TW201543149A - Coloring composition, coloring cured film and display device - Google Patents

Abstract

The present invention provides a coloring composition suitable for forming a coloring cured film having excellent heat resistance and high contrast ratio. The coloring composition is a coloring composition comprising (A) a coloring agent and (B) a polymeric compound, wherein the coloring agent comprises a fluorescence generation part and a polymer for absorbing the fluorescence generation part.

Description

Coloring composition, colored hardening film, and display element

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

When a color filter is produced using a colored radiation-sensitive composition, a method is known in which a pigment-dispersed colored radiation-sensitive composition is applied onto a substrate and dried, and then the dried coating film is irradiated with a desired pattern shape. A method of obtaining pixels of respective colors by performing radiation (hereinafter referred to as "exposure") and developing (for example, refer to Patent Documents 1 and 2). Further, a method of forming a black matrix by using a photopolymerizable composition in which carbon black is dispersed is also known (for example, see Patent Document 3). In addition, a method of obtaining a pixel of each color by an inkjet method using a pigment-dispersed coloring resin composition is known (for example, see Patent Document 4).

In recent years, there has been an urgent demand for high contrast of liquid crystal display elements and high definition of solid-state imaging elements. In order to achieve these demands, the use of dyes as colorants has been studied. However, in general, in the case of using a dye, it is resistant to the case of using a pigment as a coloring agent. Hot problems often occur. In such a background, as a coloring composition which can form a coloring pattern excellent in heat resistance and the like, for example, Patent Document 5 proposes a coloring composition containing a dye multimer as a coloring agent.

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. 2013-28764

However, according to the study by the inventors of the present invention, the coloring pattern formed by the coloring composition described in Patent Document 5 is used, and the contrast is extremely low, and it is not suitable for each color pixel used in a color filter or the like.

Therefore, an object of the present invention is to provide a colored composition suitable for formation of a colored cured film having excellent heat resistance and high contrast. Further, an object of the present invention is to provide a colored cured film formed using the colored composition and a display element including the same.

As a result of intensive studies, the present inventors have found that the above problem can be solved by using a polymer having a site that generates fluorescence and a site that absorbs the fluorescence as a colorant.

That is, the present invention provides a colored composition comprising (A) a coloring agent and (B) a coloring composition of a polymerizable compound, and (A) a coloring agent contains a polymer having a site where fluorescence is generated and a site where the fluorescent light is absorbed (hereinafter referred to as "polymer (A1)" ").

Further, the present invention provides a coloring composition comprising (A) a coloring agent and (B) a coloring composition of a polymerizable compound, (A) a coloring agent comprising a polymer having a polymer selected from the group consisting of At least one chromophore in the chromophore and the cyanine chromophore, and at least one chromophore selected from the group consisting of a triarylmethane chromophore and a chromophore.

Furthermore, the present invention provides formation using the above colored composition A colored cured film and a display element provided with the colored cured film. Here, the "coloring cured film" means a display element, a pixel of each color used in the solid-state image sensor, a black matrix, a black spacer, and the like.

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

Therefore, the colored composition of the present invention can be extremely suitably applied to a solid-state imaging element such as a color liquid crystal display element, an organic EL display element, a display element such as an electronic paper, or a CMOS image sensor.

[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 in detail.

- (A) colorant -

The coloring composition of the present invention contains the polymer (A1) as a colorant.

The polymer (A1) is not particularly limited as long as it has a site that generates fluorescence and a site that absorbs the fluorescence. However, it is preferably an ethylenically unsaturated monomer (hereinafter referred to as a site containing a site where fluorescence is generated). A copolymer of an "unsaturated monomer (a1)") and an ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (a2)") having a site for absorbing the fluorescent light. Here, the copolymer containing the unsaturated monomer (a1) and the unsaturated monomer (a2) means a polymer having an unsaturated monomer (a1) and an unsaturated monomer (a2) as structural units.

As a part which generates fluorescence, for example, it can be mentioned Hair color group, flower blue hair color group. Further, examples of the portion that absorbs fluorescence include a triarylmethane chromophore and a chromophore.

The unsaturated monomer (a1) is, for example, a compound represented by the following formula (1-1). In addition, examples of the unsaturated monomer (a2) include compounds represented by the following formula (1-2).

(In the formula (1-1), R ¹ independently represents a hydrogen atom or a methyl group.

X ¹ independently represents a direct bond, a substituted or unsubstituted divalent hydrocarbon group, or a divalent group in which the divalent hydrocarbon group is combined with one or more linking groups including an atom other than a carbon atom and a hydrogen atom. .

P denotes a portion where fluorescence is generated.

g represents an integer of 1 or more. )

(In the formula (1-2), R ² represents a hydrogen atom or a methyl group.

X ² represents a direct bond, a substituted or unsubstituted divalent hydrocarbon group, or a divalent group in which the divalent hydrocarbon group is combined with one or more linking groups including an atom other than a carbon atom and a hydrogen atom.

Q indicates the portion where the fluorescence is absorbed.

h represents an integer of 1 or more. )

R ¹ and R ² may be appropriately selected from a hydrogen atom or a methyl group.

Examples of the divalent hydrocarbon group of X ¹ and X ² include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. In the present specification, the "alicyclic hydrocarbon group" means a concept excluding an aliphatic hydrocarbon group having no cyclic structure. The divalent aliphatic hydrocarbon group may be in any of a straight chain and a branched chain, and the divalent aliphatic hydrocarbon group and the divalent alicyclic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. In the present specification, the term "alicyclic hydrocarbon group" or "aromatic hydrocarbon group" means a group including not only a ring structure but also a group further substituted with a divalent aliphatic hydrocarbon group in the ring structure. It may contain at least an alicyclic hydrocarbon or an aromatic hydrocarbon.

As the divalent aliphatic hydrocarbon group, for example, an alkanediyl group can be mentioned. (alkanediyl group), alkenediyl group, the number of carbon atoms is preferably from 1 to 20, more preferably from 2 to 12, still more preferably from 2 to 6. Specific examples include, for example, a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,1-diyl group, and a propane-1,2-diyl group. , propane-1,3-diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane Alkane-1,4-diyl, pentane-1,5-diyl, hexane-1,5-diyl, hexane-1,6-diyl, 2-methylpropane-1,2-di Base, 2,2-dimethylpropane-1,3-diyl, ethylene-1,1-diyl, ethylene-1,2-diyl, propylene-1,2-diyl, propylene-1,3 -diyl, propylene-2,3-diyl, 1-butene-1,2-diyl, 1-butene-1,3-diyl, 1-butene-1,4-diyl, 2 -pentene-1,5-diyl, 3-hexene-1,6-diyl and the like.

The divalent alicyclic hydrocarbon group may, for example, be a cycloalkylene group or a cycloalkenylene group, and has preferably 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. Specific examples include, for example, a monocyclic ring such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutenyl group, a cyclopentenyl group, or a cyclohexene group. Hydrocarbon ring group, 1,4-extension 1,4-norbornylene group, 2,5-dip An extended group such as a 1,5-adamantyl group, a 2,6-adamantyl group or the like.

The divalent aromatic hydrocarbon group is, for example, an extended aryl group, and preferably a monocyclic to 3-ring extended aryl group having 6 to 14 carbon atoms. As a specific example, For example, a phenylene group, a biphenylene group, a naphthyl group, a phenanthrenyl group, a fluorenyl group, and the like can be given.

In the divalent group in which a divalent hydrocarbon group and one or more linking groups containing an atom other than a carbon atom and a hydrogen atom are combined, examples of the linking group include -O- and -S. -, -SO ₂ -, -CO-, -COO-, -OCO-, -CONR ³ - (R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -NR ³ - (R ³ and the above The meaning is the same), and may be one type or two or more types. The bonding position of the linking group is arbitrary, and for example, it may be at the terminal of the divalent hydrocarbon group or between the CC bonds, but it is preferably contained between one terminal or a CC bond. Further, the divalent hydrocarbon group may be bonded to the above-mentioned linking group to form a ring structure. Further, the number of carbon atoms referred to in paragraph [0019] means the total number of carbon atoms of a portion excluding a carbon atom constituting the linking group.

Specific examples of the divalent hydrocarbon group having the above-mentioned linking group between the CC bonds include, for example, -CH ₂ -CH ₂ -CH ₂ -COO-CH ₂ -CH ₂ -, -CH ₂ -CH (-CH ₃ -CH ₂ -COO-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -OCO-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -COO-CH ₂ -CH(CH ₂ -CH ₃ )-CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH(CH ₂ -CH ₃ )-CH ₂ - CH ₂ -CH ₂ -CH ₂ -, -(CH ₂ ) ₅ -COO-(CH ₂ ) ₁₁ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -C-(COO-CH ₂ -CH ₃ ) ₂ -, -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -(CH ₂ -CH ₂ -O) _n - CH ₂ -(n is an integer from 1 to 8), -(CH ₂ -CH ₂ -CH ₂ -O) _m -CH ₂ - (m is an integer from 1 to 5), -CH ₂ -CH(CH ₃ ) -O-CH ₂ -CH ₂ -, -CH ₂ -CH-(OCH ₃ )-, -CH ₂ -CH ₂ -COO-CH ₂ -CH ₂ -O-CH ₂ -CH(CH ₂ -CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -O-CO-CH ₂ -CH(CH ₂ -CH ₃ )-CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -COO-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH(CH ₂ -CH ₃ )-CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -NH-COO-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -OCO-CH ₂ -, etc., but are not limited thereto.

Further, as a divalent hydrocarbon group, it is bonded to the above-mentioned linking group. Specific examples of the group of the ring structure to be formed include, for example, the following, but are not limited thereto.

As a substituent having a divalent hydrocarbon group, a halogen can be mentioned Atom, nitro, hydroxy, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkoxy group may be in any of a straight chain and a branched chain, and the number of carbon atoms is preferably from 1 to 6. Specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The aryloxy group is preferably an aryloxy group having 6 to 14 carbon atoms, and examples thereof include a phenoxy group and a benzyloxy group. In addition, as alkoxy and aryloxy groups Examples of the substituent include a halogen atom, a nitro group, a hydroxyl group, an amine group, a carboxyl group, a sulfanyl group and the like. Further, when the divalent hydrocarbon group is a divalent aromatic hydrocarbon group, it may be substituted with a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group. The alkyl group and the alkenyl group preferably have 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a secondary group. Further, examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 1-butenyl group, a 1-pentenyl group, and a 1-hexenyl group, and a butyl group, a tributyl group, a hexyl group and the like. , 2-ethyl-2-butenyl and the like. In addition, examples of the substituent of the alkyl group and the alkenyl group include the same as the substituent of the above divalent hydrocarbon group.

P is not particularly limited as long as it is a group derived from a compound that generates fluorescence, but is preferably A chromophore or a cyan chromophore. The compound represented by the above formula (1-1) preferably has a selected from the group consisting of An ethylenically unsaturated monomer of at least one chromophore in a chromophore and a cyanine chromophore. also, Chromophore or cyan chromophore The residue obtained by removing the hydrogen atoms of the compound or the cyanine compound is a residue which can be bonded to the g X ^{1 of the} above formula (1-1).

The Q is not particularly limited as long as it is a group derived from a compound that absorbs fluorescence, but is preferably a triarylmethane chromophore or a chromophore. The compound represented by the above formula (1-2) is preferably an ethylenically unsaturated monomer having at least one chromophore selected from the group consisting of a triarylmethane chromophore and a fluorene chromophore. Further, the triarylmethane chromophore or the chromophore is a residue obtained by removing h hydrogen atoms from a triarylmethane compound or a hydrazine compound, and is a group of h of the above formula (1-2). X ² linked residues.

g and h each independently represent an integer of 1 or more, but preferably 1 or 2.

As Examples of the compound, the cyanine compound, the triarylmethane compound, and the hydrazine compound include a dye classified as a dye (Dye) in a color index (CI; issued by The Society of Dyers and Colourists). As these dyes, any of an acid dye, a direct dye, a basic dye, a salt-forming dye, an oil-soluble dye, a disperse dye, a reactive dye, a mordant dye, a vat dye, a sulphur dye, and the like can be used. However, it is preferable to use an acid dye, an oil-soluble dye, or a basic dye from the viewpoint of the compound represented by the above formula (1-1) and the compound represented by the above formula (1-2). .

As an acid dye, it is classified as C.I. in the color index. Acidic, as a direct dye, is classified as C.I. in the color index. As the oil-soluble dye, it is classified into C.I. solvent in the color index, and as a basic dye, it is classified into C.I. basic in the color index.

Following, for The compound, the cyanine compound, the triarylmethane compound, and the hydrazine compound will be described.

As The compound is preferably a compound having a structure represented by the following formula (2), and specific examples thereof include CI Basic Violet 10 (Rose Red B). Is a basic dye.

In the formula (2), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, and have an atom other than a carbon atom and a hydrogen atom between CC bonds of the hydrocarbon group. a group of a linking group, or a substituted or unsubstituted heterocyclic group.

R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group.

R ¹⁷ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -SO ₃ R ¹⁸ , -CO ₂ ^- , -CO ₂ H, -CO ₂ M, -CO ₂ R ¹⁹ , -SO ₂ NHR ²⁰ Or -SO ₂ NR ²¹ R ²² .

r represents an integer of 0 to 5, and when r is an integer of 2 or more, a plurality of R ^{17 's} may be the same or different.

R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a substituted or unsubstituted hydrocarbon group or a group having a linking group containing an atom other than a carbon atom and a hydrogen atom between CC bonds of the hydrocarbon group.

R ²¹ and R ²² each independently represent a substituted or unsubstituted hydrocarbon group, or a group having a linking group containing an atom other than a carbon atom and a hydrogen atom between CC bonds of the hydrocarbon group, or R ²¹ and R ²² are bonded to each other A substituted or unsubstituted heterocyclic group is formed.

M represents a sodium atom or a potassium atom. ]

Examples of the hydrocarbon group in R ¹¹ to R ¹⁶ and R ¹⁸ to R ²² include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

The aliphatic hydrocarbon group may be saturated or unsaturated, and examples thereof include an alkyl group, an alkenyl group, and an alkynyl group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably from 1 to 30, more preferably from 1 to 15, and particularly preferably from 1 to 8. Further, the aliphatic hydrocarbon group may be linear or branched. The alkyl group may, for example, be a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a 1-methylindenyl group, a dodecyl group or a 1-methyl group, in addition to the above specific examples. Undecyl, 1-ethylindenyl, tridecyl, tetradecyl, tertiary dodecyl, pentadecyl, 1-heptyloctyl, hexadecyl, octadecyl Wait. The alkenyl group may, for example, be 2-octenyl, (4-vinyl)-5-hexenyl or 2-decenyl, in addition to the above specific examples. Further, 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 group. a butynyl group, a 2-octynyl group, a (4-ethynyl)-5-hexynyl group, a 2-decynyl group, and the like.

The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 30 carbon atoms. The alicyclic hydrocarbon group may be saturated or unsaturated, and examples thereof include a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a bridged cyclic hydrocarbon group, a spirocyclic hydrocarbon group, a cyclic anthracene hydrocarbon group, and the like. More specifically, a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a tert-butylcyclohexyl group, a cycloheptyl group or a cyclooctyl group; a 1-cyclohexenyl group; a cycloalkenyl group; a condensed polycyclic hydrocarbon group such as a tricyclodecanyl group, a decahydro-2-naphthyl group, an adamantyl group or the like; a tricyclo[5.2.1.0 ^2,6 ]decane-8-yl group, a pentacyclic group Alkyl, different a bridged hydrocarbon group such as a dicyclopentenyl group or a tricyclopentenyl group; a monovalent group obtained by removing one hydrogen atom from a spiro[3,4]heptane or a spiro[3,4]octane; Spirocyclic hydrocarbon group; A cyclic anthracene hydrocarbon group such as a monovalent group obtained by removing one hydrogen atom such as a p-menthane, a side cedar or a decane. More preferably, the cycloalkyl group and the cycloalkenyl group have 3 to 12 carbon atoms.

As the aromatic hydrocarbon group, it is preferably 6 to 20 carbon atoms. The aryl group is more preferably an aryl group having 6 to 10 carbon atoms. Here, the "aryl group" may be a monocyclic to 3-ring aromatic hydrocarbon group, and examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, an anthryl group, a 9-fluorenyl group, and the like. Phenyl, naphthyl.

Further, the hydrocarbon group in R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² may have a linking group containing an atom other than a carbon atom and a hydrogen atom between CC bonds. In the case of having a linking group, a group having the above-mentioned linking group between the CC bonds of the aliphatic hydrocarbon group is preferred. Specific examples of the linking group include the same as described above.

The heterocyclic group may be a monocyclic heterocyclic ring or a polycyclic heterocyclic ring. The heterocyclic group may be an unsaturated ring or a saturated ring, or may have two or more kinds of hetero atoms (for example, a nitrogen atom, an oxygen atom or a sulfur atom) of the same kind or different types in the ring. The heterocyclic group is preferably a heterocyclic group having 3 to 10 carbon atoms, and examples thereof include a pyrrolidinyl group, an imidazolidinyl group, and a pyrazolyl group. Olinyl, thio Polinyl, piperidinyl, N-hexahydropyridyl (piperidino), piperazine Base, high piper a nitrogen-containing alicyclic heterocyclic group such as a homopiperazinyl group; an alicyclic heterocyclic group such as a 1,3-dioxolan-2-yl group; a pyridyl group and a pyridyl group Base, pyrimidinyl, oxime Base, quinolyl, isoquinolyl, anthracene base, Pyridyl, quin Lolinyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, benzothiazolyl, a nitrogen-containing aromatic heterocyclic group such as an azole group, a fluorenyl group, a carbazolyl group, a benzimidazolyl group or a phthalimido group; a thienyl group, a furyl group, a piperidyl group, a fluorenyl group or the like Aromatic heterocyclic group.

The heterocyclic group which is formed by bonding R ²¹ and R ^{22 to} each other may be the same as the above heterocyclic group.

Examples of the substituent of the hydrocarbon group in R ¹¹ to R ¹⁶ and R ¹⁸ to R ²² include a halogen atom, a hydroxyl group, a cyano group, a decyl group, a carboxyl group, a nitro group, an amine group, and a di(C _1-8 alkyl group). Amino, diarylamine, C _1-8 alkoxy, C _6-10 aryloxy, C _2-8 alkoxycarbonyl, C _1-8 alkylthio, C _6-10 aryl Thio group, tri(C _1-8 alkyl)carbamyl group, fluorenyl group, allyl group, C _1-8 alkylsulfonyl group, C _1-8 alkylamine sulfonyl group, heterocyclic group, aromatic hydrocarbon group And, the alicyclic hydrocarbon group, the heterocyclic group, and the aromatic hydrocarbon group may be substituted with an aliphatic hydrocarbon group. These substituents may further have a substituent. Further, the position and number of the substituent are arbitrary, and when there are two or more substituents, the substituents may be the same or different. Further, examples of the substituent of the heterocyclic group of R ¹¹ to R ¹⁴ and the substituent of the heterocyclic group in which R ²¹ and R ²² are bonded to each other include R ¹¹ to R ¹⁶ and R ¹⁸ to R ^{22 .} The substituents of the hydrocarbyl group are the same.

Among them, R ¹¹ , R ¹² , R ¹³ and R ^{14 are} preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms.

R ¹⁵ and R ^{16 are} preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

R ^{17 is} preferably -SO ₃ H, -SO ₃ R ¹⁸ , -CO ₂ H, -CO ₂ R ¹⁹ , -SO ₂ NHR ²⁰ or -SO ₂ NR ²¹ R ²² , again, as R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ^{22 are} preferably an alkyl group having 1 to 8 carbon atoms.

r is preferably 1 or 2.

As the structure having the structure represented by the above formula (2) Specific examples of the compound include, for example, a compound having a structure represented by the following formula.

When the structure represented by the above formula (2) is cationic, the structure is The compound has an anion in a manner that is electrically neutral. Examples of the anion 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 a hydroxide ion.

Further, when the structure represented by the above formula (2) is anionic, the structure having the structure The compound has a cation in an electrically neutral manner. Examples of the cation include a proton, a metal cation, a phosphonium cation, and the like. Examples of the metal cation include a monovalent metal cation such as a lithium ion, a sodium ion, a potassium ion, a cerium ion, or a cerium ion; and a divalent metal cation such as a magnesium ion, a calcium ion, a cerium ion, or a cerium ion. Examples of the phosphonium cation include an ammonium cation, a phosphonium cation, and the like. Specific examples of the ammonium cation include a cation in the compound described in paragraph [0045] of JP-A-2011-138094, and a specific example of the phosphonium cation is disclosed in JP-A-2013-190776. The cations described in paragraphs [0038] to [0040] and the like.

As the cyanine compound, it is preferred to have a formula represented by the following formula (3) Specific examples of the compound having the structure shown are, for example, a cyanine-based basic dye such as C.I. Basic Red 12.

In the formula (3), R ³¹ and R ³² each independently represent a substituted or unsubstituted hydrocarbon group.

R ³³ to R ³⁵ independently of each other represent a hydrogen atom, a halogen atom, a substituted or unsubstituted hydrocarbon group. A plurality of R ³³ and R ^{34 present} may be the same or different.

Ring Z ¹ and ring Z ² independently of each other represent a substituted or unsubstituted aromatic hydrocarbon ring.

G ¹ and G ² independently represent -O-, -S- or -CR ³⁶ R ³⁷ -. Wherein, R ³⁶ and R ³⁷ each independently represent a substituted or unsubstituted hydrocarbon group.

s represents an integer from 1 to 3. ]

Examples of the hydrocarbon group in R ³¹ to R ³⁷ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Specific examples thereof include the same ones as those in the formula (2), and the same substituents may be used.

The aromatic hydrocarbon ring in the ring Z ¹ and the ring Z ² may be a monocyclic aromatic hydrocarbon ring or a polycyclic aromatic hydrocarbon ring, and the number of carbon atoms is preferably 6 to 20, more preferably 6 to 10. . Specific examples thereof include a benzene ring, a biphenyl ring, a naphthalene ring, an anthracene ring, an anthracene ring, a phenanthrene ring, an anthracene ring, a condensed tetraphenyl ring, and a linked triphenyl ring. The substituent of the aromatic hydrocarbon ring may be the same as the substituent of the hydrocarbon group in the formula (2).

In particular, the hydrocarbon group in R ³¹ and R ³² is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 6 carbon atoms. .

R ³³ to R ^{35 are} preferably a hydrogen atom.

As the ring Z ¹ and the ring Z ² , a benzene ring is preferred.

G ¹ and G ^{2 are} preferably -O- or -CR ³⁶ R ³⁷ -, and R ³⁶ and R ^{37 are} preferably an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group is particularly preferably a methyl group or an ethyl group.

s is preferably 1 or 2, more preferably 1.

As a cyanine having the structure represented by the above formula (3) Specific examples of the compound include, for example, a compound having a structure represented by the following formula.

When the structure represented by the above formula (3) is cationic, it has The cyanine compound of this structure has an anion in an electrically neutral manner. Further, when the structure represented by the above formula (3) is anionic, the cyanine compound having such a structure has a cation which is electrically neutral. Specific examples of such anions and cations include, for example, the same as those exemplified in the above formula (2).

As the triarylmethane compound, for example, two An aminotriarylmethane dye, a triaminetriarylmethane dye, a rose acid dye having an OH group, and the like. Among them, a diaminotriarylmethane dye or a triaminetriarylmethane dye is preferred because it is excellent in color tone and excellent in sunlight fastness to other dyes. The compound having a structure represented by the following formula (4) is exemplified as a more preferable triarylmethane compound. Further, the structure represented by the following formula (4) has various resonance structures. However, in the present specification, the resonance structures are equivalent to the structure represented by the following formula (4).

[In the formula (4), Y represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group or -NR ⁵⁹ R ⁶⁰ .

R ⁴¹ to R ⁴⁴ and R ⁵⁹ to R ⁶⁰ each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group.

R ⁴⁵ to R ⁵² represent a hydrogen atom, a halogen atom, a substituted or unsubstituted hydrocarbon group, or -COOR'. Wherein R' represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.

Ar represents a substituted or unsubstituted aromatic hydrocarbon group. ]

Examples of the hydrocarbon group in Y, R ⁴¹ to R ⁵² , R ⁵⁹ to R ⁶⁰ and R′ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Specific examples thereof include the same ones as those in the formula (2), and the same substituents may be used.

The aromatic hydrocarbon group of Ar preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms. Specific examples thereof include a phenylene group, an extended naphthyl group, a diphenylene group, and a fluorene group. The substituent of the aromatic hydrocarbon group is, for example, the same as the substituent of the hydrocarbon group in the formula (2), and among them, a halogen atom is preferred.

Among them, R ⁴¹ to R ⁴⁴ , R ⁵⁹ to R ⁶⁰ and R' are preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

R ⁴⁵ to R ^{52 are} preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms.

Ar is preferably a phenyl group or a naphthyl group.

Y is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

In the present invention, among the structures represented by the above formula (4), a cation represented by the following formula (4-1) or (4-2) is particularly preferable from the viewpoint of heat resistance and solvent resistance.

In the formulae (4-1) and (4-2), Y ¹ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or -NR ⁶¹ R ⁶² .

R ⁵³ to R ⁵⁶ and R ⁶¹ to R ⁶² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

R ⁵⁷ and R ⁵⁸ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms. ]

R ⁵³ to R ^{56 are more} preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group or an ethyl group.

R ⁵⁷ and R ^{58 are} preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms.

R ⁶¹ to R ^{62 are} preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Y ^{1 is} preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Specific examples of the triarylmethane compound having a structure represented by the above formula (4) include a compound having a structure represented by the following formula.

When the structure represented by the above formula (4) is cationic, it has The triarylmethane compound of this structure has an anion in an electrically neutral manner. Further, when the structure represented by the above formula (4) is anionic, the triarylmethane compound having such a structure has a cation which is electrically neutral. Specific examples of such anions and cations include, for example, the same as those exemplified in the above formula (2).

As the hydrazine compound, it is preferred to have the following formula (5-1) Or a compound of the structure represented by (5-2), as a specific example, an oleyl oil-soluble dye of C.I. solvent green 3 etc. is mentioned, for example.

In the formula (5-1), R ⁷¹ and R ⁷² each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group. ]

[In the formula (5-2), R ⁸¹ and R ⁸² represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group.

R ⁸³ represents a substituted or unsubstituted divalent hydrocarbon group. ]

R ⁸⁴ , R ⁸⁵ and R ⁸⁶ each independently represent a substituted or unsubstituted hydrocarbon group. ]

Examples of the hydrocarbon group in R ⁷¹ , R ⁷² , R ⁸¹ , R ⁸² and R ⁸⁴ to R ⁸⁶ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Specific examples thereof are the same as those exemplified in the formula (2), and the same substituents may be used.

^Examples of the divalent hydrocarbon group in R ⁸³ include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. Specific examples of the divalent hydrocarbon group of the formulae (1-1) and (1-2) are the same as those exemplified, and the same substituents may be used.

Wherein, as R ⁷¹ and R ⁷² , a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms is preferred, and a hydrogen atom is more preferred. Or a substituted or unsubstituted phenyl group. Examples of the substituent of the alkyl group include a halogen atom, a hydroxyl group, and a cyano group. Examples of the substituent of the aryl group and the phenyl group include a halogen atom, a hydroxyl group, a cyano group, and an alkyl group having 1 to 6 carbon atoms. Base.

R ⁸¹ , R ⁸² , R ⁸⁴ , R ⁸⁵ and R ^{86 are} preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom, or a substituted or unsubstituted one. An alkyl group having 1 to 4 carbon atoms. The substituent of the alkyl group is the same as described above.

R ^{83 is} preferably an alkanediyl group having 1 to 20 carbon atoms, more preferably an alkanediyl group having 2 to 8 carbon atoms. Examples of the substituent of the alkanediyl group include the same substituents as X ¹ and X ² of the above formulae (1-1) and (1-2).

As having a knot represented by the above formula (5-1) or (5-2) Specific examples of the ruthenium compound are, for example, compounds having a structure represented by the following formula.

In addition to the above, as Compounds, for example, can also be used

CI acid red 51 (erythromycin), CI acid red 52 (acid rose red), CI acid red 87 (blush red G), CI acid red 92 (acid root red PB), CI acid red 289, CI acid red 388, Bengal Rose Red B (Edible Red No. 5), Acid Rose Red G, CI Acid Violet 9, etc. Acid dye; CI solvent red 35, CI solvent red 36, CI solvent red 42, CI solvent red 43, CI solvent red 44, CI solvent red 45, CI solvent red 46, CI solvent red 47, CI solvent red 48, CI Solvent Red 49, CI Solvent Red 72, CI Solvent Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, CI Solvent Violet 2, CI Solvent Violet 10, etc. Oil-soluble dye; CI alkaline red 1 (Rose red 6GCP), CI alkaline red 8 (Rose red G), etc. It is a basic dye or the like.

Further, as the cyanine compound, for example, CI Basic Red 13, CI Basic Red 14, CI Basic Violet 7, CI Basic Yellow 11, CI Basic Yellow 13, CI Basic Yellow 21, and CI Base can also be used. Cyanine alkaline dyes such as Sexual Yellow 28 and CI Alkaline Yellow 51.

Further, as the triarylmethane compound, for example, it is also possible to use

CI Acid Blue 1, CI Acid Blue 3, CI Acid Blue 5, CI Acid Blue 7, CI Acid Blue 9, CI Acid Blue 11, CI Acid Blue 15, CI Acid Blue 17, CI Acid Blue 19, CI Acid Blue 22, CI Acid Blue 24, CI Acid Blue 38, CI Acid Blue 48, CI Acid Blue 75, CI Acid Blue 83, CI Acid Blue 90, CI Acid Blue 91, CI Acid Blue 93, CI Acid Blue 93:1, CI Acid Blue 100, CI Acid Blue 103, CI Acid Blue 104, CI Acid Blue 109, CI Acid Blue 110, CI Acid Blue 119, CI Acid Blue 147, CI Acid Blue 269, CI Acid blue 123, CI acid blue 213, CI direct blue 41, CI acid purple 17, CI acid purple 19, CI acid purple 21, CI acid purple 23, CI acid purple 25, CI acid purple 38, CI acid purple 49, CI Triarylmethane acid dyes such as acid violet 72; CI basic violet 1 (methyl violet), CI basic violet 3 (crystal violet), CI alkaline violet 14 (magenta), CI alkaline blue 1 (Basic Cyanine 6G), CI Basic Blue 5 (Alkaline Cyanine EX), CI Basic Blue 7 (Victoria Pure Blue), CI Basic Blue 26 (Victoria Blue B conc.) , a triarylmethane-based basic dye such as CI basic green 1 (bright green GX), CI basic green 4 (malachite green), or a triarylmethane-based direct dye such as CI Direct Blue 41.

Further, as the ruthenium compound, for example, it is also possible to use

CI Acid Blue 23, CI Acid Blue 25, CI Acid Blue 27, CI Acid Blue 35, CI Acid Blue 40, CI Acid Blue 41, CI Acid Blue 43, CI Acid Blue 45, CI Acid Blue 47, CI Acid Blue 49, CI Acid Blue 51, CI Acid Blue 53, CI Acid Blue 55, CI Acid Blue 56, CI Acid Blue 62, CI Acid Blue 68, CI Acid Blue 69, CI Acid Blue 78, CI Acid Blue 80, CI Acid Blue 81: 1. CI Acid Blue 11, CI Acid Blue 124, CI Acid Blue 127, CI Acid Blue 127:1, CI Acid Blue 140, CI Acid Blue 150, CI Acid Blue 175, CI Acid Blue 215, CI Acid Blue 230, CI Acid dyes of acid blue 277, CI acid blue 344, CI acid violet 41, CI acid violet 42, CI acid violet 43, CI acid green 25, CI acid green 27, etc.; direct dyes such as CI direct violet 17; C.I. Solvent red 172, C.I. Solvent red 222, C.I. Solvent violet 60 and the like are hydrazine-based oil-soluble dyes.

As the compound represented by the above formula (1-1), the above formula The method for synthesizing the compound represented by (1-2) is not particularly limited, and a conventionally known method can be used. For example, it can be obtained by introducing a group having an ethylenically unsaturated group into a basic skeleton of the above dye having a functional group by a usual organic synthesis method, or introducing a group having an ethylenically unsaturated group to a synthetic raw material of the dye. , synthetic dyes. More specifically, the descriptions of Japanese Patent Laid-Open Publication No. 2013-178478, JP-A-2013-173850, JP-A-2013-210621, and JP-A-2013-028764.

Then, the polymer (A1) can be produced by copolymerizing a compound represented by the above formula (1-1) and a compound represented by the above formula (1-2). A conventionally known method can be used for the copolymerization reaction, and for example, the same method as the (C) binder resin described later can be employed.

In the polymer (A1), the content and the absorption of the portion where the fluorescence is generated The ratio of the content of the fluorescent portion is preferably 99/1 to 50/50, more preferably 97/3 to 60/40, and more preferably 95/5, based on the molar ratio (the former/the latter). ~70/30, and even better 90/10~70/30. Further, when the polymer (A1) is a copolymer comprising an unsaturated monomer (a1) and an unsaturated monomer (a2), the number of moles of the unsaturated monomer (a1) is set to p, and the unsaturated single is used. When the number of moles of the body (a2) is q, it is preferred that the molar ratio (p/q) of the monomer is within the above range.

In particular, when the polymer (A1) is a copolymer comprising an unsaturated monomer (a1) and an unsaturated monomer (a2), the unsaturated monomer (a1) and the unsaturated monomer (a2) The copolymerization ratio (p/q), in terms of mass ratio, is preferably 97/3 to 40/60, more preferably 95/5 to 65/35, and still more preferably 90/10 to 70/30.

The polymer (A1) may have an unsaturated monomer (a1) and an insufficient A copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as "unsaturated monomer (a3)") other than the monomer (a2) is used as a structural unit.

As a specific example of such an unsaturated monomer (a3), an example is mentioned. For example, it can be cited

(meth)acrylic acid, maleic acid, maleic anhydride, mono[2-(methyl)acryloxyethyl) succinate, ω-carboxypolycaprolactone mono(meth)acrylate, ethylene An ethylenically unsaturated monomer having a carboxyl group such as a benzoic acid; an N-position substituted maleimide such as N-phenylmaleimide or N-cyclohexylmaleamide; styrene , α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, aromatic vinyl compound such as vinyl naphthalene; (meth)acrylic acid Ester, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate , polyethylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2~10) Mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylate Ester, tricyclo [5.1.02 ^2,6 ]decane-8-yl ester, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, (methyl) 4-hydroxyphenyl acrylate, pair Ethylene oxide modified (meth) acrylate of phenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, 3-[(meth) propylene (meth) acrylate such as decyloxymethyl]oxetane, 3-[(meth)acryloxymethyl]-3-ethyloxetane; cyclohexylvinyl Ether, different Vinyl ether, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3-(vinyloxymethyl)-3-ethyl a vinyl ether such as oxetane; a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, or polyoxyalkylene The terminal has a mono (meth) acrylonitrile-based macromonomer.

Among them, from the viewpoint of heat resistance, solvent resistance, transfer resistance, and dispersibility, the unsaturated monomer (a3) is preferably an ethylenically unsaturated monomer having a carboxyl group or a (meth) acrylate. .

When the polymer (A1) is a copolymer further comprising an unsaturated monomer (a3) as a structural unit, the copolymerization ratio of the unsaturated monomer (a3) in all the structural units of the polymer (A1) is preferably the following kind. That is, the copolymerization ratio of the unsaturated monomer (a3) is preferably from 30 to 97% by mass, more preferably from 40 to 95% by mass, particularly preferably from 50 to 90% by mass, based on the entire structural unit. By copolymerizing the unsaturated monomer (a3) in such a range, a coloring composition excellent in heat resistance, solvent resistance, transfer resistance, and dispersibility can be easily obtained.

The polystyrene-equivalent weight average molecular weight (Mw) of the polymer (A1) measured by gel permeation chromatography (hereinafter abbreviated as GPC) (eluent solvent: tetrahydrofuran) is usually from 1,000 to 100,000, preferably 3,000. ~50000, more preferably 3000~10000. By becoming such a way, Contrast, heat resistance, solvent resistance, dye transfer resistance, film properties, electrical properties, pattern shape, and resolution can be improved.

In addition, the weight average molecular weight (Mw) of the polymer (A1) and The ratio of the number average molecular weight (Mn) (Mw/Mn) is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. In addition, the Mn is a polystyrene-equivalent number average molecular weight measured by GPC (eluent solvent: tetrahydrofuran).

The colored composition of the present invention may be other than the polymer (A1) Mix other colorants. The other coloring agent is not particularly limited, and the color and the material can be appropriately selected depending on the application. Examples of the other coloring agents include pigments and dyes other than the polymer (A1), and other coloring agents may be used singly or in combination of two or more. Among them, from the viewpoint of obtaining pixels having high luminance, contrast, and coloring power, an organic pigment is preferable as the pigment, and an organic dye is preferable as the dye. Examples of the organic dye include those described in paragraphs [0071] to [0074].

As an organic pigment, for example, a color index can be cited. A compound as described below classified as a pigment.

CI pigment red 166, CI pigment red 177, CI pigment red 224, CI pigment red 242, CI pigment red 254, CI pigment red 264; CI pigment green 7, CI pigment green 36, CI pigment green 58, CI pigment green 59; CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 80; CI Pigment Yellow 14, CI Pigment Yellow 83, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 179, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 211, CI Pigment Yellow 215; C.I. Pigment Orange 38; C.I. Pigment Violet 23.

Further, a red pigment represented by the following formula,

Japanese Special Publication No. 2001-081348, Japan Special The lake pigments described in Japanese Laid-Open Patent Publication No. 2011-145346, and the Japanese Patent Publication No. 2011-145346, and the like.

In the present invention, any other pigments that are mixed can be passed A recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or the like, and a combination thereof are used for purification. Further, these pigments may be used by modifying the surface of the particles by a resin as desired. For example, a vehicle resin described in JP-A-2001-108817 or a commercially available resin for pigment dispersion can be used as the resin for modifying the surface of the pigment particles. As a resin coating method of the surface of the carbon black, for example, Japanese Laid-Open Patent Publication No. Hei 9-71733, The method described in Japanese Laid-Open Patent Publication No. Hei 9-95625, and the like. Further, the organic pigment can be used by miniaturizing the primary particles by so-called salt milling. As a method of salt milling, for example, the method disclosed in Japanese Laid-Open Patent Publication No. Hei 8-179111 can be employed.

In addition, in the present invention, it is possible to mix with any other The toner further contains a well-known dispersant and a dispersing aid together. Examples of the known dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, and a polyoxyethylene alkyl phenyl ether dispersant. A polyethylene glycol diester dispersing agent, a sorbitan fatty acid ester dispersing agent, a polyester dispersing agent, an acrylic dispersing agent, and the like, and a dispersing aid may, for example, be a pigment derivative.

Such dispersants can be obtained commercially, for example Examples of the acrylic dispersant include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (above, BYK-Chemie (BYK)), and the like, and as an urethane-based dispersant, Examples thereof include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, BYK-Chemie (BYK)), Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), and the like. Examples of the polyethyleneimine-based dispersing agent include Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), and examples of the polyester-based dispersing agent include Adisper PB821, Adisper PB822, Adisper PB880, and Adisper PB881 (above, Ajinomoto Fine-Techno shares). Co., Ltd.) and BYK-LPN21324 (BYK-Chemie (BYK) company) and so on.

Further, as the pigment derivative, specifically, it can be mentioned A sulfonic acid derivative such as copper phthalocyanine, diketopyrrolopyrrole or quinophthalone is obtained.

Content ratio of other colorants when other colorants are included In the case of the total content of the coloring agent, it is preferably 70% by mass or less, and more preferably 50 parts by mass or less. The lower limit value is not particularly limited, and may be 0.01% by mass or more.

From the formation of heat resistance, solvent resistance, inhibition of transfer and bright In view of the high color purity of the pixel or the black matrix or the black spacer having excellent light-shielding properties, the content ratio of the (A) coloring agent is usually from 3 to 70% by mass, preferably 5, based on the solid content of the coloring composition. ~60% by mass, more preferably 5 to 30% by mass. Here, the solid content means a component other than the solvent described later.

- (B) Polymeric Compound -

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

Specific examples of the compound having two or more (meth) acryloyl fluorenyl groups include polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid. An ester-modified polyfunctional (meth) acrylate, an alkylene oxide-modified polyfunctional (meth) acrylate, a polyfunctional amine obtained by reacting a hydroxyl group-containing (meth) acrylate with a polyfunctional isocyanate Carbamate (meth)acrylic acid An ester, 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, as the aliphatic polyhydroxy compound, for example, Examples thereof include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and trivalent glycerol, trimethylolpropane, neopentyl alcohol, and dipentaerythritol. The above aliphatic polyhydroxy compound. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol tri(methyl). 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 acid anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride; and pyromellitic acid II. A tetrabasic acid dianhydride such as an anhydride, a biphenyltetracarboxylic dianhydride, or a benzophenone tetracarboxylic dianhydride.

In addition, as a polyfunctional (meth) propyl modified by caprolactone The enoate is, for example, a compound described in paragraphs [0015] to [0018] of JP-A-11-44955. The polyfunctional (meth) acrylate modified by the alkylene oxide may, for example, be bisphenol A di(meth)acrylate modified from at least one selected from the group consisting of ethylene oxide and propylene oxide. At least one modified isocyanuric acid tri(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide, and modified by at least one selected from the group consisting of ethylene oxide and propylene oxide Trimethylolpropane tri(meth)acrylate, modified from at least one selected from the group consisting of ethylene oxide and propylene oxide Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate modified by at least one selected from the group consisting of ethylene oxide and propylene oxide, selected from ethylene oxide and At least one modified dipentaerythritol penta (meth) acrylate in propylene oxide, and at least one modified dipentaerythritol hexa selected from the group consisting of ethylene oxide and propylene oxide Methyl) acrylate or the like.

Further, examples of the compound having two or more N-alkoxymethylamino groups include a melamine structure and a benzoquinone structure. Structure, compound of urea structure, and the like. Also, melamine structure, benzoquinone Structure means having more than one of three Ring or phenyl substituted three The chemical structure of the ring as a basic skeleton is composed of melamine and benzoquinone. Or the concept of their condensate. 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)benzoquinone , N, N, N', N'-tetrakis(alkoxymethyl) glycoluril, and the like.

Among these polymerizable compounds, a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid or a polyfunctional (methyl group modified by caprolactone) is preferred. Acrylate, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate having carboxyl group, N, N, N', N', N", N"-hexa (alkoxy) Methyl)melamine, N,N,N',N'-tetrakis(alkoxymethyl)benzoquinone . The trivalent or higher aliphatic polyhydroxy compound is obtained from the viewpoint of high strength of the colored layer, excellent surface smoothness of the colored layer, and difficulty in generation of dirt and film residue on the substrate of the unexposed portion and the light shielding layer. Among the polyfunctional (meth) acrylates obtained by the reaction of acrylic acid, particularly preferred are trimethylolpropane triacrylate, neopentyl alcohol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Alcohol hexaacrylate; in a polyfunctional (meth) acrylate having a carboxyl group, a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, and dipentaerythritol pentaacrylate and amber are particularly preferred. A compound obtained by reacting an acid anhydride.

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

The content of the (B) polymerizable compound in the present invention is relative to (A) 100 parts by mass of the colorant, preferably 10 to 1000 parts by mass, more preferably 20 to 800 parts by mass, still more preferably 100 to 700 parts by mass, particularly preferably 200 to 400 parts by mass. By such an aspect, it is possible to improve the curability and the alkali developability.

-(C) Adhesive Resin -

The coloring composition of the present invention may contain a binder resin (except that the polymer (A1) is not included). Thereby, the alkali solubility of the coloring composition, the adhesion to the substrate, the storage stability, and the like can be improved. The binder resin is not particularly limited as long as it does not correspond to the polymer (A1), but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. In particular, a polymer having a carboxyl group (hereinafter referred to as a "carboxyl group-containing polymer") is exemplified, and examples thereof include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated". A copolymer of a monomer (c1)") and another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (c2)").

Examples of the unsaturated monomer (c1) include (meth)acrylic acid, maleic acid, maleic anhydride, and succinic acid mono [2-(methyl) propylene oxime. Oxyethyl]ester, ω-carboxypolycaprolactone mono(meth)acrylate, p-vinylbenzoic acid, and the like.

These unsaturated monomers (c1) may be used singly or in combination of two or more.

Further, as the unsaturated monomer (c2), for example, The N-position substituted maleimide, aromatic vinyl compound, (meth) acrylate, vinyl ether exemplified in the unsaturated monomer (a3) has a single (methyl group) at the end of the polymer molecular chain. The macromonomer of the acrylonitrile group, etc., as a specific example, the same as the above.

The unsaturated monomer (c2) may be used singly or in combination of two or more.

Copolymerization of unsaturated monomer (c1) with unsaturated monomer (c2) The copolymerization ratio of the unsaturated monomer (c1) in the copolymer is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass. By copolymerizing the unsaturated monomer (c1) in such a range, a coloring composition excellent in alkali developability and storage stability can be obtained.

As a total of unsaturated monomer (c1) and unsaturated monomer (c2) Specific examples of the polymer include, for example, JP-A-7-140654, JP-A-H08-259876, JP-A-10-31308, JP-A-10-300922, and JP-A-K. A copolymer disclosed in, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

Further, in the present invention, for example, such as Japanese Patent Laid-Open No. 5-19467 Bulletin, Japanese Unexamined Patent Publication No. 6-230212, Japan It is also disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A carboxyl group-containing polymer such as a polymerizable unsaturated bond is used as a binder resin.

Gel permeation chromatography of adhesive resin in the present invention (hereinafter, abbreviated as GPC) (eluent solvent: tetrahydrofuran), the polystyrene-equivalent weight average molecular weight (Mw) is usually from 1,000 to 100,000, preferably from 3,000 to 50,000. By adopting such a state, the residual film ratio, the pattern shape, the heat resistance, the electrical characteristics, and the resolution of the film are further improved, and the generation of dry foreign matter during coating can be suppressed at a high level.

In addition, the weight average of the binder resin in the present invention The ratio of the amount of particles (Mw) to the number average molecular weight (Mn) (Mw/Mn) is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. In addition, the term "Mn" as used herein means a polystyrene-equivalent number average molecular weight measured by GPC (eluent solvent: tetrahydrofuran).

The binder resin in the present invention can be known by a known method For example, the structure, Mw, and Mw/Mn can be controlled by the method disclosed in Japanese Laid-Open Patent Publication No. 2003-222717, JP-A-2006-259680, and International Publication No. 2007/029871.

In the present invention, (C) the binder resin may be used alone or Mix two or more types.

In the present invention, the content of the (C) binder resin is relative to (A) The coloring agent is usually 10 to 1000 parts by mass, preferably 20 to 500 parts by mass, based on 100 parts by mass. By setting it as such an aspect, alkali developability, storage stability of a coloring composition, and chromaticity characteristic can be improved further.

-(D) Photopolymerization initiator -

The colored composition of the present invention may contain a photopolymerization initiator. Thereby, it is possible to impart radiation sensitivity to the colored composition. The photopolymerization initiator used in the present invention is a compound which generates an active species which can initiate polymerization of the above polymerizable compound 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, polynuclear oxime compound, diazo compound, sulfimine sulfonate Imidosulfonates are compounds and the like.

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 the group of the compound and the O-mercapto lanthanide compound.

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

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

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

Further, when a biimidazole-based compound is used as a photopolymerization initiator, it is preferred to use a hydrogen donor in combination from the viewpoint of improving sensitivity. The term "hydrogen donor" as used herein means a compound capable of supplying a hydrogen atom to a radical generated by a biimidazole compound by exposure. As the hydrogen donor, for example, 2-mercaptobenzothiazole or 2-indolylbenzene can be mentioned. A thiol-based hydrogen donor such as azole or an amine such as 4,4'-bis(dimethylamino)benzophenone or 4,4'-bis(diethylamino)benzophenone Hydrogen. In the present invention, the hydrogen donor may be used alone or in combination of two or more. However, from the viewpoint of further improving the sensitivity, it is preferred to combine one or more kinds of thiol-based hydrogen donors and one or more amine-based hydrogen donors. use.

In addition, as three Specific examples of the compound can be exemplified by 2,4,6-paran (trichloromethyl)-all. 2-methyl-4,6-bis(trichloromethyl)-all three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-all three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-all three 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-all three , 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-all three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-all three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-all three , 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-all three Three of the halogenated methyl groups a compound.

Further, as a specific example of the O-indenyl lanthanide compound, Take 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzamide), 1-[9-ethyl-6-(2-A Benzomethylene)-9H-carbazolyl-3-yl]-ethanone 1-(O-acetamidine), 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranyl) Methoxybenzylidene)-9H-carbazolyl-3-yl]-ethanone 1-(O-acetamidine), 1-[9-ethyl-6-{2-methyl-4- (2,2-Dimethyl-1,3-dioxolanyl)methoxybenzylidene}-9H-carbazolyl-3-yl]-ethanone 1-(O-acetamidine) Wait. As a commercial item of the O-mercapto fluorene-based compound, NCI-831, NCI-930 (above, ADEKA Co., Ltd.) can be used.

In the present invention, a combination of a acetophenone-based compound or the like is used. When a photopolymerization initiator other than the imidazole compound is used, a sensitizer can be used in combination. As such a sensitizer, for example, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4- Diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5 - bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(2-B Base amino) chalcone and the like.

In the present invention, the content of the photopolymerization initiator is relative to (B) 100 parts by mass of the polymerizable compound is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass. By setting it as such an aspect, it is excellent in hardenability and film characteristics.

- solvent -

The colored composition of the present invention contains the above components (A) and (B) and other components added arbitrarily. However, it is usually prepared by mixing an organic solvent as a liquid composition.

The organic solvent is appropriately selected and used as long as the components (A) and (B) constituting the colored composition and other components are dispersed or dissolved, and are not reacted with these components and have moderate volatility.

Among such organic solvents, for example,

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol single positive 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 (poly)alkylene glycol monoalkyl ethers such as monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; An alkyl lactate such as an ester or ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tertiary butanol, octanol, 2-ethylhexanol, cyclohexanol, etc. (cyclo)alkyl alcohol; keto alcohol such as diacetone alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol single Ethyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxy acetate (poly)alkyl diol monoalkyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether and the like glycol ether; tetrahydrofuran a cyclic ether; a ketone of methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone or the like; Diacetate such as propylene glycol diacetate, 1,3-butanediol diacetate or 1,6-hexanediol diacetate; methyl 3-methoxypropionate, 3-methyl Ethyl oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate, etc. Alkoxycarboxylate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, butyric acid Ethyl ester, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl ethyl acetate, ethyl acetate, 2 - fatty acid alkyl esters such as ethyl acetobutanoate; aromatic hydrocarbons such as toluene and xylene; N,N-dimethylformamide, N,N-dimethylacetamide, N-A A guanamine such as a pyrrolidone or an indoleamine or the like.

Among these organic solvents, solubility, pigment dispersibility, From the viewpoint of coatability and the like, preferred are propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxy group. Butyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butanediol diacetate, 1, 6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3 -methoxybutyl propionate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, butyric acid Butyl ester, ethyl pyruvate, and the like.

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

The content of the organic solvent is not particularly limited, except for coloring The total concentration of each component other than the organic solvent of the composition is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass. By setting it as such a thing, the coloring agent dispersion liquid which is excellent in dispersibility and stability, and the coloring composition which is excellent in applicability 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 fluorine-based surfactant; an organic ruthenium-based surfactant; Surfactant; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, N-(2-aminoethyl)-3-aminopropyl Methyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-epoxypropoxy Propyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyl An adhesion promoter such as dimethoxy decane, 3-chloropropyltrimethoxy decane, 3-methyl propylene oxypropyl trimethoxy decane, 3-mercaptopropyltrimethoxy decane; Antioxidant such as 2-thiobis(4-methyl-6-tertiary butylphenol), 2,6-di-tertiary butylphenol; 2-(3-tert-butyl-5-methyl Ultraviolet absorption of -2-hydroxyphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, etc. a coagulation preventing agent such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, Residue improver of 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, etc.; succinic acid mono[2-(methyl)propenyloxyethyl]ester, o-benzene A developability improving agent such as mono[2-(methyl)acryloxyethyl)dicarboxylate or ω-carboxypolycaprolactone mono(meth)acrylate.

[Coloring cured film and method of forming the same]

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

Hereinafter, for the display element and the solid-state imaging element The colored cured film used in the color filter and a method of forming the same will be described.

As a method of manufacturing a color filter, the first method is as follows. First, on the surface of the substrate, a light shielding layer (black matrix) is formed in such a manner as to divide a portion where the pixels are formed, as needed. Next, on the substrate, for example, a blue liquid composition of the radiation-sensitive coloring composition of the present invention is applied, 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. Thereafter, by post-baking, a pixel array in which a blue pixel pattern (colored cured film) is arranged in a predetermined array is formed.

Next, use each of the radiation sensitivity of green or red In the colored composition, coating, prebaking, exposure, development, and post-baking of each of the radiation-sensitive coloring compositions were carried out in the same manner as described above, and a green pixel array and a red pixel array were sequentially formed on the same substrate. Thereby, an image in which three primary colors of blue, green, and red are arranged on the substrate is obtained. Color filter for the array. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above.

The above black matrix can be made by sputtering using photolithography A metal thin film such as chromium which is formed by vapor deposition or deposition is formed into a desired pattern. However, a radiation-sensitive coloring composition in which a black coloring agent is dispersed may be used, and may be formed in the same manner as in the case of forming the above-described pixel.

As a substrate used when forming a color filter, an example Examples thereof include glass, organic hydrazine, polycarbonate, polyester, aromatic polyamine, polyamidimide, and polyimine.

Further, these substrates may be subjected to an appropriate pretreatment such as drug treatment, plasma treatment, ion plating, sputtering, gas phase reaction method, or vacuum vapor deposition by a decane coupling agent or the like as desired.

When a radiation-sensitive coloring composition is coated on a substrate, A suitable coating method such as a spray method, a roll coating method, a spin coating method, a slit die coating method (slit coating method), or a bar coating method may be employed, but it is particularly preferable to use a spin coating method. Slot die coating method.

The prebaking is usually 70~110 °C, about 1~10 minutes.

The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, in terms of film thickness after drying.

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

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

Further, as the alkali developing solution, for example, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-diazabicyclo-[5.4. An aqueous solution of 0]-7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene.

In the alkali developer, for example, methanol and B may be added in an appropriate amount. A water-soluble organic solvent such as an alcohol, a surfactant, or the like. Further, after alkaline 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 liquid coating (liquid pool) development method, or the like can be used. The developing conditions are preferably 5 to 300 seconds at normal temperature.

Post-baking conditions are usually 10~60 at 180~280°C Minutes or so.

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 manufacturing 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 such as a blue thermosetting coloring composition is ejected into the formed partition walls by an inkjet device, and then prebaked to evaporate the solvent. Next, the coating film is exposed as needed, and then cured by post-baking to form a blue pixel pattern.

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

Moreover, the partition wall not only functions as a shading function, but also serves to make Since the thermosetting coloring compositions of the respective colors discharged into the cells do not have a function of color mixing, the film thickness is thicker than that of the black matrix used in the first method described above. Therefore, the partition wall is usually formed using a black radiation sensitive composition.

The substrate used for forming the color filter and 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 inkjet method is equivalent to the height of the partition wall.

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

The radiation-sensitive coloring composition of the present invention can also be adapted It is used for the formation of any of the color solidified films, the black matrix, the black spacer, and the like used in the color filter described above.

The color filter including the colored cured film of the present invention thus formed has extremely high brightness and color purity, and thus is used in a color liquid crystal display element, a color image pickup element, a color sensor, an organic EL display element, an electronic paper, or the like. Extremely useful. Further, the display element to be described later may have at least one colored cured film formed using the radiation-sensitive coloring composition of the present invention.

[display component]

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

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

A color liquid crystal display element having the colored cured film of the present invention, except for a cold cathode fluorescent tube (CCFL: Cold Cathode Fluorescent) In addition to Lamp, a backlight unit with a white LED as a light source can also be provided. Examples of the white LED include a combination of a red LED, a green LED, and a blue LED, and white LEDs obtained by color mixing; a combination of blue LEDs, red LEDs, and green phosphors, and white color by color mixing. Light white LED; combined blue LED, red illuminating phosphor and green illuminating phosphor, white LED obtained by color mixing; white light obtained by color mixing of blue LED and YAG phosphor White LED; combined blue LED, orange illuminating phosphor and green illuminating phosphor, white LED obtained by color mixing; combined ultraviolet LED, red luminescent phosphor, green luminescent phosphor and blue A light-emitting phosphor, a white LED or the like which obtains white light by color mixing.

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

Further, an organic EL having the colored cured film of the present invention The display element can have a suitable structure, and for example, a structure disclosed in Japanese Laid-Open Patent Publication No. Hei 11-307242 can be cited.

In addition, the electronic paper provided with the colored cured film of the present invention may have a suitable structure, and for example, a structure disclosed in Japanese Laid-Open Patent Publication No. 2007-41169 can be cited.

[Solid image sensor]

The solid-state imaging device of the present invention includes the colored cured film of the present invention. Further, the solid-state image sensor of the present invention can adopt an appropriate structure. For example, in one embodiment, by using the coloring composition of the present invention, a coloring pixel (coloring cured film) is formed on a semiconductor substrate such as a CMOS substrate by the same operation as described above, whereby color separation and color reproduction can be achieved. Solid-state imaging element with excellent performance.

[Examples]

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

<Synthesis of Colorants> (Synthesis Example 1)

A 100 mL three-necked flask equipped with a stir bar and a reflux cooling tube and a thermometer was sufficiently substituted with nitrogen, and 15.0 g of cyclohexanone was charged, and heated to an internal temperature of 80 ± 2 ° C under a nitrogen stream. On the other hand, 4.00 g of the dye monomer (A1) shown below, 0.50 g of the dye monomer (A3) shown below, 6.00 g of methyl methacrylate, and 4.50 g of methyl group were mixed. Acrylic acid, 2.18 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., trade name V-65), 45.0 g as a polymerization initiator The solution prepared by cyclohexanone was kept at an internal temperature of 80 ± 2 ° C, and was dropped by using a pump for 2 hours. After the completion of the dropwise addition, stirring was continued for another hour at the same temperature. Thereafter, the reaction liquid was cooled to room temperature, and added dropwise to a large amount of hexane. The obtained colored solid was dried under reduced pressure at 50 ° C to obtain 13.9 g of polymer (1). The Mw of the obtained polymer (1) was 5,100. The polymer (1) corresponds to the polymer (A1).

Synthesis Example 2~10

In the same manner as in Synthesis Example 1, except that the type and amount of the monomer used in the polymerization were changed as shown in Table 1, the polymers (2) to (10) were obtained. The structures of the coloring monomers (A1) to (A4) are as described above. The polymers (2) to (4) and the polymers (9) to (10) correspond to the polymer (A1). The polymers (5) to (8) are not polymers (A1).

The symbols used in Table 1 are as follows.

MMA: Methyl methacrylate

MA: methacrylic acid

In the table, "p/q" indicates that the number of moles of the compound represented by the formula (1-1) used in the polymerization is p, and the number of moles of the compound represented by the formula (1-2) is set. Mo ratio when q.

Further, the dye monomers (A1) to (A4) were each synthesized by referring to the following publication.

The dye monomer (A1) is synthesized in accordance with Synthesis Example 2 described in paragraphs [0145] to [0146] of JP-A-2013-178478. Equivalent to having A chromophore ethylenically unsaturated monomer.

The dye monomer (A2) was synthesized in accordance with Example 1-1 described in paragraphs [0096] to [0097] of JP-A-2013-173850. It is equivalent to an ethylenically unsaturated monomer having a cyanine chromophore.

The dye monomer (A3) is produced by the production of the dye monomer (A1-1) described in paragraphs [0149] to [0150] of JP-A-2013-210621. It corresponds to an ethylenically unsaturated monomer having a triarylmethane chromophore.

Pigment monomer (A4): "Monomer 1" described in paragraph [0501] of JP-A-2013-028764. It is equivalent to an ethylenically unsaturated monomer having a chromophore.

<Preparation of colorant solution> Preparation Example 1

10 parts by weight of the obtained polymer (1) was dissolved in 90 parts by weight of propylene glycol monomethyl ether to prepare a colorant solution (A-1).

Preparation 2~14

In the preparation example 1, the colorant solutions (A-2) to (A-14) were prepared in the same manner as in Production Example 1, except that the type and amount of the solute and the solvent were changed as shown in Table 2. In Table 2, propylene glycol monomethyl ether is described as "PGME".

<Synthesis of binder resin> Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 100 parts by mass of propylene glycol monomethyl ether acetate was placed and nitrogen substitution was carried out. 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 this temperature for 1 hour. 2-hydroxyethyl acrylate 15 Parts by mass, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid mono(2-propenyloxyethyl) and 2,2' A mixed solution of 6 parts by mass of azobis(2,4-dimethylvaleronitrile), and polymerization was maintained at this temperature for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and further polymerization was carried out for 1 hour to obtain a binder resin solution (solid content concentration: 33% by mass). The obtained binder resin had an Mw of 12,200 and an Mn of 6,500. This binder resin was referred to as "adhesive resin (C1)".

<Preparation and evaluation of coloring composition> [Preparation of coloring composition] Example 1

16.5 parts by mass of the coloring agent solution (A-1) as the coloring agent (A), and 23.3 parts by mass of the binder resin (C1) solution as the (C) binder resin, as the (B) polymerizable compound a mixture of tetraol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) 9.9 parts by mass, 2-benzyl-2 as (D) photopolymerization initiator -dimethylamino-1-(4- 1.8 parts by mass of phenyl phenyl)butan-1-one (trade name: Irgacure 369, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 0.1 parts by mass of NCI-930 (manufactured by ADEKA CORPORATION), and Megafac F as a fluorine-based surfactant 0.05 parts by mass of 554 (manufactured by DIC Corporation) and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a colored composition (S-1) having a solid concentration of 20% by mass.

[Evaluation of contrast]

The obtained coloring composition was applied onto a glass substrate using a spin coater, and then prebaked for 10 minutes on a hot plate at 80 ° C to form a coating film having a film thickness of 2.5 μm.

Next, after the substrate was cooled to room temperature, radiation of each wavelength of 365 nm, 405 nm, and 436 nm was exposed to each coating film at a exposure amount of 2000 J/m ² without using a high-pressure mercury lamp. Thereafter, a developing solution composed of a 0.04% by mass aqueous potassium hydroxide solution at 23 ° C was sprayed onto the substrate at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm) for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and further baked in a clean oven at 200 ° C for 30 minutes to form a cured film for evaluation.

The substrate on which the cured film was formed was sandwiched between two deflecting plates, and irradiated with a fluorescent lamp (wavelength range of 380 to 780 nm) from the back side while rotating the deflecting plate on the front side, using a luminance meter LS-100 (Minolta Co., Ltd.) The maximum and minimum values of the transmitted light intensity are measured. Moreover, the value obtained by dividing the maximum value by the minimum value is taken as the contrast ratio. The evaluation results are shown in Table 3. It should be noted that the contrast ratio is larger as the value is larger.

[Evaluation of heat resistance]

The colored composition (S-1) was applied onto a soda glass substrate having a SiO ₂ film on the surface where eluted sodium ions were formed by a spin coater, and then prebaked for 2 minutes on a hot plate at 90° C. to form a film. A coating film having a thickness of 2.5 μm.

Next, after the substrate was cooled to room temperature, radiation of respective wavelengths of 365 nm, 405 nm, and 436 nm was exposed to each of the coating films with a high pressure mercury lamp through a mask at an exposure amount of 400 J/m ² . Thereafter, a developing solution composed of a 0.04% by mass aqueous potassium hydroxide solution at 23 ° C was sprayed onto the substrates at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm), thereby performing shower development for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and further baked in a clean oven at 200 ° C for 30 minutes to form a dot pattern on the substrate.

The color point analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) was used to measure the chromaticity coordinate value (x, y) and the stimulus value (Y) in the CIE color system using a C light source and a 2 degree field of view. .

Next, the substrate was additionally baked at 230 ° C for 90 minutes, and then the chromaticity coordinate value (x, y) and the stimulating value (Y) were measured, and the color change before and after the additional baking, that is, ΔE ^* ab was evaluated. As a result, the case where the value of ΔE ^* ab was less than 3.0 was evaluated as "○", the case of 3.0 or more and less than 5.0 was evaluated as "Δ", and the case of 5.0 or more was evaluated as "x". The evaluation results are shown in Table 3. Further, it can be said that the smaller the ΔE ^* ab value, the better the heat resistance.

Examples 2 to 6 and Comparative Examples 1 to 6

In the same manner as in Example 1, except that the type and amount of each component were changed as shown in Table 3, the colored compositions (S-2) to (S-12) were prepared. Next, evaluation was performed in the same manner as in Example 1 except that the coloring compositions (S-2) to (S-12) were used instead of the coloring composition (S-1). The results are shown in Table 3.

Claims (6)

A coloring composition comprising (A) a coloring agent and (B) a coloring composition of a polymerizable compound, (A) a coloring agent comprising a polymer having a portion that generates fluorescence and a portion that absorbs the fluorescent light . A colored composition comprising (A) a coloring agent and (B) a coloring composition of a polymerizable compound, (A) a coloring agent comprising a polymer having a polymer selected from the group consisting of At least one chromophore in the chromophore and the cyanine chromophore, and at least one chromophore selected from the group consisting of a triarylmethane chromophore and a chromophore. The colored composition of claim 1 or 2, wherein the polymer comprises At least one chromophore ethylenically unsaturated monomer in the chromophore and the cyanine chromophore, and at least one chromophore having a selected from the group consisting of a triarylmethane chromophore and a chromophore A copolymer of an ethylenically unsaturated monomer as a structural unit of an ethylenically unsaturated monomer. A colored composition according to claim 1 or 2, which further comprises (C) a binder resin. A colored hardening film formed by using the coloring composition according to any one of claims 1 to 4. A display element comprising the colored cured film of claim 5.