TW201321449A - Coloring agent, coloring composition, color filter and display element - Google Patents

Abstract

The present invention provides a coloring composition which can form a coloring layer capable of existing a good voltage holding ratio, high contrast and high thermal resistance at the same time while using dye as a coloring agent. The coloring composition is characterized in comprising the following components (A), (B) and (C): (A) a coloring agent containing the dye represented by the following formula (1), (B) a binder resin, and (C) a crosslinking agent. In formula (1), X- represents an anion, a represents an integer which is determined so that the compound is electrically neutral, m represents an integer of 0 to 5, R1 to R4 respectively represent a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms and the like, R5 respectively represents -SO3- and the like, R6 represents an monovalent saturated hydrocarbon group and the like, R7 represents an monovalent hydrocarbon group and the like, R8 and R9 respectively represent a monovalent saturated aliphatic hydrocarbon group and the like, R10 represents a monovalent hydrocarbon group and the like, R11 represents a monovalent hydrocarbon group and the like, Q represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms and the like, and M represents a sodium atom and the like. However, the compound meets the requirements of one or more of (i) to (vi) as below. (i) One or more of R1 to R4 is an aromatic hydrocarbon group having at least one substituent selected from a group consisting of -SO2-O-N=CR7R10, -SO2NHNHR7, -SO2SR7 and -SO2NHSO2R11. (ii) One or more of R1 to R4 is an aromatic hydrocarbon group having at least one substituent selected from a group consisting of -SO2NHR8 and -SO2NR8R9. However, the monovalent saturated aliphatic hydrocarbon groups represented by R8 and R9 have 11 or more carbon atoms. (iii) One or more of R1 to R4 is -R6, or a hydrocarbon group having at least one substituent selected from a group consisting of -R6, -OR6, -CO2R6 and -SO3R6. However, the monovalent saturated hydrocarbon group represented by R6 has 11 or more carbon atoms. (iv) There are m numbers of R5 in which one or more of R5 is -SO2-O-N=CR7R10, -SO2NHNHR7, -SO2SR7 and -SO2NHSO2R11. (v) There are m numbers of R5 in which one or more of R5 is -SO2NHR8 and -SO2NR8R9. However, the monovalent saturated aliphatic hydrocarbon groups represented by R8 and R9 have 11 or more carbon atoms. (vi) There are m numbers of R5 in which one or more of R5 is -CO2R6 and -SO3R6. However, the monovalent saturated hydrocarbon group represented by R6 has 11 or more carbon atoms.

Description

Colorant, coloring composition, color filter, and display element

The present invention relates to a colorant, a coloring composition, a color filter, and a display element, and more particularly to a color suitable for a transmissive 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 coloring agent used for the production of a filter, a colored composition containing the coloring agent, a color filter including a coloring layer formed using the colored composition, and a display element including the color filter.

In the production of a color filter using a colored radiation-sensitive composition, it is known that a pigment-dispersed colored radiation-sensitive composition is applied onto a substrate and dried, and then the dried coating film is irradiated with radiation (hereinafter referred to as "exposure". A method of obtaining a pixel of each color by developing it into a desired pattern shape (Patent Documents 1 to 2). Further, a method of forming a black matrix by using a photopolymerizable composition in which carbon black is dispersed is also known (Patent Document 3). Further, a method of obtaining a pixel of each color by a liquid-jet method using a pigment-dispersed colored resin composition is also known (Patent Document 4).

In recent years, there has been a strong demand for high contrast of liquid crystal display elements and high definition of solid-state imaging elements. In order to achieve these, applications of dyes as colorants have been studied. For example, in Patent Document 5, the use of a specific dibenzopyran dye is proposed.

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. 2010-254964

However, if the dye proposed in Patent Document 5 is used, there is a problem that the contrast of the pixel is lowered. On the other hand, if a dye is used, the problem of deterioration of the voltage holding ratio and heat resistance of the color filter will occur in large quantities. Therefore, development of a coloring composition suitable for production of a color filter capable of achieving both good voltage holding ratio, high contrast, and high heat resistance is strongly demanded.

Therefore, an object of the present invention is to provide a coloring composition capable of forming a coloring layer capable of achieving both a good voltage holding ratio, high contrast, and high heat resistance when a dye is used as a coloring agent, and providing a coloring agent applicable to the coloring composition. . Further, an object of the present invention is to provide a color filter including a coloring layer formed of the coloring composition, and a display element including the color filter.

In view of the facts, the inventors of the present invention conducted intensive studies and found that the above problems can be solved by using a dye having a specific structure as a coloring agent, and completed the present invention.

That is, the present invention provides a coloring composition comprising the following components (A), (B) and (C): (A) a coloring agent containing a dye represented by the following formula (1), and (B) a bonding agent Resin and (C) crosslinker.

[In the formula (1), X ^- represents an anion; a is an integer determined by making the compound electrically neutral; and m represents an integer of 0 to 5. When m is an integer of 2 or more, a plurality of R ^{5 's} may be the same or different; and R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms ( The hydrogen atom contained in the aromatic hydrocarbon group may be a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NH ₂ , -SO ₂ NHR ⁸ , -SO ₂ NR ⁸ R ⁹ , -SO ₂ -ON=CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ is substituted by NHSO ₂ R ¹¹ ); R ⁵ each independently represents -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , - SO ₂ NHR ⁸ , -SO ₂ NR ⁸ R ⁹ , -SO ₂ -ON=CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹ ; R ⁶ represents monovalent saturation a hydrocarbon group (the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and the -CH ₂ - contained in the saturated hydrocarbon group may be substituted by -O-, -CO- or -NR ⁷ -); R ⁷ represents a monovalent value a hydrocarbon group (the hydrogen atom contained in the hydrocarbon group may be substituted by a halogen atom or -R ¹¹ which may be bonded by -O- or -CO-); and R ⁸ and R ⁹ each independently represent a monovalent saturated aliphatic hydrocarbon group ( The saturation Fatty aliphatic hydrocarbon contained in the hydrogen atom may be -OH, a halogen atom, -Q, -CH = CH ₂ or -CH = substituted CHR ^6, -CH saturated aliphatic hydrocarbon which contains ₂ - may be replaced by -O- , -S-, -CO-, -NH- or -NR ⁶ - is substituted); R ¹⁰ represents a hydrogen atom, a monovalent hydrocarbon group (the hydrogen atom contained in the hydrocarbon group may be substituted by a halogen atom or -R ¹¹ ), The hydrocarbon group may be bonded with -O- or -CO-) or -R ¹¹ ; R ¹¹ represents a monovalent hydrocarbon group which may have a substituent; Q represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a carbon atom number of 3 a monovalent heterocyclic group of ～10 (the aromatic hydrocarbon group and one or more hydrogen atoms contained in the heterocyclic group are at least selected from the group consisting of -R ⁶ , —OR ⁶ and —CH=CHR ⁶ One of the substituted, the aromatic hydrocarbon group and the remaining hydrogen atom contained in the heterocyclic group may be substituted by -OH, -NO ₂ , -CH=CH ₂ or a halogen atom; and M represents a sodium atom or a potassium atom.

The compound satisfies one or more of the following requirements (i) to (vi).

(i) One or more of R ¹ to R ⁴ have a group selected from the group consisting of -SO ₂ -ON=CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ and -SO ₂ NHSO ₂ R ¹¹ An aromatic hydrocarbon group of at least one substituent in the group.

(ii) One or more of R ¹ to R ⁴ is an aromatic hydrocarbon group having at least one substituent selected from the group consisting of -SO ₂ NHR ⁸ and -SO ₂ NR ⁸ R ⁹ . The monovalent saturated aliphatic hydrocarbon group represented by R ⁸ and R ⁹ has 11 or more carbon atoms.

(iii) at least one of R ¹ to R ⁴ is -R ⁶ or has at least one selected from the group consisting of -R ⁶ , -OR ⁶ , -CO ₂ R ⁶ and -SO ₃ R ⁶ A substituted aromatic hydrocarbon group. The monovalent saturated hydrocarbon group represented by R ⁶ has 11 or more carbon atoms.

(iv) One or more of R ⁵ having m are -SO ₂ -ON=CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹ .

(v) One or more of R ⁵ having m are -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ . The monovalent saturated aliphatic hydrocarbon group represented by R ⁸ and R ⁹ has 11 or more carbon atoms.

one or more of -CO ₂ R ^6, or ^{_{-SO 3 R 6 R 5 (vi}} ) having m in. The monovalent saturated hydrocarbon group represented by R ⁶ has 11 or more carbon atoms. 〕

Moreover, the present invention provides a color filter including a coloring layer formed using the colored composition, and a display element including the color filter. Here, the "colored layer" means each color pixel, black matrix, black spacer, or the like used for the color filter.

Further, the present invention provides a dye represented by the above formula (1).

When the colored composition of the present invention is used, a coloring layer excellent in voltage holding ratio, contrast, and heat resistance can be formed. Therefore, the coloring composition of the present invention is extremely suitable for color filters for display elements, solid photos The production of various color filters typified by color filters for color separation of elements, color filters for organic EL display elements, and color filters for electronic paper.

[Formation of 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.

- (A) colorant -

The coloring composition of the present invention contains the dye represented by the above formula (1) (hereinafter referred to as "dye (a1)") as the coloring agent (A).

In the formula (1), examples of X ^- include a halogen ion, a boron anion, a phosphate anion, a carboxylic acid anion, a sulfate anion, an organic sulfonate anion, a nitrogen anion, a methide anion, and the like.

The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ and Q is preferably a monovalent aryl group having 6 to 10 carbon atoms, and more specifically, a phenyl group. , benzyl, o-tolyl, m-tolyl, p-tolyl, naphthyl and the like. Further, examples of the halogen atom which may be substituted on the above aromatic hydrocarbon group include a fluorine atom, a chlorine atom and a bromine atom.

The monovalent saturated hydrocarbon group in R ⁶ may be any of a saturated aliphatic hydrocarbon group and a saturated alicyclic hydrocarbon group. Further, the saturated aliphatic hydrocarbon group may be in any of a linear form and a branched form. The saturated aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, and specific examples thereof include an alkyl group having 1 to 20 carbon atoms, and examples thereof include a methyl group and an ethyl group. , propyl, isopropyl, butyl, isobutyl, secondary butyl, tert-butyl, hexyl, heptyl, octyl, 2-ethylhexyl, decyl, decyl, undecyl, 1-methylindenyl, 2-methylindenyl, dodecyl, 1-methylundecyl, 1-ethylindenyl, tridecyl, tetradecyl, tertiary dodecane Base, pentadecyl, 1-heptyloctyl, hexadecyl, octadecyl, nonadecyl, eicosyl-1-yl and the like. The -CH ₂ - contained in the monovalent saturated hydrocarbon group may be substituted by -O-, -CO- or -NR ⁷ - as a group in which -CH ₂ - contained in the monovalent saturated hydrocarbon group is substituted with -O- Examples thereof include methoxypropyl group, ethoxypropyl group, methoxyhexyl group, ethoxypropyl group, 2-ethylhexyloxypropyl group and the like.

In addition, the saturated alicyclic hydrocarbon group is preferably a saturated alicyclic hydrocarbon group having 3 to 30 carbon atoms, and specific examples thereof include a cycloalkyl group having 3 to 30 carbon atoms and a saturated condensed compound. A cyclic hydrocarbon group, a saturated bridged cyclic hydrocarbon group, a saturated spirohydrocarbyl group or the like. More specifically, it may, for example, be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a tertiary butylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group or a decahydro-2-naphthyl group. , tricyclo [5.2.1.0 ^2,6 ]decane-8-yl, pentacyclopentadecyl, isobornyl, adamantyl and the like. Among them, a saturated alicyclic hydrocarbon group having 3 to 12 carbon atoms is preferred, and a saturated alicyclic hydrocarbon group having 3 to 8 carbon atoms is more preferred.

Further, examples of the halogen atom which may be substituted on the above saturated hydrocarbon group include the same halogen atoms as described above.

Examples of -CO ₂ R ⁶ include a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, an isopropyloxycarbonyl group, a butyloxycarbonyl group, an isobutyloxycarbonyl group, a pentyloxycarbonyl group, and an isopenic group. Base oxycarbonyl, neopentyloxycarbonyl, cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, ring Octyloxycarbonyl, mercaptooxycarbonyl, mercaptooxycarbonyl, tricyclodecyloxycarbonyl, methoxypropyloxycarbonyl, ethoxypropyloxycarbonyl, hexyloxypropyloxycarbonyl, 2-ethyl Hexyloxypropyloxycarbonyl, methoxyhexyloxycarbonyl, undecylcarbonyl, dodecylcarbonyl, tetradecylcarbonyl, tertiary dodecylcarbonyl, hexadecylcarbonyl, octadecane Alkylcarbonyl and the like.

Examples of -SO ₃ R ⁶ include a methylsulfonyl group, an ethylsulfonyl group, a hexylsulfonyl group, a sulfonyl group, an undecylsulfonyl group, a dodecylsulfonyl group, and a tetradecane. Sulfosyl group, tertiary dodecylsulfonyl group, cetylsulfonyl group, octadecylsulfonyl group and the like.

The monovalent hydrocarbon group in R ⁷ , R ¹⁰ and R ¹¹ may be any of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. Further, the aliphatic hydrocarbon group may be in any of a linear form and a branched form. The aliphatic hydrocarbon group and the alicyclic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Further, the position of the unsaturated bond of the unsaturated hydrocarbon group may be any position in the molecular chain and at the end of the molecular chain, and may be present at any position. In addition, examples of the monovalent hydrocarbon group to be bonded by -O- or -CO- in R ⁷ include an alkoxy group, a phenoxy group, an alkylcarbonyl group, a benzamidine group and the like.

Examples of the substituent of the monovalent hydrocarbon group in R ¹¹ include a halogen atom, an alkyl group having 1 to 20 carbon atoms, a trifluoromethyl group, an amine group, and a nitro group. When the position and the number of the substituent are arbitrary, and when there are two or more substituents, the substituents may be the same or different. Further, specific examples of the halogen atom which may be substituted on the hydrocarbon group and the alkyl group having 1 to 20 carbon atoms include the same groups as described above.

The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and specific examples thereof include an alkyl group having 1 to 20 carbon atoms and an alkenyl group having 2 to 16 carbon atoms. An alkynyl group having 2 to 12 carbon atoms. Specific examples of the alkyl group include the same groups as described above. Further, examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 1-butenyl group, a 1,3-butadienyl group, a 1-pentenyl group, a 2-pentenyl group, and a 1-hexenyl group. 2-Ethyl-2-butenyl, 2-octenyl, (4-vinyl)-5-hexenyl, 2-decenyl and the like. Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a 1-pentynyl group, a 3-pentynyl group, a 1-hexynyl group, and a 2-ethyl-2-butyne group. A group, a 2-octynyl group, a (4-ethynyl)-5-hexynyl group, a 2-decynyl group or the like.

The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 30 carbon atoms, and specific examples thereof include a cycloalkyl group having 5 to 18 carbon atoms, a cycloalkenyl group, and a fused polycyclic ring. Hydrocarbyl group, bridged cyclic hydrocarbon group, spirohydrocarbyl group, cyclic terpene group, and the like. As these specific examples, in addition to the above, a dicyclopentenyl group, a tricyclopentenyl group, etc. may be mentioned.

The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and specific examples thereof include the same groups as described above.

Further, examples of the halogen atom which may be substituted on the above hydrocarbon group include the same halogen atom as described above.

Wherein R ^{7 is} preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, more preferably an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and even more preferably a carbon number of carbon atoms; An alkyl group of 1 to 15 and an aromatic hydrocarbon group having 6 to 10 carbon atoms. As the aromatic hydrocarbon group, an aromatic hydrocarbon group to which -O- or -CO- is bonded is also preferable.

Further, R ^{10 is} preferably an aliphatic hydrocarbon group, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms, and R ^{11 is} preferred as a fragrance. The hydrocarbon group is more preferably an aryl group having 6 to 10 carbon atoms.

The monovalent saturated aliphatic hydrocarbon group in R ⁸ and R ⁹ may be either linear or branched. The saturated aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group having 1 to 24 carbon atoms, and specific examples thereof include, in addition to the alkyl group having 1 to 20 carbon atoms in the above R ⁶ , Mono-1-yl, docosa-1-yl, eicosyl-1-yl, tetracos-1-yl and the like. Examples of the halogen atom which may be substituted on the above saturated aliphatic hydrocarbon group include the same halogen atoms as described above.

Examples of -SO ₂ NHR ⁸ include methylamine sulfonyl group, ethylamine sulfonyl group, propylamine sulfonyl group, isopropylamine sulfonyl group, butylamine sulfonyl group, and isobutylamine. Sulfonyl, pentylamine sulfonyl, isoamylamine sulfonyl, neopentylamine sulfonyl, hexylamine sulfonyl, heptylamine sulfonyl, octylamine sulfonyl, 2-B Hexylaminosulfonyl, decylamine sulfonyl, decylamine sulfonyl, undecylamine sulfonyl, 1-methylindenyl, 2-methyldecylamine sulfonyl, twelve Alkylamine sulfonyl, 1-methylundecylamine sulfonyl, 1-ethyldecylamine sulfonyl, tridecylamine sulfonyl, tetradecylamine sulfonyl, three Grade dodecylamine sulfonyl, pentadecylamine sulfonyl, 1-heptyloctylamine sulfonyl, hexadecylamine sulfonyl, octadecylamine sulfonyl, twenty Dialkyl-1-ylamine sulfonyl group and the like.

Examples of the monovalent heterocyclic group having 3 to 10 carbon atoms in Q include a pyrrolidinyl group, an imidazolidinyl group, a pyrazolyl group, a piperidinyl group, an N-hexahydropyridyl group, and a piperidine. Base base, Olinyl group, sulfur Alicyclic heterocyclic group such as phenyl group, pyridyl group, pyridyl Base, pyrimidinyl, oxime Base, quinolyl, isoquinolyl, anthracene base, Pyridyl, quin Lolinyl, thienyl, furyl, piperanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, An aromatic heterocyclic group such as an azolyl group, a fluorenyl group, a carbazolyl group, a benzimidazolyl group or a fluorenyl group. The halogen atom which may be substituted on the above heterocyclic group may be the same halogen atom as described above.

m is an integer of 0 to 5, preferably 0 to 3, more preferably 1 or 2.

M is a sodium atom or a potassium atom.

In addition, the dye (a1) needs to satisfy one or more of the following requirements (i) to (vi).

(i) One or more of R ¹ to R ⁴ have a group selected from the group consisting of -SO ₂ -ON=CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ and -SO ₂ NHSO ₂ R ¹¹ An aromatic hydrocarbon group of at least one substituent in the group.

(ii) One or more of R ¹ to R ⁴ is an aromatic hydrocarbon group having at least one substituent selected from the group consisting of -SO ₂ NHR ⁸ and -SO ₂ NR ⁸ R ⁹ . The monovalent saturated aliphatic hydrocarbon group represented by R ⁸ and R ⁹ has 11 or more carbon atoms.

(iii) at least one of R ¹ to R ⁴ is -R ⁶ or has at least one selected from the group consisting of -R ⁶ , -OR ⁶ , -CO ₂ R ⁶ and -SO ₃ R ⁶ A substituted aromatic hydrocarbon group. The monovalent saturated hydrocarbon group represented by R ⁶ has 11 or more carbon atoms.

(iv) One or more of R ⁵ having m are -SO ₂ -ON=CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹ .

(v) One or more of R ⁵ having m are -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ . The monovalent saturated aliphatic hydrocarbon group represented by R ⁸ and R ⁹ has 11 or more carbon atoms.

one or more of -CO ₂ R ^6, or ^{_{-SO 3 R 6 R 5 (vi}} ) having m in. The monovalent saturated hydrocarbon group represented by R ⁶ has 11 or more carbon atoms.

In addition, when the dye (1a) satisfies one or more of the necessary conditions (i), (ii), and (iv) to (vi), -R ⁶ and -OR ^{6 of the} necessary condition (iii) are not necessarily required. carbon atoms, -CO ₂ R ^6, -SO ₃ R ⁶ is R ⁶ represents a monovalent saturated hydrocarbon group is 11 or more.

Further, the dye (1a) satisfies the necessary conditions (i) ~ (v) when at least one of, a necessary condition is not always necessary (vi) a -CO ₂ R ^6, -SO ₃ R ⁶ R ⁶ is represented by The monovalent saturated hydrocarbon group has 11 or more carbon atoms.

In this case, the monovalent saturated hydrocarbon group represented by R ⁶ is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a carbon number. It is an alkyl group of 1 to 4.

Further, when the dye (1a) satisfies one or more of the requirements (i) and (iii) to (vi), -SO ₂ NHR ⁸ and -SO ₂ NR ⁸ R ^{9 of the} necessary condition (ii) are not necessarily required. The monovalent saturated aliphatic hydrocarbon group represented by R ⁸ and R ⁹ has a carbon number of 11 or more.

Further, when the dye (1a) satisfies one or more of the necessary conditions (i) to (iv) and (vi), -SO ₂ NHR ⁸ and -SO ₂ NR ⁸ R ^{9 of the} necessary condition (V) are not necessarily required. The monovalent saturated aliphatic hydrocarbon group represented by R ⁸ and R ⁹ has a carbon number of 11 or more.

In this case, the monovalent saturated aliphatic hydrocarbon group represented by R ⁸ and R ⁹ is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and still more. Preferably, it is an alkyl group having 1 to 6 carbon atoms.

In the formula (1), a is an integer determined by making the dye (a1) electrically neutral, and the dye (a1) in which a is 0 is a fragrance in which one of R ¹ to R ⁴ is substituted by -SO ₃ ^- One of the group of hydrocarbon groups or R ⁵ having m units is -SO ₃ ^- . Specifically, it can be represented by the following formula (1-1). On the other hand, when one or more of R ¹ to R ⁴ in the dye (a) in which a is 1 is a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms having a substituent, the aromatic hydrocarbon group has -SO A substituent other than ₃ ^- is used as a substituent, and R ⁵ is not -SO ₃ ^- . Specifically, it can be represented by the following formula (1-2).

[In the formula (1-1), R ¹ to R ⁵ and m have the same meanings as R ¹ to R ⁵ and m in the above formula (1), respectively. Among them, one of R ¹ to R ⁴ is an aromatic hydrocarbon group substituted by -SO ₃ ^- , or one of R ⁵ having m is -SO ₃ ^- . 〕

[In the formula ^{(1-2), X -, R} 1 ~ R 5 , respectively, and m (1) X in the above formula ^-, R ¹ ~ R ⁵ and m have the same meaning. When one or more of R ¹ to R ⁴ is a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms having a substituent, the aromatic hydrocarbon group has a substituent other than -SO ₃ ^- as a substituent, and R ⁵ is not -SO ₃ ^- . 〕

Moreover, as a more preferable aspect, the compound represented by following formula (2) is mentioned.

In the formula (2), R ^1a to R ^4a each independently represent a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms (the hydrogen atom contained in the aromatic hydrocarbon group may be a halogen atom) , -R ⁶ , -OH, -OR ⁶ , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NH ₂ , -SO ₂ NHR ⁸ , -SO ₂ NR ⁸ R ⁹ , -SO ₂ -ON=CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹ substituted); R ^5a each independently represents - SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ , -SO ₂ NR ⁸ R ⁹ , -SO ₂ -ON=CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹ ; R ⁶ represents a monovalent saturated hydrocarbon group (the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and the saturated hydrocarbon group -CH ₂ - may be substituted by -O-, -CO- or -NR ⁷ -); R ⁷ represents a monovalent hydrocarbon group (the hydrogen atom contained in the hydrocarbon group may be substituted by a halogen atom or -R ¹¹ , which may R- and -CO- linkage; R ⁸ and R ⁹ each independently represent a monovalent saturated aliphatic hydrocarbon group (the hydrogen atom contained in the saturated aliphatic hydrocarbon group may be -OH, a halogen atom, -Q, -CH) =CH ₂ or - Substituting CH=CHR ⁶ , the -CH ₂ - contained in the saturated aliphatic hydrocarbon group may be substituted by -O-, -S-, -CO-, -NH- or -NR ⁶ -); R ¹⁰ represents a hydrogen atom a monovalent hydrocarbon group (the hydrogen atom contained in the hydrocarbon group may be substituted by a halogen atom or -R ¹¹ , the hydrocarbon group may be bonded by -O- or -CO-) or -R ¹¹ ; R ¹¹ represents a group which may have a substituent a valent hydrocarbon group; Q represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a monovalent heterocyclic group having 3 to 10 carbon atoms (the aromatic hydrocarbon group and one or more hydrogens contained in the heterocyclic group) The atom is substituted with at least one selected from the group consisting of -R ⁶ , -OR ⁶ and -CH=CHR ⁶ , and the aromatic hydrocarbon group and the remaining hydrogen atoms contained in the heterocyclic group may be -OH, -NO ₂ , -CH=CH ₂ or a halogen atom;) M represents a sodium atom or a potassium atom.

N represents an integer from 0 to 4. When n is an integer of 2 or more, a plurality of R ^5a may be the same or different, and the compound satisfies one or more of the following requirements (i) to (vi).

(i) One or more of R ^1a to R ^4a have a group selected from the group consisting of -SO ₂ -ON=CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ and -SO ₂ NHSO ₂ R ¹¹ An aromatic hydrocarbon group of at least one substituent in the group.

(ii) One or more of R ^1a to R ^4a is an aromatic hydrocarbon group having at least one substituent selected from the group consisting of -SO ₂ NHR ⁸ and -SO ₂ NR ⁸ R ⁹ . The monovalent saturated aliphatic hydrocarbon group represented by R ⁸ and R ⁹ has 11 or more carbon atoms.

(iii) at least one of R ^1a to R ^4a is -R ⁶ or has at least one selected from the group consisting of -R ⁶ , -OR ⁶ , -CO ₂ R ⁶ and -SO ₃ R ⁶ A substituted aromatic hydrocarbon group. The monovalent saturated hydrocarbon group represented by R ⁶ has 11 or more carbon atoms.

(iv) One or more of the n R ^5a are -SO ₂ -ON=CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹ .

(v) One or more of the n R ^5a are -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ . The monovalent saturated aliphatic hydrocarbon group represented by R ⁸ and R ⁹ has 11 or more carbon atoms.

(vi) One or more of the n R ^5a are -CO ₂ R ⁶ or -SO ₃ R ⁶ . The monovalent saturated hydrocarbon group represented by R ⁶ has 11 or more carbon atoms. 〕

In the formula (2), the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^1a to R ^4a and the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in the above R ¹ to R ⁴ are The same meaning and the specific manner are the same as the above description. Further, specific embodiments of R ⁶ to R ¹¹ , Q and M are also the same as described above.

Further, -SO ₃ ^{- is} preferably in the ortho or para position of the phenyl group, more preferably in the ortho position.

The dye (a1) can be produced by a suitable method, and examples thereof include the same methods as those of the examples of JP-A-2010-254964. The dye (a1) thus obtained is soluble in various organic solvents typified by a ketone such as cyclohexanone, and has excellent heat resistance.

In the present invention, the dye (a1) may be used singly or in combination of two or more.

The colored composition of the present invention may further contain another coloring agent (hereinafter also referred to as "coloring agent (a2)") as a coloring agent together with the dye (a1). The coloring agent (a2) is not particularly limited, and colors and materials can be appropriately selected depending on the application.

As the other coloring agent (a2), a pigment, a dye other than the dye (a1), and a natural coloring matter may be used. However, in the sense of obtaining a pixel having high luminance and color purity, an organic pigment is preferred. Organic dyes, especially organic pigments.

As the above-mentioned organic pigment, for example, a compound classified as a pigment in a pigment index (CI; issued by The Society of Dyers and Colourists Co., Ltd.) may be mentioned, and among them, JP-A-2001-081348 and JP-A-2010-026334 are preferred. Japanese Gazette, Japanese Laid-Open Patent Publication No. 2010-191304, Japanese Laid-Open Patent Publication No. 2010-237384, and Japanese Laid-Open The lake pigment, CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, CI Pigment Red 242, etc. described in Japanese Laid-Open Patent Publication No. 2011-145346, and the like. 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. Organic pigments other than lake pigments such as CI Pigment Yellow 180, CI Pigment Yellow 211, CI Pigment Orange 38, and CI Pigment Violet 23. Further, among the lake pigments, preferred are triarylmethane-based lake pigments, dibenzopyran-based lake pigments, azo-based lake pigments, more preferably triarylmethane-based lake pigments and dibenzos. Pipelanescent lake pigment.

The coloring composition of the present invention is preferably used for the formation of blue pixels. In this case, as the (A) coloring agent, at least one selected from the group consisting of a blue pigment, a blue dye, a violet pigment, and a violet dye is preferably used as the other coloring agent together with the coloring agent. In this case, the content ratio of the coloring agent is preferably from 0.1 to 80% by mass, more preferably from 1 to 80% by mass, still more preferably from 5 to 60% by mass, particularly preferably from 10 to 40% by mass, based on the total coloring agent. .

When a pigment is used as the colorant (a2) in the present invention, the pigment may be purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Further, the pigment may be used by modifying the surface of the particles with a resin as needed. For example, a resin which is described in JP-A-2001-1088147 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 for the surface of carbon black, For example, a method described in, for example, JP-A-H09-71733, JP-A-H09-95625, JP-A-9-124969, and the like can be employed. Further, the organic pigment is preferably used by refining primary particles by a so-called salt milling method. As the salt milling method, for example, a method disclosed in Japanese Laid-Open Patent Publication No. Hei 08-179111 can be employed.

When a pigment is used as the colorant (a2) in the present invention, a known dispersant and dispersing aid may be further contained. Examples of the known dispersant include a polyurethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, and a polyoxyethylene alkylphenyl ether dispersant. A polyethylene glycol diester-based dispersing agent, a sorbitan fatty acid ester-based dispersing agent, a polyester-based dispersing agent, an acrylic dispersing agent, and the like, and a dispersing aid may, for example, be a pigment derivative.

Such a dispersing agent can be obtained commercially. For example, as an acrylic dispersing agent, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK) can be mentioned as Examples of the polyurethane dispersing agent include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, BYK), and Solsperse 76500 (manufactured by LUBRIZOL Co., Ltd.) For example, Solsperse 24000 (manufactured by LUBRIZOL Co., Ltd.) may be used as the dispersing agent for polyethyleneimine, and examples of the polyester dispersing agent include Adisper PB821, Adisper PB822, Adisper PB880, and Adisper PB881 (above by AJINOMOTO FINE). TECHNO AG system) and so on.

In addition, specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and a sulfonic acid derivative of quinacridone.

In the present invention, the coloring agent (a2) may be used singly or in combination of two or more.

The content of the colorant (A) is usually from 5 to 70% by mass, preferably from 5 to 70% by mass, based on the solid content of the coloring composition, from the viewpoint of forming a pixel having high luminance and excellent color purity or forming a black matrix having excellent light shielding properties. 5 to 60% by mass. Here, the solid component is a component other than the solvent described later.

- (B) Adhesive Resin -

The (B) binder resin in the present invention is not particularly limited, but 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 "carboxyl group-containing polymer") is preferable, and examples thereof include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer (b1). And a copolymer of another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (b2)").

Examples of the unsaturated monomer (b1) include (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono[2-(methyl)acryloxyethyl ester, and ω-carboxyl polymerization. Caprolactone mono(meth)acrylate, p-vinylbenzoic acid, and the like.

These unsaturated monomers (b1) may be used alone or in combination of two or more.

Further, examples of the unsaturated monomer (b2) include N-phenylmaleimide, N-substituted mercaptoimine such as N-cyclohexylmaleimide; and styrene; , an aromatic vinyl compound such as α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, terpene; methyl (meth)acrylate , n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate Ester, 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 ~10) Mono(meth)acrylate, polypropylene glycol (degree of polymerization 2~10) mono(meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclic [5.2 .1.0 ^2,6 】decane-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, (meth) acrylate 4-hydroxy benzene Ethylene oxide modified (meth)acrylic acid of ester and p-anisyl Ester, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)propenyloxymethyl]oxetane, 3- (Meth) acrylate such as [(meth)acryloxymethyl]-3-ethyloxetane; cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclic [5.2. 1.0 ^2,6 ] Vinyl-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, vinyl ether such as 3-(vinyloxymethyl)-3-ethyloxetane a macromolecular single molecule having a mono(meth)acryloyl group at the end of a polymer molecular chain such as polystyrene, poly(methyl) methacrylate, poly(methyl) methacrylate, or polyoxyalkylene Body and so on.

These unsaturated monomers (b2) may be used alone 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 5 to 50 mass. %, more preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, a coloring composition excellent in alkali developability and storage stability can be obtained.

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-10-10 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. Copolymer.

In addition, in the present invention, for example, Japanese Laid-Open Patent Publication No. Hei 5-19467, Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. As a binder resin, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acrylonitrile group in a side chain is used as disclosed in JP-A-2008-181095, and the like.

The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter referred to as GPC) (dissolving solvent: tetrahydrofuran) in the present invention is usually from 1,000 to 100,000, preferably from 3,000 to 50,000. . When the Mw is too small, the residual film ratio of the film to be obtained may be lowered, the pattern shape, heat resistance, and the like may be impaired, and electrical characteristics may be deteriorated. On the other hand, if the film size is too large, the resolution may be lowered or the pattern shape may be impaired. When the coating by the slit nozzle method is applied, dry foreign matter is likely to be generated.

Further, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin in the present invention is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. In addition, Mn referred to herein means a polystyrene-converted number average molecular weight measured by GPC (solution solvent: tetrahydrofuran).

The binder resin in the present invention can be produced by a known method, and a method disclosed in, for example, JP-A-2003-222717, JP-A-2006-259680, and International Publication No. 07/029871, and the like can be employed. Control its structure, Mw, Mw / Mn.

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

In the present invention, the content of the binder resin is usually 10 to 1000 parts by mass, preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. If the content of the binder resin is too small, for example, the alkali developability may be lowered, and the storage stability of the obtained colored composition may be lowered. On the other hand, if too much, the relative colorant concentration is lowered to achieve a target color density as a film. It may become difficult.

-(C) Crosslinker -

In the present invention, the (C) crosslinking agent means a compound having two or more polymerizable groups. The polymerizable group may, for example, be an ethylenically unsaturated group, an epoxyethyl group, an oxetanyl group or an N-alkoxymethylamino group. In the present invention, the (C) crosslinking agent 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. An ester-modified polyfunctional (meth) acrylate, an alkylene oxide-modified polyfunctional (meth) acrylate, a polyfunctional polyamine obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate A carbamic acid ester (meth) acrylate, a polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group and an acid anhydride, or the like.

Here, examples of the aliphatic polyhydroxy compound include a divalent aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol, or polypropylene glycol, glycerin, trimethylolpropane, and pentaerythritol. A trivalent or higher aliphatic polyhydroxy compound such as 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, glycerin dimethacrylate, and the like. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include an anhydride of a dibasic acid such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, and pyromellitic anhydride. A tetrabasic dianhydride such as biphenyltetracarboxylic dianhydride or benzophenone tetracarboxylic dianhydride.

In addition, as the above-mentioned caprolactone-modified polyfunctional (meth) acrylate, for example, the compounds described in paragraphs [0015] to [0018] of JP-A-11-44955 can be mentioned. As the above modified alkylene oxide The functional (meth) acrylate may, for example, be a di(meth)acrylate modified with at least one selected from the group consisting of ethylene oxide of bisphenol A and propylene oxide of bisphenol A, and is selected from three At least one modified tri(meth)acrylate of polyethylene oxide of polyisocyanate and propylene oxide of isocyanuric acid, ethylene oxide selected from trimethylolpropane and three At least one modified tri(meth)acrylate of propylene oxide of methylolpropane, at least one modified by at least one selected from the group consisting of ethylene oxide selected from pentaerythritol and propylene oxide of pentaerythritol Acrylate, tetra(meth)acrylate modified by at least one of ethylene oxide selected from pentaerythritol and propylene oxide of pentaerythritol, ethylene oxide selected from dipentaerythritol, and dipentaerythritol At least one modified penta(meth)acrylate in propylene oxide, at least one modified hexa(meth)acrylic acid from ethylene oxide selected from dipentaerythritol and propylene oxide of dipentaerythritol Ester and 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. Furthermore, the so-called melamine structure and benzoguanamine structure means having one or more three Ring or phenyl substituted three The chemical structure of the ring as a basic skeleton is also 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 crosslinking agents, polyfunctional (meth) propyl which is obtained by reacting an aliphatic polyhydroxy compound having 3 or more elements with (meth)acrylic acid is preferred. Polyenoate, caprolactone modified polyfunctional (meth) acrylate, polyfunctional polyurethane (meth) acrylate, polyfunctional (meth) acrylate having carboxyl group, N, N, N',N',N",N"-hexa(alkoxymethyl)melamine, N,N,N',N'-tetrakis(alkoxymethyl)benzoguanamine. The aliphatic polyhydroxy group having three or more members is considered to be excellent in the strength of the colored layer and the surface smoothness of the colored layer, and it is difficult to cause scum, film residue, and the like on the substrate of the unexposed portion and the light shielding layer. Among the polyfunctional (meth) acrylates obtained by reacting a compound with (meth)acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like are particularly preferable. Among the polyfunctional (meth) acrylates having a carboxyl group, a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, and a compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride are particularly preferable.

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

The content of the (C) crosslinking agent in the present invention is preferably from 10 to 1,000 parts by mass, particularly preferably from 20 to 500 parts by mass, per 100 parts by mass of the (A) coloring agent. At this time, if the content of the crosslinking agent is too small, sufficient hardenability may not be obtained. On the other hand, when the content of the crosslinking agent is too large, when the alkali developability is imparted to the colored composition of the present invention, the alkali developability is lowered, and the dross is easily generated on the substrate of the unexposed portion or on the light shielding layer. Trends such as film residue.

-Photopolymerization initiator -

The coloring composition of the present invention may contain a photopolymerization initiator. Thereby, it is possible to impart radiation sensitivity to the colored composition. In the present invention The photopolymerization initiator to be used is a compound which can generate an active species capable of initiating polymerization of the above (C) crosslinking agent by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam or X-ray.

Examples of such a photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a biimidazole compound, and the like. Compound, O-mercapto oxime compound, sulfonium salt compound, benzoin compound, benzophenone compound, α-diketone compound, polycyclic guanidine compound, diazo compound, quinone A sulfonate-based compound or a phosphonium salt-based compound.

In the present invention, the photopolymerization initiator may be used singly or in combination of two or more. The photopolymerization initiator is preferably selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, and three. At least one of a compound and an O-mercapto lanthanide compound. Further, two or more kinds selected from these compounds may be used in combination.

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

Further, specific examples of the acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2-N- Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-N- Polinylphenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-N- Polinylphenyl)butan-1-one and the like.

Further, specific examples of the biimidazole-based compound include 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.

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

In addition, as the above three Specific examples of the compound can be exemplified by 2,4,6-tris(trichloromethyl) symmetry III. 2-methyl-4,6-bis(trichloromethyl) symmetry three 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)symmetric three 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl) symmetric three 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)symmetric three 2-[2-(3,4-Dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)symmetric three 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl) symmetry three 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)symmetric three 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)symmetric three Three with a halogenated methyl group a compound.

Further, specific examples of the O-fluorenyl fluorene-based compound include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzylidenefluorene). Ethylketone, 1-[9-ethyl-6-(2-methylbenzylidenyl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-, 1-(O-ethylindenyl) Ethylketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene]- 9H-carbazol-3-yl]-, 1-(O-ethylindenyl) and the like. As a commercial item of the O-mercapto fluorene-based compound, NCI-831, NCI-930 (above, manufactured by ADEKA CORPORATION), or the like can be used.

In the present invention, when a photopolymerization initiator other than a biimidazole-based compound such as an acetophenone-based 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) crosslinking agent. In this case, if the content of the photopolymerization initiator is too small, the hardening due to exposure may become insufficient. On the other hand, if the amount is too large, the formed coloring layer tends to fall off from the substrate during development.

- solvent -

The colored composition of the present invention is a colored composition containing the above components (A) to (C) and optionally added other components, and is usually prepared by mixing a solvent to prepare a liquid composition. The solvent is appropriately selected and used as long as it dissolves or dissolves the components (A) to (C) constituting the coloring composition or other components, and does not react with these components, and has a 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, and diethylene glycol monomethyl. Ether, 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 (poly) olefinic diol monoalkyl ethers such as tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; alkyl lactate such as methyl lactate or ethyl lactate; methanol, ethanol, propanol, butyl Alcohol, isopropanol, isobutanol, tertiary butanol, octanol, 2-ethylhexanol, cyclohexanol and other (cyclo)alkyl alcohols; ketone alcohols such as diacetone alcohol; Methyl 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 Acetate, dipropylene glycol monomethyl ether acetate, acetic acid-3-methoxybutyl ester, acetic acid-3-methyl-3-methoxybutyl ester, etc. (poly) olefinic diol monoalkyl ether Acetate Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone Ketones; diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate; methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate Alkoxycarboxylates; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, butyl Acid ethyl ester, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, Other esters such as 2-oxobutyric acid ethyl ester; aromatic hydrocarbons such as toluene and xylene; N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone Such as decylamine or indoleamine.

Among these solvents, (poly)alkylene glycol monoalkyl ethers, alkyl lactates, (poly)alkylene glycol monoalkyl groups are preferred from the viewpoints of solubility, pigment dispersibility, coating properties and the like. Ether acetates, 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, diglyme, diethylene glycol methyl ethyl ether, Cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methoxypropionic acid ester, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, isobutyl acetate, n-amyl formate , isoamyl acetate, n-butyl propionate, 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. When the solvent is used in combination, it is preferred to at least (poly)alkylene glycol monoalkyl ethers and (poly)alkylene glycol monoalkyl ether acetates, (poly) alkene glycol monoalkyl ethers. Acetate esters are used in combination with alkoxycarboxylates, alkyl lactates and (poly)alkylene glycol monoalkyl ether acetates.

The content of the solvent is not particularly limited, and the total concentration of each component of the solvent excluding the composition is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass. In this state, a colored dispersion having good dispersibility and stability, and a colored composition having good coatability and stability can be obtained.

-additive-

The colored composition of the present invention may 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-based surfactant or a lanthanoid surfactant; and ethylene. Trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2-aminoethyl)-3-aminopropylmethyl dimethyl Oxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxy Baseline, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane , adhesion promoters such as 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane; 2,2-thiobis(4- Antioxidant such as methyl-6-tertiary butylphenol), 2,6-ditributylphenol; 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5- Ultraviolet absorbers such as chlorobenzotriazole and alkoxybenzophenone; anti-agglomerating agents such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, and mesaconic acid , 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4 - residue improving agent such as amine-1,2-butanediol; succinic acid mono [2-(methyl) propylene oxiranyl ethyl] ester, phthalic acid mono [2-(methyl) propylene oxy group A developer improving agent such as ethyl ester or ω-carboxy polycaprolactone mono(meth) acrylate.

The coloring composition of the present invention can be produced by a suitable method, and the method disclosed in the method of the present invention, for example, is disclosed in JP-A-2008-58642, JP-A-2010-132874, and the like. When both the dye and the pigment are used as the coloring agent, as disclosed in Japanese Laid-Open Patent Publication No. 2010-132874, the dye may be passed through the first filter to pass the dye passing through the first filter. The solution is mixed with a separately prepared pigment dispersion or the like so that the resulting colored composition is prepared through the second filter. Further, a method may be employed in which the dye and the components (B) to (C) and other components used as needed are dissolved in a solvent, so that the obtained solution passes through the first filter and passes through the first filter. Solution and separately prepared pigment dispersion The mixing was carried out, and the obtained colored composition was prepared by passing through a second filter. Further, after the dye solution is passed through the first filter, the dye solution that has passed through the first filter, the components (B) to (C), and other components used as needed may be mixed and dissolved. The obtained solution was passed through a second filter, and the solution passed through the second filter was further mixed with the separately prepared pigment dispersion, and the obtained colored composition was prepared by passing through a third filter.

[Color filter and method of manufacturing the same]

The color filter of the present invention has a coloring layer formed using the colored composition of the present invention.

As a method of manufacturing a color filter, the following method is mentioned first. First, a light shielding layer (black matrix) is formed on the surface of the substrate as needed to partition a portion where the pixels are formed. Next, a liquid composition of the colored radiation-sensitive composition of the present invention containing red, for example, dye (a1), is applied onto the substrate, and then pre-baked to evaporate the solvent to form a coating film. Next, the coating film was exposed through a photomask, and then developed using an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Then, by performing post-baking, a pixel array in which red pixel patterns are arranged in a predetermined array is formed.

Next, using each of the green or blue colored radiation-sensitive components, coating, prebaking, exposing, developing, and post-baking each of the colored radiation-sensitive compositions are performed in the same manner as described above, and green is sequentially formed on the same substrate. Pixel array and blue pixel array. Thereby, a color filter in which a pixel array of three primary colors of red, green, and blue is disposed on the substrate is obtained. However, in the present invention, as long as red, green and blue At least one of the colored pixels may be formed of the colored composition of the present invention. Further, the order in which the pixels of the respective colors are formed is not limited to the above order.

Further, the black matrix can be formed by forming a metal thin film such as chromium which is formed by sputtering or vapor deposition into a desired pattern by photolithography, but a colored radiation-sensitive composition in which a black pigment is dispersed can also be used. It 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, for these substrates, an appropriate pretreatment such as a reagent treatment such as a decane coupling agent, a plasma treatment, ion plating, sputtering, a gas phase reaction method, or a vacuum vapor deposition may be carried out as needed.

When the colored radiation-sensitive 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, or a bar coating method can be employed, and it is particularly preferable to use a spinning method. Coating method, slot die coating method.

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. In addition, the conditions of heat drying are usually dried at 70 to 110 ° C for about 1 to 10 minutes.

The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, as the film thickness after drying.

Examples of the light source used for forming the pixel and/or the 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, a medium pressure mercury lamp, a low pressure mercury lamp, and the like. Light source, argon ion laser, YAG laser, XeCl excimer laser, nitrogen laser, etc. A laser light source or the like is preferable, but a radiation having a wavelength in the range of 190 to 450 nm is preferable.

The exposure amount of the radiation is generally preferably from 10 to 10000 J/m ² .

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

An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the alkali developer. Further, after alkali development, water washing is usually carried out.

As the development treatment method, a shower development method, a spray development method, a dip development method, a dipping type (liquid coating) development method, or the like can be employed. The developing conditions are preferably carried out at room temperature for 5 to 300 seconds.

The post-baking conditions are usually about 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.

In addition, as a second method of producing a color filter, a method of obtaining pixels of respective colors by an inkjet method disclosed in Japanese Laid-Open Patent Publication No. Hei 07-318723, and the like. In this method, first, a partition wall having a light blocking function is formed on the surface of the substrate. Next, a liquid composition of the colored thermosetting composition of the present invention containing, for example, red of the dye (a1) is ejected into the formed partition walls by an inkjet apparatus, and then prebaked to evaporate the solvent. Next, the coating film is exposed as needed, and then cured by post-baking to form a red pixel pattern.

Next, using a green or blue colored thermosetting composition, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate in the same manner as described above. Thereby, a color filter in which pixel patterns of three primary colors of red, green, and blue are arranged on the substrate is obtained. However, in the present invention, at least one of the red, green, and blue pixels may be formed of the coloring composition of the present invention. In addition, the order in which the pixels of the respective colors are formed is not limited to the above order.

Further, the partition wall not only has a light-shielding function, but also has a function of not color-mixing the coloring compositions of the respective colors discharged into the partition. Therefore, the film thickness is thicker than that of the black matrix used in the first method. Therefore, the partition walls are usually formed using a black radiation sensitive composition.

The substrate used for forming the color filter, the light source of the radiation, and the method and conditions of the prebaking and postbaking are the same as those of the first method described above. Thus, the film thickness of the pixel formed by the ink jet method is the same as the height of the partition wall.

On the pixel pattern thus obtained, a protective film is formed as needed, and then 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 can usually be formed using a radiation-sensitive composition, but a spacer having a light-shielding property (black spacer) can also be formed. At this time, the colored composition of the present invention can be suitably used for the formation of the black spacer by using the colored radiation-sensitive composition in which the black colorant is dispersed.

Since the color filter of the present invention thus obtained has extremely high luminance and color purity, it is extremely useful for a color liquid crystal display element, a color image pickup element, a color sensor, an organic EL display element, an electronic paper, and the like.

[display component]

The display element of the present invention includes the color filter 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 color filter of the present invention may be of a transmissive type or a reflective type, and may have an appropriate structure. 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 substrate for driving and a substrate on which the color filter is formed may be opposed to each other via a liquid crystal layer; A substrate having a color filter formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate on which an ITO (tin-doped indium oxide) electrode is formed may be opposed to the liquid crystal layer. structure. The latter structure has an advantage of being able to remarkably increase the aperture ratio and obtain a bright and high-definition liquid crystal display element.

A color liquid crystal display element having the color filter of the present invention may include 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 combination of a red LED, a green LED, and a blue LED is obtained by color mixing, and a combination of a blue LED, a red LED, and a green phosphor to obtain white light by color mixing. LED, a combination of a blue LED, a red phosphor, and a green phosphor, a white LED that is white-lighted by color mixing, and a white LED that is white light by a color mixture of a blue LED and a YAG-based phosphor, a combination of blue Color LED, orange phosphor and green phosphor are white LEDs obtained by color mixing, combined with UV LED, red luminescent phosphor, green A white LED or the like which obtains white light by color mixing by a color light-emitting phosphor and a blue light-emitting phosphor.

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

In addition, the organic EL display element having the color filter of the present invention may have a suitable structure, and a structure disclosed in, for example, Japanese Laid-Open Patent Publication No. Hei 11-307242.

Further, the electronic paper including the color filter of the present invention may have a suitable structure, and a structure disclosed in, for example, Japanese Laid-Open Patent Publication No. 2007-41169.

[Examples]

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 the colorant> Synthesis Example 1

Into a 100 mL eggplant type flask to which a stir bar was added, 25.2 g of chloroform and 1.72 g of dehydrated DMF were added, and the mixture was cooled to 10 ° C or lower under a nitrogen stream, and 2.27 g (1.38 mL, 19.1 mmol) of sulfite chloride was added and stirred at the same temperature. 30 minutes. Then, 3.5 g (5.17 mmol) of acid red 289 was added, and the mixture was further stirred at 35 ° C for 3 hours under a nitrogen stream. 0.246 g (0.149 mL, 2.07 mmol) of sulfinium chloride was further stirred at the same temperature for further 1.5 hours. The reaction mixture was cooled to 5 ° C, and 3.26 g (17.6 mmol) of dodecylamine and 5.46 g (54.0 mmol) of triethylamine were added at the same temperature and stirred for 10 minutes, and stirring was continued at 40 ° C for a total of 15 hours. After the reaction mixture was concentrated under reduced pressure using a rotary evaporator, 12.3 g of methanol was added, and the obtained solution was concentrated again until the liquid amount was about half. Next, 17.8 g of methanol and 1.23 g of acetic acid were added, and the resulting mixture was stirred at room temperature for 30 minutes. Then, the above mixture was added dropwise to a large amount of water to precipitate a red solid, which was filtered by suction and washed with water. The obtained solid was sufficiently washed with a small amount of diisopropyl ether and then with hexane, and then dried under reduced pressure at 60 ° C for 12 hours to obtain 4.13 g of a solid (yield: 97.2%). It was confirmed by mass spectrometry that the obtained red solid was a compound represented by the following formula (A1). This compound was used as a coloring agent (A-1).

Synthesis Example 2

A coloring agent was synthesized in the same manner as in Synthesis Example 1 except that methyl ethyl hydrazine was used instead of dodecylamine in Synthesis Example 1. It was confirmed by mass spectrometry that the obtained solid was a compound represented by the following formula (A2). This compound was used as a coloring agent (A-2).

Synthesis Example 3

A coloring agent was synthesized in the same manner as in Synthesis Example 1 except that benzamidine was used instead of dodecylamine in Synthesis Example 1. It was confirmed by mass spectrometry that the obtained solid was a compound represented by the following formula (A3). This compound was used as a coloring agent (A-3).

Synthesis Example 4

A coloring agent was synthesized in the same manner as in Synthesis Example 1 except that 1-dodecyl mercaptan was used instead of dodecylamine in Synthesis Example 1. It was confirmed by mass spectrometry that the obtained solid was a compound represented by the following formula (A4). This compound was used as a coloring agent (A-4).

Synthesis Example 5

A coloring agent was synthesized in the same manner as in Synthesis Example 1 except that p-toluenesulfonamide was used instead of dodecylamine in Synthesis Example 1. It was confirmed by mass spectrometry that the obtained solid was a compound represented by the following formula (A5). This compound was used as a coloring agent (A-5).

Synthesis Example 6

A coloring agent was synthesized in the same manner as in Synthesis Example 1 except that Acid Red 52 was used instead of Acid Red 289 in Synthesis Example 1. It was confirmed by mass spectrometry that the obtained solid was a compound represented by the following formula (A6). This compound was used as a coloring agent (A-6).

Comparative Synthesis Example 1

The synthesis of the dye was carried out in accordance with the description of Synthesis Example 1 of JP-A-2010-254964. The obtained compound was used as a coloring agent (A-7).

Solubility evaluation

The color former (A-1) obtained in Synthesis Example 1 was weighed, and cyclohexanone was added so that the colorant concentration was 0.1% by weight, 1% by weight, and 5% by weight. These samples were stirred at 25 ° C for 1 hour using a stirring rotor, and then the dissolved state was visually confirmed visually. As a result, it was confirmed that the colorant (A-1) was completely dissolved at 5 wt% with respect to cyclohexanone.

The solubility of the colorant (A-2) to the colorant (A-7) and the acid red 289 was also evaluated. The colorant (A-2) to the colorant (A-6) were completely dissolved at 5 wt% with respect to cyclohexanone. The colorant (A-7) completely dissolved at 1% by weight, but did not dissolve at 5% by weight. Further, Acid Red 289 did not dissolve at 0.1% by weight.

<Preparation and evaluation of dye solution> Preparation Example 1

The dye solution (A-1) was prepared by mixing 5 parts by mass of the colorant (A-1) and 95 parts by mass of ethyl lactate as a solvent.

Preparation examples 2 to 6

A dye solution (A-2) was prepared in the same manner as in Preparation Example 1 except that the colorant (A-2) to the colorant (A-6) were used instead of the colorant (A-1) in Preparation Example 1. ) ~ dye solution (A-6).

Preparation Example 7

In the preparation example 1, the coloring agent (A-7) was used instead of the coloring agent (A-1), but the coloring agent (A-7) was not completely dissolved in ethyl lactate, and the residue after dissolution was observed. The obtained dye suspension was used as a dye solution (A-7).

Preparation Example 8

In the preparation example 1, acid red 289 was used instead of the coloring agent (A-1), but acid red 289 was not dissolved in ethyl lactate. The obtained dye suspension was used as a dye solution (A-8).

<Preparation of Pigment Dispersion> Preparation Example 9

15 parts by mass of CI Pigment Blue 15:6 as a colorant, 12.5 parts by mass (solid content concentration: 40% by mass) of BYK-LPN21116 (manufactured by BYK Corporation) as a dispersing agent, and 72.5 parts by mass of propylene glycol monomethyl ether acetate The ester was treated as a solvent by a bead mill to prepare a pigment dispersion (A-1).

<(B) Synthesis of binder resin> Synthesis Example 7

100 parts by mass of propylene glycol monomethyl ether acetate was placed in a flask equipped with a cooling tube and a stirrer, and nitrogen substitution was performed. The mixture 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, and methyl group were added dropwise at the same temperature for 1 hour. 15 parts by mass of 2-hydroxyethyl acrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, and mono(2-propenyloxyethyl) succinate A mixed solution of 15 parts by mass of an ester and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was allowed to stand at this temperature for 2 hours. Then, the temperature of the reaction solution was raised to 100 ° C, and further polymerization was carried out for 1 hour to obtain a binder resin solution (solid content concentration: 33% by mass). The obtained binder resin had a Mw of 12,200 and an Mn of 6,500. This binder resin is referred to as "adhesive resin (B1)".

<Preparation and evaluation of coloring composition> Example 1

13.5 parts by mass of the pigment dispersion liquid (A-1), 7.2 parts by mass of the dye solution (A-1), and 9.9 parts by mass of a binder resin (B1) solution as a binder resin, manufactured by Toagosei Co., Ltd. as a crosslinking agent. M-402 (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 15.4 parts by mass of 2-benzyl-2-dimethylamino-1-(4-N- as a photopolymerization initiator 1.8 parts by mass of a morphylphenyl)butan-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: IRGACU RE369), 0.2 parts by mass of Megaface F-554 (manufactured by DIC Corporation) as a surfactant, and a solvent Ethyl lactate was mixed to prepare a colored composition having a solid concentration of 20% by mass.

The obtained colored composition was applied onto a glass substrate by a spin coater, and then prebaked for 10 minutes using a hot plate at 80 ° C to form three coating films having different film thicknesses.

Next, after the substrate was cooled to room temperature, the radiation including the wavelengths of 365 nm, 405 nm, and 436 nm was exposed to an exposure amount of 2000 J/m ² by a high pressure mercury lamp without a mask. In this manner, a blue evaluation cured film was formed on the substrate.

[Contrast evaluation]

The substrate on which the cured film was formed was sandwiched between two polarizing plates, and the polarizing plate of the front side was rotated while irradiating the fluorescent lamp (wavelength range: 380 to 780 nm) from the back side, and the brightness meter LS-100 (manufactured by Minolta Co., Ltd.) was used. The maximum and minimum values of the transmitted light intensity were measured. Then, for each of the cured films, a value obtained by dividing the maximum value by the minimum value was used as the contrast ratio. By The measurement result was obtained, and the contrast ratio of the chromaticity coordinate value y=0.080 was obtained. The evaluation results are shown in Table 1.

Evaluation of heat resistance

The substrate on which the cured film was formed was post-baked in a clean oven at 230 ° C for 1 hour. The color difference (ΔEab*) was measured on the substrate before and after the baking. Then, the case where ΔEab* is less than 3.0 is evaluated as “◎”, the case of 3.0 or more and less than 5.0 is evaluated as “○”, and the case of 5.0 or more is evaluated as “×”. The evaluation results are shown in Table 1.

Evaluation of voltage retention rate (%)

The obtained coloring composition is spin-coated on a soda-lime glass substrate on which a SiO ₂ film for preventing elution of sodium ions is formed on the surface, and an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape, and then 100 ° C is used. The hot plate was prebaked for 1 minute to form a film having a film thickness of 2.0 μm. Next, the film was exposed at an exposure amount of 700 J/m ² without passing through the mask. Then, the substrate was immersed in a developing solution containing a 0.04% by mass aqueous potassium hydroxide solution at 23 ° C for 1 minute, and after development, it was washed with ultrapure water, air-dried, and further post-baked at 230 ° C for 30 minutes. The film is hardened to form a permanent cured film. Next, the substrate on which the pixel was formed and the substrate on which the ITO electrode was deposited in a predetermined shape were bonded together with a sealant in which 1.8 mm of glass beads were mixed, and then a liquid crystal (MLC6608) manufactured by Merck was injected to prepare a liquid crystal cell. Next, the liquid crystal cell was placed in a constant temperature layer at 60° C., and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage retention ratio measurement system (VHR-1A type, TOYO Technica Co., Ltd.). The applied voltage at this time was a square wave of 5.5 V, and the measurement frequency was 60 Hz. Here, the voltage holding ratio is a value obtained by using (a liquid crystal cell potential difference after 16.7 microseconds / a voltage applied at 0 microseconds). When the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot maintain the applied voltage at a predetermined level for 16.7 microseconds, and the liquid crystal cannot be sufficiently aligned, which may cause "burning" of image sticking or the like.

Examples 2 to 6 and Comparative Examples 1 to 2

In the same manner as in Example 1, except that the type and amount of the pigment dispersion liquid and the dye solution were changed as shown in Table 1, a colored composition was prepared. Then, the obtained colored composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Claims (6)

A coloring composition comprising the following components (A), (B), and (C): (A) a coloring agent containing a dye represented by the following formula (1), (B) a binder resin, and (C) Crosslinker; In the formula (1), X ^- represents an anion, a is an integer determined by making the compound electrically neutral, and m represents an integer of 0 to 5. When m is an integer of 2 or more, a plurality of R ⁵ may be the same. R ¹ to R ^{4 may} each independently represent a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NH ₂ , -SO ₂ NHR ⁸ , -SO ₂ NR ⁸ R ⁹ , -SO ₂ -ON=CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹ is substituted, and R ^{5 is} independently represented - SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ , -SO ₂ NR ⁸ R ⁹ , -SO ₂ -ON =CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹ , and R ⁶ represents a monovalent saturated hydrocarbon group, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom. contained in the saturated hydrocarbon group -CH ₂ - may be -O -, - CO-, or -NR ⁷ - substituted, R ⁷ represents a monovalent hydrocarbon group, a hydrogen atom contained in the hydrocarbon group may be a halogen atom, or -R ¹¹ is Substituting the hydrocarbon group may be linked by -O- or -CO-, R ⁸ and R ⁹ each independently represents a monovalent saturated aliphatic hydrocarbon group, a hydrogen atom of the saturated aliphatic hydrocarbon may be contained -OH, a halogen atom, - Substituting Q, -CH=CH ₂ or -CH=CHR ⁶ , the -CH ₂ - contained in the saturated aliphatic hydrocarbon group may be -O-, -S-, -CO-, -NH- or -NR ⁶ - Substituted, R ¹⁰ represents a hydrogen atom, a monovalent hydrocarbon group or R ¹¹ , and the hydrogen atom contained in the hydrocarbon group may be substituted by a halogen atom or -R ¹¹ , and the hydrocarbon group may be bonded by -O- or -CO-, and R ¹¹ represents a monovalent hydrocarbon group which may have a substituent, and Q represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a monovalent heterocyclic group having 3 to 10 carbon atoms, and the aromatic hydrocarbon group and the heterocyclic group are contained One or more hydrogen atoms are substituted with at least one selected from the group consisting of -R ⁶ , -OR ⁶ and -CH=CHR ⁶ , and the aromatic hydrocarbon group and the remaining hydrogen contained in the heterocyclic group The atom may be substituted by -OH, -NO ₂ , -CH=CH ₂ or a halogen atom, and M represents a sodium atom or a potassium atom; wherein the compound satisfies one or more of the following requirements in (i) to (vi) , (i) R ¹ ~ R ⁴ is selected from one or more packets _{^{-SO 2 -ON = CR 7 R 10}} , -SO 2 NHNHR 7, at least one aromatic hydrocarbon substituent group -SO ₂ SR ⁷ and -SO ₂ NHSO ₂ R ¹¹ in, (ii) R ¹ One or more of ~R ⁴ is an aromatic hydrocarbon group having at least one substituent selected from the group consisting of -SO ₂ NHR ⁸ and -SO ₂ NR ⁸ R ⁹ , wherein R ⁸ and R ^{9 are} represented by The monovalent saturated aliphatic hydrocarbon group has 11 or more carbon atoms, and (iii) one or more of R ¹ to R ⁴ are -R ⁶ or have a selected from the group consisting of -R ⁶ , -OR ⁶ , and -CO ₂ R ^{6 .} And an aromatic hydrocarbon group having at least one substituent in the group of -SO ₃ R ⁶ wherein the monovalent saturated hydrocarbon group represented by R ⁶ has 11 or more carbon atoms, and (iv) has m of R ⁵ One or more of -R ₂ -ON=CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹ , (v) one or more of m having ⁵ -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ , wherein the monovalent saturated aliphatic hydrocarbon group represented by R ⁸ and R ⁹ has 11 or more carbon atoms, and (vi) has 1 of m of R ⁵ The above is -CO ₂ R ⁶ or -SO ₃ R ⁶ , wherein the monovalent saturated hydrocarbon group represented by R ⁶ has 11 or more carbon atoms. The coloring composition of claim 1, wherein in the above formula (1), a = 0, and any one of R ¹ to R ⁴ is an aromatic hydrocarbon group substituted by -SO ₃ ^- or has m One of R ⁵ is -SO ₃ ^- . The coloring composition of the first aspect of the invention, wherein the dye represented by the above formula (1) is a dye represented by the formula (2); In the formula (2), R ^1a to R ^4a each independently represent a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be a halogen atom. -R ⁶ , -OH, -OR ⁶ , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NH ₂ , -SO ₂ NHR ⁸ , -SO ₂ NR ⁸ R ⁹ , -SO ₂ -ON=CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹ is substituted, and R ^5a each independently represents -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ , -SO ₂ NR ⁸ R ⁹ , -SO ₂ -ON=CR ⁷ R ¹⁰ ,- SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹ , R ⁶ represents a monovalent saturated hydrocarbon group, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and the -CH contained in the saturated hydrocarbon group ₂ - may be substituted by -O-, -CO- or -NR ⁷ -, and R ⁷ represents a monovalent hydrocarbon group, and the hydrogen atom contained in the hydrocarbon group may be substituted by a halogen atom or -R ¹¹ , and the hydrocarbon group may be -O - link or -CO-, R ⁸ and R ⁹ each independently represents a monovalent saturated aliphatic hydrocarbon group, a hydrogen atom of the saturated aliphatic hydrocarbon may be contained -OH, a halogen atom, -Q, -CH = CH ₂ Substituted -CH = CHR ^6, -CH saturated aliphatic hydrocarbon which contains ₂ - may be -O -, - S -, - CO -, - NH- or -NR ⁶ - substituted, R ¹⁰ represents a hydrogen atom a monovalent hydrocarbon group or -R ¹¹ , the hydrogen atom contained in the hydrocarbon group may be substituted by a halogen atom or -R ¹¹ , the hydrocarbon group may be bonded by -O- or -CO-, and R ¹¹ represents a monovalent group which may have a substituent In the hydrocarbon group, Q represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a monovalent heterocyclic group having 3 to 10 carbon atoms, and the aromatic hydrocarbon group and one or more hydrogen atoms contained in the heterocyclic group. Substituted by at least one selected from the group consisting of -R ⁶ , -OR ⁶ and -CH=CHR ⁶ , the aromatic hydrocarbon group and the remaining hydrogen atoms contained in the heterocyclic group may be -OH, - NO ₂ , -CH=CH ₂ or a halogen atom, M represents a sodium atom or a potassium atom, and n represents an integer of 0 to 4. When n is an integer of 2 or more, a plurality of R ^5a may be the same or different; Wherein the compound satisfies one or more of the following requirements (i) to (vi), and (i) one or more of R ^1a to R ^4a have a selected from the group consisting of -SO ₂ -ON=CR ⁷ R ¹⁰ , in the group of -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ and -SO ₂ NHSO ₂ R ¹¹ One or more of R ^1a to R ^4a having at least one substituent, and at least one substitution having a group selected from the group consisting of -SO ₂ NHR ⁸ and -SO ₂ NR ⁸ R ⁹ The aromatic hydrocarbon group of the group, wherein the monovalent saturated aliphatic hydrocarbon group represented by R ⁸ and R ⁹ has 11 or more carbon atoms, and (iii) one or more of R ^1a to R ^4a is -R ⁶ or has an optional one. An aromatic hydrocarbon group containing at least one substituent in the group of -R ⁶ , -OR ⁶ , -CO ₂ R ⁶ and -SO ₃ R ⁶ wherein the number of carbon atoms of the monovalent saturated hydrocarbon group represented by R ⁶ 11 or more, (iv) one or more of n R ^5a are -SO ₂ -ON=CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹ , (v) One or more of n R ^5a are -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ , wherein the monovalent saturated aliphatic hydrocarbon group represented by R ⁸ and R ⁹ has 11 carbon atoms In the above, (vi) one or more of the n R ^5a are -CO ₂ R ⁶ or -SO ₃ R ⁶ , and the number of carbon atoms of the monovalent saturated hydrocarbon group represented by R ⁶ is 11 or more. A color filter comprising a coloring layer formed using the coloring composition according to any one of claims 1 to 3. A color liquid crystal display element comprising the color filter of item 4 of the patent application. A dye represented by the following formula (1), In the formula (1), X ^- represents an anion, a is an integer determined by making the compound electrically neutral, and m represents an integer of 0 to 5. When m is an integer of 2 or more, a plurality of R ⁵ may be the same. R ¹ to R ^{4 may} each independently represent a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NH ₂ , -SO ₂ NHR ⁸ , -SO ₂ NR ⁸ R ⁹ , -SO ₂ -ON=CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹ is substituted, and R ^{5 is} independently represented - SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ , -SO ₂ NR ⁸ R ⁹ , -SO ₂ -ON =CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹ , and R ⁶ represents a monovalent saturated hydrocarbon group, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom. contained in the saturated hydrocarbon group -CH ₂ - may be -O -, - CO-, or -NR ⁷ - substituted, R ⁷ represents a monovalent hydrocarbon group, a hydrogen atom contained in the hydrocarbon group may be a halogen atom, or -R ¹¹ is Substituting the hydrocarbon group may be linked by -O- or -CO-, R ⁸ and R ⁹ each independently represents a monovalent saturated aliphatic hydrocarbon group, a hydrogen atom of the saturated aliphatic hydrocarbon may be contained -OH, a halogen atom, - Substituting Q, -CH=CH ₂ or -CH=CHR ⁶ , the -CH ₂ - contained in the saturated aliphatic hydrocarbon group may be -O-, -S-, -CO-, -NH- or -NR ⁶ - Substituted, R ¹⁰ represents a hydrogen atom, a monovalent hydrocarbon group or -R ¹¹ , and the hydrogen atom contained in the hydrocarbon group may be substituted by a halogen atom or -R ¹¹ which may be bonded by -O- or -CO-, R ¹¹ A monovalent hydrocarbon group which may have a substituent, and Q represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a monovalent heterocyclic group having 3 to 10 carbon atoms, and the aromatic hydrocarbon group and the heterocyclic group One or more hydrogen atoms contained are substituted with at least one selected from the group consisting of -R ⁶ , -OR ⁶ and -CH=CHR ⁶ , and the aromatic hydrocarbon group and the rest of the heterocyclic group The hydrogen atom may be substituted by -OH, -NO ₂ , -CH=CH ₂ or a halogen atom, and M represents a sodium atom or a potassium atom; wherein the compound satisfies one or more of the following (i) to (vi) ^{conditions, (i) R 1 ~ R} 4 is selected from one or more packets having _{^{-SO 2 -ON = CR 7 R 10}} , -SO 2 NHNHR 7, at least one aromatic hydrocarbon substituent group -SO ₂ SR ⁷ and -SO ₂ NHSO ₂ R ¹¹ in, (ii) R ¹ One or more of ~R ⁴ is an aromatic hydrocarbon group having at least one substituent selected from the group consisting of -SO ₂ NHR ⁸ and -SO ₂ NR ⁸ R ⁹ , wherein R ⁸ and R ^{9 are} represented by The monovalent saturated aliphatic hydrocarbon group has 11 or more carbon atoms, and (iii) one or more of R ¹ to R ⁴ are -R ⁶ or have a selected from the group consisting of -R ⁶ , -OR ⁶ , and -CO ₂ R ^{6 .} And an aromatic hydrocarbon group having at least one substituent in the group of -SO ₃ R ⁶ wherein the monovalent saturated hydrocarbon group represented by R ⁶ has 11 or more carbon atoms, and (iv) has m of R ⁵ One or more of -R ₂ -ON=CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹ , (v) one or more of m having ⁵ -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ , wherein the monovalent saturated aliphatic hydrocarbon group represented by R ⁸ and R ⁹ has 11 or more carbon atoms, and (vi) has 1 of m of R ⁵ The above is -CO ₂ R ⁶ or -SO ₃ R ⁶ , wherein the monovalent saturated hydrocarbon group represented by R ⁶ has 11 or more carbon atoms.