oxygen atom, a carbonyl group, or -NR ⁸ -, a hydrogen atom of the heterocyclic group may be contained, -OH or -Z substituted by -R ^8; M represents a sodium atom Or a potassium atom; Z represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 4 to 10 carbon atoms; however, the hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group may pass through -OH, -R ⁸ , -OR ⁸ , -NO ₂ , -CH=CH ₂ , -CH=CHR ⁸ or a halogen atom substitution].

The saturated hydrocarbon group of R ⁸ may be linear, branched or cyclic as long as it has a carbon number of 1 to 20, and may have a crosslinked structure. Specific examples thereof include a saturated aliphatic hydrocarbon group and a saturated alicyclic hydrocarbon group. Examples of the saturated aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, and an anthracene group. , eleven, 1-methylindenyl, dodecyl, 1-methylundecyl, 1-ethylindenyl, thirteenyl, tetradecyl, tertiary, twelve, fifteen, An alkyl group of 1-heptyloctyl, hexadecyl or octadecyl. Examples of the saturated alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a tert-butylcyclohexyl group, a cycloheptyl group, and a cyclooctyl group; a tricyclic fluorenyl group and a decahydrol group; A condensed polycyclic hydrocarbon group such as a 2-naphthyl group or an adamantyl group. Examples of the group having an oxygen atom between the CC bonds of the saturated hydrocarbon group include a methoxypropyl group, an ethoxypropyl group, a 2-ethylhexyloxypropyl group, and a methoxyhexyl group. Among them, as the saturated hydrocarbon group of R ⁸ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferred, and a linear or branched alkyl group having 1 to 6 carbon atoms is more preferred.

Examples of the chain alkyl group having 1 to 20 carbon atoms and the cycloalkyl group having 3 to 30 carbon atoms which are R ⁹ and R ¹⁰ may be the same as those described above. Among them, R ⁹ and R ^{10 are} preferably a linear or branched alkyl group having 6 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms.

The substituted or unsubstituted heterocyclic group having 2 to 10 carbon atoms which is formed by bonding R ⁹ and R ^{10 to} each other may be a monocyclic heterocyclic group, a polycyclic heterocyclic group, an unsaturated ring or a saturated ring. Specific examples thereof include pyrrolyl group, pyridyl group, indenyl group, isodecyl group, quinolyl group, isoquinolyl group, oxazolyl group, phenanthryl group, acridinyl group, furyl group, and piperidyl group ( Pyranyl), isobenzofuranyl, isochromanyl, Base, thienyl, thianthrenyl, brown Phenooxatin, thiophene Base. Examples of the substituent of the heterocyclic group include a halogen group, a hydroxyl group, an alkoxy group, an amine group, and an alkyl group. Further, examples of the aromatic heterocyclic group having 4 to 10 carbon atoms of Z include a furyl group, a thienyl group, a pyridyl group, and a pyrrolyl group. Azolyl, different Azolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, pyrimidinyl and the like.

Examples of the aromatic hydrocarbon group belonging to R ¹ , R ² , R ³ , R ⁴ and Z include a phenyl group and a naphthyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The -OR ⁸ which is a genus of R ¹ , R ² , R ³ and R ⁴ is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, and examples thereof include a methoxy group. Alkoxy groups such as ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, di-butoxy, n-pentyloxy, isopentyloxy, n-hexyloxy, etc. Methoxymethoxy, ethoxyethoxy, and the like.

Examples of -SO ₃ R ⁸ which are R ¹ , R ² , R ³ , R ⁴ and R ⁷ include a methylsulfonyl group, an ethylsulfonyl group, a hexylsulfonyl group, a sulfonyl group, and the like. Further, examples of -CO ₂ R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a cyclohexyloxycarbonyl group, and a methoxypropoxycarbonyl group. Further, R ⁹ and R ¹⁰ which are -SO ₂ NHR ⁹ and -SO ₂ NR ⁹ R ^{10 are} preferably a branched alkyl group having 6 to 8 carbon atoms, an alicyclic hydrocarbon group having 5 to 7 carbon atoms, Allyl group, aralkyl group having 8 to 10 carbon atoms, hydroxy-substituted alkyl group having 2 to 8 carbon atoms, alkyl group having 2 to 8 carbon atoms having an oxygen atom between CC bonds, and aryl group having 6 to 10 carbon atoms .

The alkyl group having 1 to 8 carbon atoms which is a group of R ⁵ and R ⁶ is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be a straight chain or a branched chain. chain.

A representative example of the cation represented by the above formula (1) is, for example, a cation represented by the following formula:

The cation having a methine skeleton is preferably a cation represented by the following formula (2) or (3):

[In the formula (2), R ²¹ to R ²⁶ each independently represent a hydrogen atom or an alkyl group; and the rings Z ¹ and Z ² independently of each other represent an aromatic ring having a hydrogen atom which may pass through a halogen atom or a nitro group. And an alkyl group having 1 to 8 carbon atoms, a fluoroalkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkylcarbonyl group having 2 to 6 carbon atoms; and g is an integer of 1 to 4].

[In the formula (3), R ²⁷ to R ³⁰ each independently represent a hydrogen atom or an alkyl group; and the rings Z ³ and Z ⁴ independently of each other represent an aromatic ring having a hydrogen atom which may pass through a halogen atom or a nitro group. , an alkyl group having 1 to 8 carbon atoms, a fluoroalkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkylcarbonyl group having 2 to 6 carbon atoms; Q represents an oxygen atom or a sulfur atom; An integer from 1 to 4].

The alkyl group of R ²¹ to R ³⁰ is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. As a specific example, the same as the above may be mentioned.

The aromatic ring of the ring Z ¹ to Z ⁴ is preferably an aromatic ring having 6 to 10 carbon atoms, more preferably a benzene ring or a naphthalene ring. The aromatic ring may be substituted by a halogen atom, a nitro group, an alkyl group having 1 to 8 carbon atoms, a fluoroalkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. Examples of the halogen atom, the alkyl group having 1 to 8 carbon atoms, and the alkoxy group having 1 to 6 carbon atoms are the same as those described above. The fluoroalkyl group having 1 to 8 carbon atoms is preferably a fluoroalkyl group having 1 to 4 carbon atoms. As a specific example, a part or all of the hydrogen atom of the alkyl group is substituted by a fluorine atom, and particularly preferably Fluoroalkyl. Further, the aromatic ring may be substituted by an alkylcarbonyl group having 2 to 6 carbon atoms, and is preferably an alkylcarbonyl group, preferably an alkylcarbonyl group having 2 to 5 carbon atoms. Specific examples thereof include an ethyl group, a propyl group, a butyl group, a pentamidine group and the like.

g and h are preferably 1 or 2.

A representative example of the cation represented by the above formula (2) is, for example, a cation represented by the following formula:

A representative example of the cation represented by the above formula (3) is, for example, a cation represented by the following formula:

Hereinafter, the anion of the metal complex will be described.

The anion of the metal complex is not particularly limited, but is preferably an anion having a metal complex of an azo compound on the ligand. Here, the azo compound refers to a general term for a compound having at least one azo group in the molecule. As such a ligand, a ligand represented by the following formula (a):

[In the formula (a), the ring Z ⁵ independently of each other represents a substituted or unsubstituted heterocyclic group, and the ring Z ⁶ independently of each other represents a substituted or unsubstituted aromatic hydrocarbon group, and t ¹ and t ² independently represent 0 or 1].

In the present invention, specific examples of the anion having a metal complex of an azo compound on a ligand include an anion represented by the following formula (4):

[In the formula (4), the ring Z ⁵ independently of each other represents a substituted or unsubstituted heterocyclic group, the ring Z ⁶ independently of each other represents a substituted or unsubstituted aromatic hydrocarbon group, and M ¹ represents iron, nickel, copper or aluminum. t ¹ and t ² represent 0 or 1 independently of each other.

The heterocyclic group of the ring Z ⁵ may be a monocyclic heterocyclic group or a polycyclic heterocyclic group. The heterocyclic group is preferably a monovalent heterocyclic group having 3 to 10 carbon atoms, and specific examples thereof include a pyrrolidinyl group, an imidazolidinyl group, and a pyrazolidinyl group. Olinyl, thio Polinyl, piperidinyl, N-hexahydropyridyl (piperidino), piperazine Piperazinyl, high piper Other alicyclic heterocyclic groups such as a nitrogen-containing alicyclic heterocyclic group, 1,3-dioxolan-2-yl group, pyridyl group, pyridyl group Base, pyrimidinyl, oxime Base, quinolyl, isoquinolyl, anthracene base, Pyridyl, quin Lolinyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, benzothiazolyl, Other aromatic heterocyclic groups such as a nitrogen-containing aromatic heterocyclic group such as an azolyl group, a fluorenyl group, a carbazolyl group, a benzimidazolyl group or a quinone imine group, a thienyl group, a furyl group, a piperidyl group or a fluorenyl group. Among them, a nitrogen-containing aromatic heterocyclic group is preferred, and a pyridyl group or a pyrazolyl group is more preferred.

The heterocyclic group may further have a substituent within the scope not departing from the gist of the invention. The position and number of the substituent are arbitrary, and when there are two or more substituents, the substituents may be the same or different. Examples of such a substituent include a halogen atom, a hydroxyl group, a cyano group, a decyl group, a carboxyl group, a nitro group, an amine group, a dialkylamino group, a diarylamino group, an alkoxy group, an aryloxy group, and an alkoxy group. A carbonyl group, an alkylthio group, an arylthio group, a trialkylsulfonyl group, a decyl group, an allyl group, an alkylsulfonyl group, an alkylamine sulfonyl group, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or the like. These substituents may further have a substituent. Among them, the substituent of the heterocyclic group is preferably a hydroxyl group, a cyano group, an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

In addition to the saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms described in the formula (1), an unsaturated aliphatic hydrocarbon group such as an alkenyl group or an alkynyl group may be mentioned as the aliphatic hydrocarbon group. The alkenyl group is preferably an alkenyl group having 2 to 16 carbon atoms, and examples thereof include a vinyl group, a 1-propenyl group, a 1-butenyl group, a 1,3-butadienyl group, a 1-pentenyl group, and a 2-pentyl group. Alkenyl, 1-hexenyl, 2-ethyl-2-butenyl, 2-octenyl, (4-vinyl)-5-hexenyl, 2-decenyl and the like. The alkynyl group is preferably an alkynyl group having 2 to 12 carbon atoms, and examples thereof include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a 1-pentynyl group, a 3-pentynyl group, and a 1-hexyne group. A group, 2-ethyl-2-butynyl, 2-octynyl, (4-ethynyl)-5-hexynyl, 2-decynyl, and the like. As aroma The hydrocarbon group is preferably a carbon number of 6 to 20, more preferably 6 to 10. Specific examples of the aromatic hydrocarbon group include a monocyclic to tricyclic aromatic hydrocarbon group having 6 to 14 carbon atoms such as a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, an anthracenyl group or a 9-fluorenyl group.

The aromatic hydrocarbon group of the ring Z ⁶ preferably has a carbon number of 6 to 20, more preferably a carbon number of 6 to 10. As a specific example, the same as the above may be mentioned, and among them, a phenyl group is preferable. As the substituent of the aromatic hydrocarbon group, in addition to those shown in the description of the heterocyclic group of the ring Z ⁵ , a sulfonic acid group, an amine sulfonyl group, an alkyl sulfonyl group, and two bonds may be mentioned. a group of an alkyl amide group, that is, a group in which an alkyl group of one alkyl guanamine group is bonded to another amide group of another alkyl guanamine group (hereinafter, only referred to as "bonded with 2 alkane" Alkyl-based group"). Among them, preferred are a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkoxy group, a sulfonic acid group, an alkylsulfonyl group, an aminesulfonyl group, an alkylaminesulfonyl group, an alkylguanamine group, a bond. There are two alkylguanamine groups and aliphatic hydrocarbon groups. The alkyl moiety of the alkylsulfonyl group, the amine sulfonyl group, and the alkylamine sulfonyl group, and the aliphatic hydrocarbon group may further have a substituent.

The anion represented by the following formula (4) is preferably an anion represented by the following formula (4-1) or (4-2):

In the formula (4-1), R ⁴¹ each independently represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, and R ⁴² independently represents an alkyl group having 1 to 8 carbon atoms, a halogen atom, and a nitro group. -SO ₃ H, -SO ₂ R ⁴⁴ , -SO ₂ NH ₂ , -SO ₂ NHR ⁴⁵ , or -NHCO-R ⁴⁶ -NHCOR ⁴⁷ , R ⁴³ independently of each other represents nitro, -SO ₃ H, -SO ₂ NH ₂ , or -SO ₂ NHR ⁴⁸ , R ⁴⁴ , R ⁴⁵ , R ⁴⁷ and R ⁴⁸ each independently represent a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, and R ⁴⁶ represents an alkyl group having 1 to 6 carbon atoms. The base, M ² represents iron, nickel, copper or aluminum, and p and q independently represent an integer of 0 to 2, and t ² independently represents 0 or 1].

In the formula (4-2), R ⁵¹ independently represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, and R ⁵² independently represents an alkyl group having 1 to 8 carbon atoms and a carbon number of 1 to 8. Alkoxy group, halogen atom, hydroxyl group, cyano group, nitro group, sulfonic acid group, -SO ₂ NHR ⁵⁴ , or -NHCOR ⁵⁵ , R ⁵³ independently of each other represents an alkyl group having 1 to 8 carbon atoms or a cyano group, R ⁵⁴ And R ⁵⁵ independently of each other represents an alkyl group having 1 to 8 carbon atoms, M ³ represents iron, nickel, copper or aluminum, and x and y independently represent an integer of 0 to 2, and t ² independently represents 0 or 1] .

The alkyl group having 1 to 8 carbon atoms of R ⁴¹ , R ⁴² , R ⁴⁴ , R ⁴⁵ , R ⁴⁷ , R ⁴⁸ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ and R ⁵⁵ may be linear or branched as Specific examples thereof are the same as those described above. Among them, an alkyl group having 1 to 6 carbon atoms is preferred, and an alkyl group having 1 to 4 carbon atoms is more preferred.

Examples of the substituent of the alkyl group of R ⁴¹ include a hydroxyl group and -COOR ⁴⁹ . R ⁴⁹ is an alkyl group having 1 to 8 carbon atoms and may be a straight chain or a branched chain.

Further, examples of the substituent of the alkyl group of R ⁴⁴ , R ⁴⁵ , R ⁴⁷ and R ⁴⁸ include an alkoxy group having 1 to 6 carbon atoms.

Further, examples of the substituent of the alkyl group of R ⁵¹ include a hydroxyl group, -COOR ⁵⁶ , -OCOR ⁵⁶ , -CO-R ⁵⁷ -OH, -COR ⁵⁶ and -CONHR ⁵⁸ . R ⁵⁶ and R ⁵⁸ are each independently an alkyl group having 1 to 8 carbon atoms or a phenyl group, and the alkyl group may be a straight chain or a branched chain. R ⁵⁷ is an alkanediyl group having 1 to 6 carbon atoms and may be a straight chain or a branched chain. Specific examples of the alkyl group having 1 to 6 carbon atoms include a methylene group, an ethyl group, an ethyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, and a propane-1. 2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4- Diki, pentane-1,4-diyl, pentane-1,5-diyl, hexane-1,5-diyl, hexane-1,6-diyl and the like.

The alkanediyl group having 1 to 6 carbon atoms of R ⁴⁶ may be a straight chain or a branched chain.

As M ² and M ³ , iron, nickel, copper, preferably iron, nickel, and more preferably iron are preferable.

p is preferably 0 or 1.

q is preferably 1 or 2.

x is preferably 0 or 1.

y is preferably 2, and in this case, it is preferred that the two R ⁵³ on the hetero ring may be the same or different.

The coloring agent can also have A salt exchange reaction of a cation of a skeleton or a cation having a methine skeleton with a compound containing an anion of a metal complex.

Contained as having a cationic compound of the skeleton, which can be used well-known The basic dye may, for example, be CI Basic Violet 11 or Rose Bengal 6G. Is a basic dye. Among them, rose red 6G is preferred.

As the compound containing a cation having a methine skeleton, a well-known multi-methyl basic dye can be used, and examples thereof include CI basic red 12, CI basic red 13, CI basic red 14, and CI basic violet. 7. Multiple methylation of CI alkaline purple 16, CI alkaline yellow 1, CI basic yellow 11, CI basic yellow 13, CI basic yellow 21, CI basic yellow 28, CI basic yellow 51, etc. Basic dyes. Among them, preferred are C.I. Basic Red 12, C.I. Basic Red 13, C.I. Basic Red 14.

Further, in the present invention, "basic dye" means an ionic dye having a cationic moiety as a chromophore, and an ionic dye which forms a salt with the cationic moiety is also a basic dye.

In the compound containing the anion of the metal complex, the compound containing the anion of the metal complex of the azo compound on the ligand can be azo compound synthesized by, for example, the method described in JP-A-2011-148993. It is synthesized by reaction with a compound containing iron, nickel, copper or aluminum.

The coloring composition of the present invention may be used by mixing other coloring agents other than the coloring agent. The coloring agent is not particularly limited, and a color or a material may be appropriately selected depending on the application, and any of pigments, dyes, and natural colors other than the coloring agent may be used, but in the sense of obtaining a pixel having high luminance and color purity, It is preferably an organic pigment or an organic dye, more preferably an organic pigment.

As the above-mentioned organic pigment, for example, a compound classified as a pigment in a color index (CI; issued by The Society of Dyers and Colourists Co., Ltd.) is preferable, and it is preferably disclosed in JP-A-2001-081348 and JP-A-. Japanese Unexamined Patent Application Publication No. Publication No. Publication No. Publication No. Publication No. Publication No. Publication No. Publication No. Publication No. Publication No. JP-A-A Such as the lake pigment, CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Blue 15:6, CI Pigment Blue 80, CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, CI Pigment Yellow 211, CI Pigment Orange 38, CI Pigment Violet 23, etc. Organic pigments other than lake pigments. Further, among the lake pigments, a triarylmethane-based lake pigment is preferred. a lake pigment, an azo lake pigment, more preferably a triaryl methane lake pigment and It is a lake pigment.

Further, as the above organic dye, it is preferably a dye, a triarylmethane dye, a methine dye, an anthraquinone dye, an azo dye, etc., more preferably an anion having no metal complex A methine dye which is a dye and an anion which does not have a metal complex. More specifically, JP-A-2010-32999, JP-A-2010-254964, JP-A-2011-138094, International Publication No. 10/123071, and JP-A-2011-116803 The organic dyes described in Japanese Laid-Open Patent Publication No. 2011-174987, and Japanese Laid-Open Patent Publication No. 2011-174987.

In the present invention, the pigment and the dye may be used alone or in combination of two or more.

In the present invention, when a pigment is used as the other coloring agent, the pigment may be purified by a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or the like. Further, the pigment may be modified with a resin surface as needed to be used. For example, a vehicle resin described in JP-A-2001-108817 or a commercially available resin for dispersing various pigments is used as the resin for modifying the surface of the particles of the pigment. As a resin coating method of the carbon black surface, for example, Japanese Patent Laid-Open No. Hei 9-71733, Japanese Patent Laid-Open A method described in, for example, Japanese Laid-Open Patent Publication No. Hei 9-124969. Further, the organic pigment may be used after grinding the primary particles by so-called salt milling. As the salt milling method, for example, a method disclosed in Japanese Laid-Open Patent Publication No. Hei 08-179111 can be employed.

Further, in the present invention, it is also possible to further contain a known dispersing agent and dispersing aid together with other coloring agents which are arbitrarily mixed. Examples of the known dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene alkyl phenyl ether dispersant, and polyethylene. A diol diester type dispersing agent, a sorbitan fatty acid ester type dispersing agent, a polyester type dispersing agent, an acryl type dispersing agent, etc., and a dispersing auxiliary agent, a pigment derivative etc. are mentioned.

Such a dispersing agent can be obtained by a commercial method. For example, as an acrylic dispersing agent, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK-Chemie (BYK)) And as the urethane-based dispersing agent, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, BYK-Chemie (BYK)), Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), etc., and examples of the polyethyleneimine-based dispersant include Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), and examples of the polyester-based dispersant include Ajisper PB821 and Ajisper PB822. Ajisper PB880, Ajisper PB881 (above is Ajinomoto Fine-Techno Co., Ltd.) and the like.

In addition, specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and quinoline yellow sulfonic acid derivatives.

In the present invention, other colorants may be used singly or in combination of two or more.

When other coloring agents are used, the content of the coloring agent is preferably from 1 to 80% by mass, more preferably from 2 to 50% by mass, even more preferably from 3 to 30% by mass, based on the total content of the coloring agent, particularly preferably 5~20% by mass.

The content ratio of the (A) coloring agent is usually 5 to 70 in the solid content of the coloring composition, based on the viewpoint of forming a heat resistance, a pixel having high luminance and excellent color purity, or a black matrix or a black spacer having excellent light blocking properties. The mass% is preferably from 5 to 60% by mass. The term "solid content" as used herein means a component other than the solvent described later.

- (B) Adhesive Resin -

The (B) adhesive resin which is a colored composition of the present invention is not particularly limited, and is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter referred to as "a polymer having a carboxyl group") is preferable, and an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer (b1)" is exemplified. ") Copolymer with other copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (b2)").

The unsaturated monomer (b1) may, for example, be (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2-(methyl)acryloxyethyl)ester, or ω-carboxyl polymerization. Caprolactone mono(meth)acrylate, p-vinylbenzoic acid, and the like.

These unsaturated monomers (b1) can be used singly or in combination of two or more.

Further, as the unsaturated monomer (b2), for example, an N-position substituted maleimide such as N-phenylmaleimide or N-cyclohexylmaleimide; An aromatic vinyl compound such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylepoxypropyl ether, acenaphthylene; For example, methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, Benzyl (meth)acrylate, polyethylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isodecyl (meth) acrylate, Tricyclo[methyl]acrylic acid [5.2.1.0 ^2,6 ]decane-8-yl ester, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, (meth)acrylic acid Ethylene oxide modification of 4-hydroxyphenyl ester and p-cumylphenol (methyl) Ethacrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acrylomethoxymethyl]epoxypropane, 3-[ (Meth) acrylate such as (meth)acrylomethoxymethyl]-3-ethyl propylene oxide; such as cyclohexyl vinyl ether, isodecyl vinyl ether, tricyclo [5.2.1.0 ^{2, 6]} decan-8-yl vinyl ether, pentacyclopentadecane alkenyl vinyl ether, 3- (vinyloxy methyl) -3-ethyl propylene oxide and the like vinyl ethers; such as polystyrene A macromonomer having a mono(meth)acrylonitrile group at the terminal of a polymer molecular chain such as poly(methyl) acrylate, poly(meth) acrylate or polyoxyalkylene.

These unsaturated monomers (b2) may be used singly or in combination of two or more.

In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably from 5 to 50% by mass, more preferably from 10%. 40% by mass. In this range, the unsaturated monomer (b1) is copolymerized to obtain a color-developing composition excellent in alkali developability and storage stability.

Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Copolymer.

In the present invention, Japanese Laid-Open Patent Publication No. Hei 5-19467, Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth)acrylonyl group in a side chain is used as an adhesive resin, as disclosed in Japanese Laid-Open Patent Publication No. 2008-181095.

The weight average molecular weight (Mw) of the adhesive resin of the present invention, which is measured by gel permeation chromatography (hereinafter referred to as GPC) (dissolved solvent: tetrahydrofuran), is usually 1,000 to 100,000, preferably 3,000. 50,000. By adopting such a form, the residual film ratio, the pattern shape, the heat resistance, the electrical characteristics, and the resolution of the film can be further improved, and the generation of dry impurities during coating can be suppressed to a high degree.

Further, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the adhesive resin of the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. Further, the term "Mn" as used herein means the number average molecular weight converted to polystyrene measured by GPC (eluent solvent: tetrahydrofuran).

The adhesive resin of the present invention can be produced by a known method, and can be disclosed by, for example, JP-A-2003-222717, JP-A-2006-259680, and International Publication No. 07/029871. Methods to control its structure or Mw, Mw / Mn.

In the present invention, the adhesive resin may be used singly or in combination of two or more.

In the present invention, the content of the adhesive resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. By adopting such a form, the alkali developability, the storage stability of the colored composition, and the chromaticity characteristics can be further improved.

- (C) Polymeric Compound -

In the present invention, the "polymerizable compound" means a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an epoxy group, an oxypropylene group, and an N-alkoxymethylamino group. In the present invention, the polymerizable compound is preferably a compound having two or more (meth)acryl fluorenyl groups or a compound having two or more N-alkoxymethylamino groups.

Specific examples of the compound having two or more (meth) acryloyl fluorenyl groups include polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid, and modified by caprolactone. a polyfunctional (meth) acrylate, an alkylene oxide modified polyfunctional (meth) acrylate, a polyfunctional amine group obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate An acid ester (meth) acrylate or a polyvalent (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group with an acid anhydride.

Here, as the aliphatic polyhydroxy compound, for example, a dihydric aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol, or polypropylene glycol; for example, glycerin, trimethylolpropane, and neopentyl A trihydric or higher aliphatic polyhydroxy compound such as tetraol or dipentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol tri(meth)acrylate. , dipentaerythritol penta (meth) acrylate, glycerol dimethacrylate, and the like. Examples of the polyfunctional isocyanate include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. The acid anhydride may, for example, be an acid anhydride of a dibasic acid such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride or hexahydrophthalic anhydride, such as pyromellitic anhydride. a tetrabasic acid dianhydride such as biphenyltetracarboxylic dianhydride or benzophenone tetracarboxylic dianhydride.

In addition, the polyfunctional (meth) acrylate which is modified by the caprolactone is, for example, a compound described in paragraphs [0015] to [0018] of JP-A-11-44955. Examples of the polyalkylene (meth)acrylate modified with the alkylene oxide include bisphenol A di(meth)acrylate modified from at least one selected from the group consisting of ethylene oxide and propylene oxide. At least one modified from ethylene oxide and propylene oxide a tris(meth)acrylate polycyanate, trimethylolpropane tri(meth)acrylate modified from at least one selected from the group consisting of ethylene oxide and propylene oxide, selected from the group consisting of ethylene oxide and At least one modified pentaerythritol tri(meth)acrylate in propylene oxide, neopentyltetrakis(meth)acrylate modified from at least one selected from the group consisting of ethylene oxide and propylene oxide An ester, at least one modified from at least one selected from the group consisting of ethylene oxide and propylene oxide, modified with at least one selected from the group consisting of ethylene oxide and propylene oxide Dipentaerythritol hexa(meth) acrylate or the like.

In addition, examples of the compound having two or more N-alkoxymethylamino groups include a compound having a melamine structure, a benzoguanamine structure, and a urea structure. Moreover, the melamine structure and the benzoguanamine structure refer to having one or more three Ring or phenyl substituted three The chemical structure of the ring as a basic skeleton is a concept including melamine, benzoguanamine or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N,N,N',N',N",N"-hexa(alkoxymethyl)melamine, N, N,N',N'-tetrakis(alkoxymethyl)benzoguanamine, N,N,N',N'-tetrakis(alkoxymethyl)glycolil, and the like.

Among these polymerizable compounds, a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid or a polyfunctional group modified by caprolactone is preferred (A) Acrylate, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate having carboxyl group, N, N, N', N', N", N"-hexa (alkoxy) Methyl) melamine, N, N, N', N'-tetrakis(alkoxymethyl)benzoguanamine. The strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and it is difficult to produce scum and residual film on the unexposed portion of the substrate and the light shielding layer. Among the polyfunctional (meth) acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, trimethylolpropane triacrylate and pentaerythritol triacrylate are particularly preferred. Dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, in a polyfunctional (meth) acrylate having a carboxyl group, particularly preferably obtained by reacting pentaerythritol triacrylate with succinic anhydride A compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride.

In the present invention, the (C) polymerizable compound may be used singly or in combination of two or more.

The content of the (C) polymerizable compound of the present invention is preferably from 10 to 1,000 parts by mass, more preferably from 20 to 700 parts by mass, even more preferably from 100 to 500 parts by mass, per 100 parts by mass of the (A) coloring agent. By adopting such a form, it is possible to further improve the curability and the alkali developability, and it is possible to suppress the occurrence of scum, residual film, or the like on the unexposed portion of the substrate or the light shielding layer at a high level.

-Photopolymerization initiator -

The coloring composition of the present invention may be doped with a photopolymerization initiator. Thereby, the coloring composition can be imparted with radiation linearity. The photopolymerization initiator used in the present invention is a compound which can generate an active species which can initiate polymerization of the above polymerizable compound by exposing radiation such as visible light, ultraviolet light, far ultraviolet ray, electron beam or X-ray.

As such a photopolymerization initiator, for example, a thioxanthone compound, an acetophenone compound, a biimidazole compound, and the like are mentioned. A compound, an O-indenyl hydrazine compound, an onium salt compound, a benzoin compound, a benzophenone compound, an α-diketone compound, a polynuclear hydrazine compound, a diazo compound, a quinone sulfinate compound, or the like.

In the present invention, the photopolymerization initiator may be used singly or in combination of two or more. As the photopolymerization initiator, it is preferably selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, and three At least one of the group of the compound and the O-mercaptopurine compound.

In a preferred photopolymerization initiator of the present invention, specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone. , 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyl Thioxanthone and the like.

Further, as a specific example of the above acetophenone compound, 2-methyl-1-[4-(methylthio)phenyl]-2- Olinone propan-1-one, 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Polinylphenyl)butan-1-one and the like.

Further, as a specific example of the above biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2 , 2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6 -Trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and the like.

Further, when a biimidazole compound is used as a photopolymerization initiator, it is preferred to use a hydrogen donor in combination based on the viewpoint of improving sensitivity. The term "hydrogen donor" as used herein refers to a compound capable of supplying a hydrogen atom to a radical generated by a biimidazole compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzoene. A thiol hydrogen donor such as azole; an amine hydrogen donor such as 4,4'-bis(dimethylamino)benzophenone or 4,4'-bis(diethylamino)benzophenone. In the present invention, the hydrogen donors may be used singly or in combination of two or more. However, it is preferred to use one or more kinds of thiol hydrogen donors and one or more amine hydrogen donors in view of further improving the sensitivity.

Again, as the above three Specific examples of the compound include 2,4,6-paran (trichloromethyl)-all three 2-methyl-4,6-bis(trichloromethyl)-all three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-all three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-all three 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-all three , 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-all three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-all three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-all three , 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-all three Three with a halogenated methyl group Compound.

Further, as a specific example of the O-indenyl ruthenium compound, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzamide), 1 -[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethanone 1-(O-acetamidine), 1-[9-ethyl- 6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-ethanone 1-(O-acetamidine), 1-[9-ethyl -6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene}-9H-indazol-3-yl]-B Ketone 1-(O-acetamidine) and the like. As a commercial item of the O-indenyl ruthenium compound, NCI-831, NCI-930 (above, ADEKA Co., Ltd.), DFI-020, DFI-091 (above, DAITO CHEMIX Co., Ltd.), etc. can be used. .

In the present invention, when a photopolymerization initiator other than the biimidazole compound such as an acetophenone compound is used, a sensitizer may be used in combination. As such a sensitizer, for example, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-diethyl Amino acetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-double (4-Diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethylamine) Base) Chalcone and the like.

In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass, per 100 parts by mass of the (C) polymerizable compound. By adopting such a form, the hardenability and film properties can be further improved.

- solvent -

The colored composition of the present invention contains the above components (A) to (C) and any other components added arbitrarily, but usually a solvent is blended to prepare a liquid composition.

The solvent can be appropriately selected and used as long as it can disperse or dissolve the components or other components constituting the colored compositions (A) to (C), does not react with these components, and has moderate volatility.

Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethylene glycol. Monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether , propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, Dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether (poly) alkanediol monoalkyl ether; methyl lactate, ethyl lactate, etc. Alkyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tertiary butanol, octanol, 2-ethylhexanol, cyclohexanol, etc. (cyclo)alkyl alcohols Ketone alcohols such as diacetone alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, etc. Glycol monoalkyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2- Ketones such as heptanone and 3-heptanone; diacetates such as propylene glycol diacetate, 1,3-butanediol diacetate, and 1,6-hexanediol diacetate; 3-methoxy Methyl propyl propionate, ethyl 3-methoxypropionate , alkoxycarboxylates such as methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate Class; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, butyric acid Propyl ester, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutyrate Other esters such as esters; An aromatic hydrocarbon such as toluene or xylene; a decylamine such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone; or an indoleamine.

Among these solvents, (poly)alkylene glycol monoalkyl ethers, alkyl lactates, (poly)alkylene glycol monoalkyl ether acetates are preferred from the viewpoints of solubility, pigment dispersibility, coating properties and the like. Esters, other ethers, ketones, diacetates, alkoxycarboxylates, other esters, particularly preferably propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3 -heptanone, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Ester, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, propionic acid N-butyl ester, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate and the like.

In the present invention, the solvent may be used singly or in combination of two or more.

The content of the solvent is not particularly limited, but the total concentration of each component excluding the solvent of the coloring composition is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass. By adopting such a form, a colorant dispersion having good dispersibility and stability, and a coloring composition excellent in coatability and stability can be obtained.

-additive-

The colored composition of the present invention may also contain various additives as needed.

Examples of the additive include a filler such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); a surfactant such as a fluorine surfactant or a polyfluorene surfactant; and a vinyl group; Trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Baseline, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane , 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, An adhesion promoter such as 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane; 2,2-thiobis(4- Methyl-6-tertiary butyl phenol), 2,6-di-tertiary butyl phenol, neopentyl alcohol tetrakis[3-(3,5-di-tertiary butyl-4-hydroxyphenyl) Propionate], 3,9-bis[2-[3-(3-tri-butyl-4-hydroxy-5-methylphenyl)-propenyloxy]-1,1-dimethylethyl Base]-2 , 4,8,10-tetraoxa-spiro[5.5]undecane, thiodiethylene bis[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate] Oxidizing agent; ultraviolet absorbers such as 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and alkoxybenzophenone; Agglutinating agent; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1 a residue improving agent such as pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol; succinic acid mono[2-( Methyl) propylene oxiranyl ethyl] A developer improving agent such as an ester, a mono[2-(methyl)acryloxyethyl) phthalate, or an ω-carboxypolycaprolactone mono(meth)acrylate.

The colored composition of the present invention can be prepared by an appropriate method, and examples of the preparation method include those disclosed in JP-A-2008-58642 and JP-A-2010-132874. When both the dye and the pigment are used as the coloring agent, the dye solution passing through the first filter and the separately prepared pigment dispersion may be used after passing the dye solution through the first filter as disclosed in Japanese Laid-Open Patent Publication No. 2010-132874. A method in which the mixture is mixed and the obtained colored composition is passed through a second filter. Further, the dye and the components (B) to (C) and other components used as needed may be dissolved in a solvent, and the resulting solution may be passed through the first filter, and then the solution passing through the first filter may be separately prepared. A method in which the pigment dispersion liquid is mixed and the obtained colored composition is passed through a second filter. In addition, after passing the dye solution through the first filter, the dye solution passing through the first filter may be mixed with the above components (B) to (C) and other components as needed. The solution obtained by dissolving and passing the obtained solution through the second filter, and further mixing the solution passing through the second filter with the separately prepared pigment dispersion, and then passing the obtained colored composition through a third filter.

Colored cured film and method of producing the same

The colored cured film of the present invention is formed by using the colored composition of the present invention, and specifically refers to each color pixel, black matrix, black spacer, or the like used for a display element or a solid-state imaging element.

Hereinafter, a colored cured film for a color filter and a method for forming the same will be described.

As a method of manufacturing a color filter, the first method can be exemplified. First, on the surface of the substrate, a light shielding layer (black matrix) is formed in such a manner as to divide the portion in which the pixels are formed. Next, a liquid composition of, for example, a red radiation sensitive coloring composition of the present invention is applied onto the substrate, and then prebaked to evaporate the solvent to form a coating film. Next, the coating film was exposed through a mask, and then developed with an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Thereafter, post-baking is performed to form a pixel array in which a red pixel pattern (colored cured film) is arranged in a predetermined arrangement.

Next, the composition is colored with each of the green or blue radiation, and the respective radiation-sensitive coloring compositions are applied, pre-baked, exposed, developed, and post-baked in the same manner as described above, and sequentially formed on the same substrate. Green pixel array and blue pixel array. Thereby, a color filter in which the pixel arrays of the three primary colors of blue, green, and red are arranged on the substrate is prepared. However, the order in which the respective color pixels are formed in the present invention is not limited to the above.

Further, the black matrix can be formed by forming a desired pattern by a photolithography method using a metal thin film such as chromium which is formed by sputtering or vapor deposition, but it is also possible to use a radiation-sensitive coloring in which black pigment is dispersed. The composition is formed in the same manner as when the above-described pixels are formed.

Examples of the substrate used for forming the color filter include glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidimide, and polyimine.

Further, such pretreatments such as drug treatment, plasma treatment, ion plating, sputtering, gas phase reaction, and vacuum vapor deposition using a decane coupling agent or the like may be performed in advance on these substrates as needed.

When the radiation sensitive coloring composition is applied to the substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method (slit coating method), or a rod coating method may be employed. However, Tejia uses spin coating and slot coating.

Prebaking is usually carried out by combining vacuum drying and heat drying. Drying under reduced pressure is usually carried out until it reaches 50 to 200 Pa. Further, the conditions for heating and drying are usually 70 to 110 ° C for about 1 to 10 minutes.

The coating thickness is a film thickness after drying, and it is usually 0.6 to 8 μm, preferably 1.2 to 5 μm.

Examples of the light source for forming radiation used in at least one selected from the group consisting of a pixel and a black matrix include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, and a medium pressure mercury lamp. Light source such as low-pressure mercury lamp or argon ion laser, YAG laser, XeCl excimer laser, nitrogen laser and other laser light sources. As the exposure light source, an ultraviolet LED can also be used. Radiation having a wavelength in the range of 190 to 450 nm is preferred.

The exposure amount of the radiation is generally preferably from 10 to 10,000 J/m ² .

Further, as the alkali developing solution, for example, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-diazabicyclo-[5.4.0] is preferable. An aqueous solution of -7-undecene or 1,5-diazabicyclo-[4.3.0]-5-decene.

A water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkali developer in an appropriate amount. In addition, cleaning is usually carried out after alkali development.

As the development treatment method, a shower development method, a spray development method, a dip development method, a paddle development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at normal temperature.

The post-baking conditions are usually 180 to 280 ° C for about 10 to 60 minutes.

The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1.0 to 3 μm.

Moreover, as a second method of producing a color filter, a method of producing each color pixel by an inkjet method disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. In this method, first, a partition wall having a light blocking function at the same time is formed on the surface of the substrate. Next, a liquid composition of, for example, a blue thermosetting coloring composition of the present invention is discharged by an inkjet device in the formed partition wall, and then prebaked to evaporate the solvent. Next, the coating film is exposed as needed, followed by post-baking to harden it to form a blue pixel pattern.

Next, using a green or red thermosetting coloring composition, a green pixel pattern and a red pixel pattern are sequentially formed on the same substrate in the same manner as described above. In this way, a color filter in which the pixel patterns of the three primary colors of blue, green, and red are arranged is disposed on the substrate. However, the order in which the respective color pixels are formed in the present invention is not limited to the above.

Further, since the partition wall does not only function as a light-shielding function, but also functions to prevent color mixing of the thermosetting coloring composition of each color discharged into the divided region, the black matrix is used in comparison with the black matrix used in the first method. The film thickness is thick. Therefore, the partition walls are usually formed using a black radiation-sensitive linear composition.

The light source of the substrate or the radiation used for forming the color filter, and the method or condition for prebaking or postbaking are the same as the first method described above. As a result, the film thickness of the pixel formed by the ink jet method is equal to the height of the partition wall.

After forming a protective film on the pixel pattern thus obtained, a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer may be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but a spacer having a light-shielding property (black spacer) can also be formed. In this case, a colored radiation linear composition in which a black colorant is dispersed is used, but the colored composition of the present invention can also be applied to the formation of the black spacer.

The colored composition of the present invention can be applied to the formation of any of the colored cured films such as the respective color pixels, the black matrix, and the black spacer used in the above color filter.

The color filter including the colored cured film of the present invention thus formed is extremely useful for color liquid crystal display elements, color image tube elements, color sensors, organic EL display elements, electronic paper, and the like because of extremely high luminance and coloring power. Further, the display element to be described later may have at least one or more colored cured films formed using the colored composition of the present invention.

Display component

The display element of the present invention comprises the colored cured film of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.

The color liquid crystal display element having the colored cured film of the present invention may be of a transmissive type or a reflective type, and an appropriate configuration may be employed. For example, a color filter may be formed on a substrate different from a driving substrate on which a thin film transistor (TFT) is disposed, and a structure in which the driving substrate and the substrate on which the color filter is formed are opposed to each other via a liquid crystal layer may be employed. Further, a substrate on which a color filter is formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed, and an ITO (tin-doped indium oxide) electrode or IZO (indium oxide and zinc oxide) may be used. The mixture is a structure in which the substrate of the electrode faces the liquid crystal layer. The latter construction has the advantage of being able to exceptionally increase the aperture ratio and obtain a bright, high-definition liquid crystal display element. Further, when the latter configuration is employed, the black matrix or the black spacer may be formed on either the substrate side on which the color filter is formed and the substrate side on which the ITO electrode or the IZO electrode is formed.

A color liquid crystal display element having the colored cured film of the present invention may be provided with a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). Examples of the white LED include a white LED in which a red LED, a green LED, and a blue LED are combined, and white light is obtained by color mixing, a combination of a blue LED, a red LED, and a green phosphor, and white light is obtained by color mixing. White LED, combined blue LED, red illuminating phosphor and green illuminating phosphor, and white LEDs obtained by color mixing, and white LEDs obtained by mixing blue LEDs with YAG phosphors Combining blue LED, orange illuminating phosphor and green illuminating phosphor, and obtaining white light white LED by combining color, combined ultraviolet LED, red luminescent phosphor, green luminescent phosphor and blue luminescent fluorescent A white LED or the like that obtains white light by color mixing.

The color liquid crystal display element having the colored cured film of the present invention can be applied to a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, or an IPS (In-Planes Switching) type. A suitable liquid crystal mode such as VA (Vertical Alignment) or OCB (Optically Compensated Birefringence).

In addition, the organic EL display element having the colored cured film of the present invention can be suitably configured, and the structure disclosed in Japanese Laid-Open Patent Publication No. Hei 11-307242 can be cited.

Further, the electronic paper sheet having the colored cured film of the present invention can be suitably configured, and the structure disclosed in Japanese Laid-Open Patent Publication No. 2007-41169 can be mentioned.

[Examples]

The embodiments of the present invention will be further specifically described below by way of examples. However, the invention is not limited to the following examples.

(Synthesis of this colorant) Synthesis Example 1

0.28 parts by mass of the compound represented by the formula (a-1) synthesized by the method described in JP-A-2011-148994 was dissolved in 5 parts by mass of dimethylformamide, and 0.092 parts by mass of ginseng (acetamidine) was further added. Acetone) Iron (III) and 0.16 parts by mass of sodium acetate were heated and stirred at 135 ° C for 24 hours. The reaction liquid was poured into 30 parts by mass of a 20% aqueous sodium chloride solution, and the precipitated solid was filtered and washed with a small amount of pure water, and then dried under reduced pressure at 60 ° C to obtain 0.27 parts by mass (a- 2) The compound shown.

0.12 parts by mass of the compound represented by the formula (a-2) and 0.052 parts by mass of the genus Rose Bengal 6G, which is a basic dye, was added to 1 part by mass of N-methylpyrrolidone to dissolve it, and stirred for 5 hours. The reaction liquid was poured into 20 parts by mass of water, and the solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 0.13 parts by mass of a compound represented by the following formula (A2). It is used as a coloring agent (A2).

Synthesis Example 2~5

A coloring agent (A3) to (A6) was synthesized in the same manner as in Synthesis Example 1 except that the type of the metal complex and/or the basic dye used as the raw material in Synthesis Example 1 was changed as shown in Table 1. .

Further, CI basic red 12 is a compound represented by the following formula:

<Preparation of colorant solution> Modulation example 1

5 parts by mass of Basic Violet 11:1 represented by the following formula was mixed with 95 parts by mass of cyclohexanone as a solvent to prepare a colorant solution (A1).

Modulation example 2

5 parts by mass of the colorant (A2) and 95 parts by mass of cyclohexanone as a solvent were mixed to prepare a colorant solution (A2).

Modulation example 3~6

The coloring agent solutions (A3) to (A6) were prepared in the same manner as in Preparation Example 2 except that the coloring agents (A3) to (A6) were used instead of the coloring agent (A2) of Preparation Example 2.

<Synthesis of Adhesive Resin> Synthesis Example 6

In a flask equipped with a cooling tube and a stirrer, 100 parts by mass of propylene glycol monomethyl ether acetate was placed and replaced with nitrogen. It was heated to 80 ° C, and 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 mass were dropped at 1 hour. 2-hydroxyethyl methacrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid mono(2-propenyloxy B A mixed solution of an ester and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was maintained at this temperature for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and further polymerization was carried out for 1 hour to obtain an adhesive resin solution (solid content concentration: 33% by mass). The obtained adhesive resin had a Mw of 12,200 and an Mn of 6,500. This adhesive resin was used as the "adhesive resin (B1)".

<Modulation and evaluation of coloring composition> Modulation of coloring composition Example 1

40.5 parts by mass of a coloring agent solution (A1) as a coloring agent (A), 3.0 parts by mass of a colorant solution (A2), and 26.3 parts by mass of an adhesive resin (B1) solution as (B) an adhesive resin, 9.9 parts by weight (C) a mixture of dicopentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd.; trade name KAYARAD DPHA) and 1.8 parts by mass of the polymerizable compound (C) Photopolymerization initiator 2-benzyl-2-dimethylamino-1-(4-N- Molecular phenyl)butane-1-one (trade name: IRGACURE 369; manufactured by Ciba Specialty Chemicals Co., Ltd.) and 0.1 part by mass of NCI-930 (made by ADEKA Co., Ltd.), 0.05 parts by mass of MEGAFACEF as a fluorine-based surfactant -554 (manufactured by DIC Corporation) and propylene glycol monomethyl ether acetate as a solvent to prepare a colored composition (S-1) having a solid content concentration of 20% by mass.

Contrast assessment

The obtained colored composition was applied onto a glass substrate by a spin coater, and then prebaked for 10 minutes on a hot plate at 80 ° C to form a coating film. The number of rotations of the spin coater was changed, and three coating films having different film thicknesses were formed in the same manner.

Next, after the substrates were cooled to room temperature, radiation of respective wavelengths of 365 nm, 405 nm, and 436 nm was exposed to the respective coating films at a exposure amount of 2,000 J/m ² without using a high-pressure mercury lamp. Thereafter, the substrate was discharged with a developing solution containing a 23 ° C, 0.04% by mass aqueous potassium hydroxide solution at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm) to carry out shower development for 90 seconds. Thereafter, the substrate was washed with ultrapure water and air-dried, and further post-baked in a clean oven at 200 ° C for 30 minutes to form a cured film for evaluation.

The substrate on which the cured film is formed is sandwiched between two deflecting plates, and the polarizing plate (wavelength range: 380 to 780 nm) is irradiated from the back side while rotating the deflecting plate on the front side, and a luminance meter LS-100 (manufactured by Minolta Co., Ltd.) is used. Measure the maximum and minimum values of the transmitted light intensity. Thereafter, for each of the cured films, a value obtained by dividing the maximum value by the minimum value was used as a contrast ratio. From the measurement results, the contrast at the chromaticity coordinate value y = 0.080 was obtained. Will comment The results are shown in Table 2. In addition, the greater the value of the contrast, the better the index.

Example 2~5

The coloring compositions (S-2) to (S-5) were prepared in the same manner as in Example 1 except that the coloring agent solution shown in Table 2 was used instead of the coloring agent solution (A2) in Example 1. Thereafter, the obtained colored composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

Comparative example 1

A coloring composition (S-6) was prepared in the same manner as in Example 1 except that the coloring agent solution (A2) in Example 1 was not used. Thereafter, the obtained colored composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

Claims (7)

A colored composition comprising (A) a colorant, (B) an adhesive resin, and (C) a coloring composition of a polymerizable compound, the coloring agent comprising: A salt of a skeleton or a cation having a methine skeleton and an anion of a metal complex, the metal constituting the metal complex is at least one selected from the group consisting of iron, nickel, copper, and aluminum. The colored composition of claim 1, wherein the anion of the metal complex is based on an azo compound on the ligand. The coloring composition of claim 2, wherein the anion of the metal complex having the azo compound as a ligand is an anion represented by the following formula (4): In the formula (4), the ring Z ⁵ independently of each other represents a substituted or unsubstituted heterocyclic group, and the ring Z ⁶ independently represents a substituted or unsubstituted aromatic hydrocarbon group, and M ¹ represents iron, nickel, copper or aluminum, t ¹ and t ² represent 0 or 1 independently of each other. The colored composition of any one of claims 1 to 3, wherein the The cation of the skeleton is a cation represented by the following formula (1): In the formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, -R ⁸ or an aromatic hydrocarbon group having 6 to 10 carbon atoms; however, the hydrogen atom contained in the aromatic hydrocarbon group may be Via a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ R ⁸ , -SO ₂ NHR ⁹ or -SO ₂ NR ⁹ R ¹⁰ substituted; R ⁵ and R ⁶ independently of each other represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; and R ⁷ represents -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ R ⁸ , -SO ₂ NHR ⁹ or -SO ₂ NR ⁹ R ¹⁰ ; r represents an integer of 0 to 5, and if r is an integer of 2 or more, plural R ⁷ may be the same or different; ⁸ represents a saturated hydrocarbon group having a carbon number of 1 to 20; but, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, and in the CC bond between the hydrocarbon group may have a saturated oxygen atom, a carbonyl group, or -NR ⁸ -; R ⁹ and R ¹⁰ independently of each other represents a chain alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms or -Z, or a substitution of 2 to 10 carbon atoms formed by bonding of R ⁹ and R ^{10 to} each other. Or an unsubstituted heterocyclic group; however, the hydrogen atom contained in the alkyl group and the cycloalkyl group may be substituted with a hydroxyl group, a halogen atom, -Z, -CH=CH ₂ or -CH=CHR ⁸ , and There may be an oxygen atom, a carbonyl group or -NR ⁸ - between the CC bond of the alkyl group and the cycloalkyl group, and the hydrogen atom contained in the heterocyclic group may be substituted by -R ⁸ , -OH or -Z; M represents a sodium atom Or a potassium atom; Z represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 4 to 10 carbon atoms; however, the hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group may pass through -OH, -R ⁸ , -OR ⁸ , -NO ₂ , -CH=CH ₂ , -CH=CHR ⁸ or a halogen atom substitution. The coloring composition according to any one of claims 1 to 3, wherein the cation having a methine skeleton is a cation represented by the following formula (2) or (3): In the formula (2), R ²¹ to R ²⁶ each independently represent a hydrogen atom or an alkyl group; and the rings Z ¹ and Z ² independently of each other represent an aromatic ring having a hydrogen atom which may pass through a halogen atom or a nitro group. The alkyl group having 1 to 8 carbon atoms, the fluoroalkyl group having 1 to 8 carbon atoms, the alkoxy group having 1 to 6 carbon atoms, and the alkylcarbonyl group having 2 to 6 carbon atoms; g is an integer of 1 to 4; In the formula (3), R ²⁷ to R ³⁰ each independently represent a hydrogen atom or an alkyl group; and the rings Z ³ and Z ⁴ independently of each other represent an aromatic ring having a hydrogen atom which may pass through a halogen atom or a nitro group. An alkyl group having 1 to 8 carbon atoms, a fluoroalkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkylcarbonyl group having 2 to 6 carbon atoms; Q represents an oxygen atom or a sulfur atom; An integer of ~4. A colored hardening film formed using the coloring composition according to any one of claims 1 to 5. A display element comprising the colored cured film of claim 6.