WO2012008360A1 - Coloring agent, coloring composition, color filter and display element - Google Patents

Abstract

Provided is a novel coloring agent which has high solubility in an organic solvent and excellent heat resistance and is useful for the formation of a color filter or the like. This coloring agent is represented by formula (1). (In formula (1), D represents a coloring agent base; R represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted divalent alicyclic hydrocarbon group, or a substituted or unsubstituted arylene group; X⁺ represents an organic ammonium ion; and m represents an integer of 1 or more.)

Description

Colorant, coloring composition, color filter and display element

The present invention relates to a colorant, a coloring composition, a color filter, and a display element. More specifically, the present invention relates to a color filter such as a transmissive or reflective color liquid crystal display element, solid-state imaging element, organic EL display element, and electronic paper. The present invention relates to a colorant suitably used for formation, a color composition containing the colorant, a color filter including a color layer containing the colorant, and a display element including the color filter.

In producing a color filter using a colored radiation-sensitive composition, a pigment-dispersed colored radiation-sensitive composition is applied on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape. There is known a method (Patent Documents 1 and 2) in which pixels of each color are obtained by irradiation (hereinafter referred to as “exposure”) and development. A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (Patent Document 3) is also known. Furthermore, a method of obtaining pixels of each color by an ink jet method using a pigment-dispersed colored resin composition is also known (Patent Document 4).

Incidentally, it is known that it is effective to use a dye as a colorant in order to realize a high contrast of a liquid crystal display element and a high definition of a solid-state image sensor. For example, Patent Document 4 proposes the use of a dye in which a sulfonic acid group directly bonded to a dye mother nucleus is in the form of an amine salt or a dye having a sulfonamide group introduced into a dye.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP-A-6-51115

However, as proposed in Patent Document 4, a dye having a sulfonic acid group directly bonded to a dye mother nucleus in the form of an amine salt, or a dye having a sulfonamide group introduced into a dye, Limited to some dye compounds having an aromatic ring such as phthalocyanine. Therefore, there is a strong demand for the development of a new colorant that can realize high contrast in liquid crystal display elements and high definition in solid-state imaging elements.

Therefore, an object of the present invention is to provide a novel colorant that is highly soluble in organic solvents, excellent in heat resistance, and useful for forming color filters and the like. Furthermore, the subject of this invention is providing the color composition containing the said coloring agent, the color filter provided with the colored layer containing the said coloring agent, and the display element which comprises the said color filter.

The present inventors have found that a compound represented by the following formula (1) can solve the above problems.

That is, the present invention provides a colorant represented by the following formula (1) (hereinafter also referred to as “the present colorant”).

[In the formula (1), D represents a colorant matrix, R represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted divalent alicyclic hydrocarbon group, or a substituted Alternatively, it represents an unsubstituted arylene group, X ⁺ represents an organic ammonium ion, and m represents an integer of 1 or more. ]

The present invention also provides a method for producing the present colorant comprising a step of reacting a dye compound having active hydrogen with a compound represented by the following formula (5) in the presence of a base.

[In Formula (5), R is synonymous with the above. ]

Furthermore, the present invention is a coloring composition containing (A) a coloring agent, (B) a binder resin and (C) a crosslinking agent, and (A) a coloring composition containing the above coloring agent as a coloring agent, The present invention provides a color filter comprising a colored layer containing the colorant and a display element comprising the color filter. Here, the “colored layer” means each color pixel, black matrix, black spacer, etc. used in the color filter.

The colorant of the present invention has high solubility in organic solvents and excellent heat resistance. And if the coloring composition containing the coloring agent of this invention is used, the color filter which has each color pixel with a high contrast can be obtained.

Accordingly, the colorant of the present invention includes various color filters including, for example, a color filter for a color liquid crystal display element, a color filter for color separation of a solid-state image sensor, a color filter for an organic EL display element, and a color filter for electronic paper. Can be used very suitably. Further, the colorant of the present invention can be suitably used for an electrophoretic display element. Furthermore, the colorant of the present invention can also be used as a pigment derivative type pigment dispersant.

Hereinafter, the present invention will be described in detail.

This colorant First, the definitions of the symbols in the formula (1).

In R of the above formula (1), the alkylene group may be linear or branched, and examples thereof include an alkylene group having 2 to 20 carbon atoms. Specifically, ethylene group, propylene group, trimethylene group, tetramethylene group, butane-1,3-diyl group, pentamethylene group, pentane-1,3-diyl group, pentane-1,4-diyl group, hexane -1,4-diyl group, hexane-1,5-diyl group, 4,4-dimethylpentane-1,3-diyl group, dodecane-1,4-diyl group and the like. The alkylene group may have a substituent, and examples of the substituent include a halo group, and among them, a fluoro group is preferable.

In R in the above formula (1), the alkenylene group may be linear or branched, and examples thereof include an alkenylene group having 3 to 6 carbon atoms. Specifically, 1-propene-1,3-diyl group, but-1-ene-1,3-diyl group, penta-1-ene-1,3-diyl group, hexa-1-ene-1, 3-diyl group and the like can be mentioned. The alkenylene group may have a substituent, and examples of the substituent include a halo group.

In R of the above formula (1), examples of the divalent alicyclic hydrocarbon group include a bicyclo [2.2.1] heptane-2,6-diyl group. The divalent alicyclic hydrocarbon group may have a substituent, and examples of the substituent include a hydroxyl group.

In R of the above formula (1), examples of the arylene group include a naphthalene-1,8-diyl group. The arylene group may have a substituent, and examples of the substituent include an alkoxy group, a halo group, a nitro group, a cyano group, and a trifluoromethyl group.

In the present invention, R is preferably an alkylene group, a fluorinated alkylene group or an alkenylene group, and more preferably an alkylene group having 2 to 5 carbon atoms, a fluorinated alkylene group having 2 to 5 carbon atoms or an alkenylene group having 3 to 6 carbon atoms. preferable.

D represents a colorant matrix. From the viewpoint of ease of production of the present colorant, D represents —NHCO—, —CONHCO—, —OH, —NH ₂ , —NH—, —COCH ₂ CO—, It is preferably a residue obtained by removing one or more active hydrogens from a dye compound having a group having active hydrogens such as —COOH and —SH.
m can be appropriately selected according to the type of the present colorant as long as it is an integer of 1 or more, but is preferably an integer of 1 to 6 from the viewpoint of ease of production of the present colorant. An integer of 4 is more preferable.
Examples of the dye compound having a group having active hydrogen include a compound represented by the following formula (6), a compound represented by the following formula (7), a compound represented by the following formula (8), and the following compound: Mention may be made of the compounds shown in groups ak.

[In the formulas (6) and (7), R ¹ to R ⁴ each independently represent a hydrogen atom, a halo group, an alkyl group, an alkoxy group, an alkyl-substituted amino group, a trifluoromethyl group, or a nitro group. ]

In the above formula (6), R ¹ to R ² each independently represent a hydrogen atom, a halo group, an alkyl group, an alkoxy group, an alkyl-substituted amino group, a trifluoromethyl group, or a nitro group. , A hydrogen atom and an alkyl group are preferable, and a hydrogen atom is particularly preferable.
In the above formula (7), R ³ to R ⁴ each independently represent a hydrogen atom, a halo group, an alkyl group, an alkoxy group, an alkyl-substituted amino group, a trifluoromethyl group or a nitro group. Of these, a halo group is preferred. Examples of the halo group include fluorine, chlorine, bromine and iodine. Among them, chlorine is preferable.
The number of carbon atoms of the alkyl group constituting R ¹ to R ^{4 and} the alkyl group constituting the alkyl-substituted amino group is preferably 1-20, and more preferably 1-12. The alkyl-substituted amino group may be mono-substituted or di-substituted. The number of carbon atoms of the alkoxy group in R ¹ to R ⁴ is preferably 1 to 8, and more preferably 1 to 4. The alkyl group and alkoxy group may be linear or branched.

In the present invention, D is a residue obtained by removing one or more active hydrogens from a dye compound having —NHCO—, —CONHCO—, particularly —NHCO—, from the viewpoint of solubility in organic solvents and heat resistance. It is preferable. That is, as this coloring agent, what has a structure represented by following formula (4) is preferable.

[In Formula (4), R and X ⁺ are synonymous with R and X ⁺ in Formula (1) above, and “*” indicates a bond. ]

X ⁺ is not particularly limited as long as it is an organic ammonium ion, but is preferably represented by the following formula (2) or the following formula (3) from the viewpoint of solubility in an organic solvent and heat resistance.

[In the formulas (2) and (3), Q ¹ to Q ⁵ each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a phenacyl group or a heterocyclic group, and Q ⁶ represents a hydrogen atom An atom, a halo group, a substituted or unsubstituted hydrocarbon group, an alkoxycarbonyl group, a carbamoyl group, or a benzyloxy group is shown. However, at least one of Q ¹ to Q ⁴ represents a substituted or unsubstituted hydrocarbon group. ]

In Q ¹ to Q ⁶ , the hydrocarbon group includes, for example, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon Examples thereof include an aralkyl group of 7 to 20. Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an alkynyl group having 2 to 20 carbon atoms. Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cycloalkyl group having 3 to 8 carbon atoms and a cycloalkenyl group having 3 to 8 carbon atoms. The alkyl group, alkenyl group and alkynyl group may be linear or branched, and the alkenyl group and alkynyl group may have an unsaturated bond in the molecule or at the terminal. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenylene group. Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, phenethyl group, trityl group, alkylene (preferably C _1-6 alkylene) -phenylene-alkylene (preferably C _1-6 alkylene) group, alkylene (preferably C _{And 1-6} alkylene) -biphenylene-alkylene (preferably C _1-6 alkylene) group. Here, “C _1-6 ” in the present specification means having 1 to 6 carbon atoms.

These hydrocarbon groups may have a substituent. Examples of the substituent include a hydroxyl group, an alkoxy group, a halo group, a nitro group, a cyano group, an amide group, a sulfonic acid group, and an alkyl (preferably C _1-6 alkyl) -carbonyl group, aryl (preferably C _6-14 aryl) -carbonyl group and the like can be mentioned. In addition, the position and number of these substituents are arbitrary, and when they have two or more substituents, the substituents may be the same or different. Here, “C _6-14 ” in this specification means that the number of carbon atoms is _6-14 .

In Q ¹ to Q ⁵ , the heterocyclic group is a monocycle formed by combining a carbon atom and at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom (preferably 3 to And groups derived from an 8-membered ring, more preferably a 5- to 6-membered ring. Specific examples include alicyclic heterocyclic groups such as pyrrolidinyl group, imidazolidinyl group, pyrazolidinyl group, piperidyl group, piperidino group, piperazinyl group, homopyrerazinyl group, morpholinyl group, theomorpholinyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl Group, quinolyl group, isoquinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, thienyl group, furyl group, pyranyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazoyl group, tetrazolyl group, thiazolyl group, oxazolyl group, indolyl group, Aromatic heterocyclic groups such as indazolyl group, benzoimidazolyl group, and purinyl group can be exemplified.

Among these, as Q ¹ to Q ⁵ , a hydrogen atom or a substituted or unsubstituted hydrocarbon group is preferable. As the hydrocarbon group, an aliphatic hydrocarbon group having 1 to 20 carbon atoms and an alicyclic hydrocarbon group having 3 to 20 carbon atoms are preferable, an alkyl group having 1 to 20 carbon atoms, and a cyclohexane having 3 to 8 carbon atoms. An alkyl group is more preferable, and an alkyl group having 1 to 20 carbon atoms is particularly preferable. Note that at least one of Q ¹ to Q ⁴ represents a substituted or unsubstituted hydrocarbon group, and examples of the hydrocarbon group include aliphatic hydrocarbon groups having 1 to 20 carbon atoms, and 3 to 20 carbon atoms. The alicyclic hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 20 carbon atoms.

In Q ⁶ , alkoxy in the alkoxycarbonyl group may be linear or branched, but preferably has 1 to 6 carbon atoms.
Among these, Q ⁶ is preferably a hydrogen atom or a substituted or unsubstituted hydrocarbon group, particularly preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Of these, X ⁺ represented by the above formula (2) is preferably a mono-, di-, tri- or tetraalkylammonium ion, particularly preferably a tetraalkylammonium ion. Specifically, tetraethyl ammonium ion, tetrabutyl ammonium ion, dimethyl (dioctadecyl) ammonium ion, tetrahexyl ammonium ion, tributyl (methyl) ammonium ion, tetradodecyl ammonium ion, tetraoctyl ammonium ion, trimethyl (hexadecyl) ammonium ion , Trioctyl (methyl) ammonium ion, tetraisopentyl ammonium ion and the like.
X ⁺ represented by the above formula (3) includes, for example, pyridinium ion, alkyl-substituted pyridinium ion, 1-alkylpyridinium ion, 1-alkyl-halo-substituted pyridinium ion, 1-alkyl-alkoxycarbonyl-substituted pyridinium ion, Examples thereof include 1-phenacylpyridinium ion, 1-alkyl-carbamoyl-substituted pyridinium ion, and 1-alkyl-benzyloxy-substituted pyridinium ion. Specifically, 2,4,6-trimethylpyridinium ion, 1-methylpyridinium ion, 1-dodecylpyridinium ion, 1-butyl-3-methylpyridinium ion, 2-bromo-1-ethylpyridinium ion, 1-ethyl -3- (hydroxymethyl) pyridinium ion, 1-ethyl-4- (methoxycarbonyl) pyridinium ion, 4-carbamoyl-1-hexadecylpyridinium ion, 2-benzyloxy-1-methylpyridinium ion, etc. .

Preferred specific examples of the compound represented by the above formula (1) are shown in the following compound groups 1 to p, but are not limited thereto.

The colorant includes, for example, a step of reacting a dye compound having active hydrogen with a compound represented by the following formula (5) in the presence of a base (hereinafter also referred to as “step 1”), and the resulting dye. The compound can be produced by subjecting the sulfonate salt of the compound to a salt exchange reaction with an organic quaternary ammonium salt (hereinafter also referred to as “step 2”).

[In Formula (5), R is synonymous with the above. ]

The dye compound having active hydrogen used in Step 1 may be synthesized by a known method or may be a commercially available product. As a commercially available product, for example, in the compound represented by the above formula (6), Z is an ethoxy group and R ¹ and R ² are hydrogen atoms (CI Pigment Violet 37), and the above formula ( The compound represented by 7) wherein R ³ and R ⁴ are chlorine atoms (CI Pigment Red 254) can be obtained from Ciba Specialty Chemicals.

Examples of the base used in Step 1 include potassium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, sodium methylate, potassium t-butoxide, triethylamine, DBU, sodium hydride and the like. .

In the above formula (5), R is preferably an alkylene group, a fluorinated alkylene group or an alkenylene group. Examples of such a compound include compounds represented by the following formula (5-1). .

[In the formula (5-1), R ^a represents ^a methylene group or alkylene group which may have ^a halo group, or an alkenylene group, and R ^b represents a hydrogen atom or an alkyl group which may have a halo group. Or a halo group, and R ^c represents a hydrogen atom or a halo group. ]

The alkylene group preferably has a carbon number of 2-4 in the R ^a, alkenylene group in R ^a is preferably from 2 carbon atoms, the alkyl group in R ^b is preferably having a carbon number of 1-3. The total carbon number of R ^a and R ^b is preferably 1 to 5.

Specific examples of the compound represented by the above formula (5) include 1,2-ethane sultone, 1,3-propane sultone, 1,4-butane sultone, 2,4-butane sultone, 1,5-pentane sultone, , 5-pentane sultone, 3,5-pentane sultone, 3,6-hexane sultone, 2,6-hexane sultone, 2,2-dimethyl-3,5-pentane sultone, 9,12-dodecane sultone, 1,3 -Propene sultone, perfluoro-1,2-ethane sultone, perfluoro-2,3-propane sultone, perfluoro-3,4-butane sultone, 1,8-naphtho sultone, 5-hydroxy-2,6-bicyclo [2. 2.1] heptane sultone (5-hydroxy-3-oxa-2-Chiatorishikuro [4.2.1.0 ^{4, 8]} nonane-2,2-Geo ), And the like.

The compound represented by the above formula (5) can be produced by a known method, for example, a method described in JP-A-5-43572, JP-A-2007-31355, etc. May be used.

Step 1 is preferably performed in a solvent. Examples of the solvent include amides such as N, N-dimethylformamide and N, N-dimethylacetamide, pyrrolidones such as N-methylpyrrolidone, N, N Examples thereof include imidazolidinone such as' -dimethylimidazolidinone, nitrile such as acetonitrile, and ether such as tetrahydrofuran.

The reaction temperature is, for example, 20 to 150 ° C., and the reaction time is, for example, 30 minutes to 48 hours.

Examples of the organic quaternary ammonium salt used in Step 2 include tetraethylammonium halide, tetrabutylammonium halide, dimethyl (dioctadecyl) ammonium halide, tetrahexylammonium halide, tributyl (methyl) ammonium halide, tetradodecylammonium halide, tetra Octyl ammonium halide, trimethyl (hexadecyl) ammonium halide, trioctyl (methyl) ammonium halide, tetraisopentyl ammonium halide, 1-butyl-3-methylpyridinium halide, 1-butyl-4-methylpyridinium halide, 1-butylpyridinium halide, 1-dodecylpyridinium halide, 1-ethyl-3- (hydroxymethyl) pyridinium ethylsulfate 1-ethyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-ethylpyridinium halide, 1-methylpyridinium halide, 1-phenacylpyridinium halide, 1-propylpyridinium halide, 1-ethyl-4- ( Methoxycarbonyl) pyridinium halide, 2,4,6-trimethylpyridinium p-toluenesulfonate, 2,6-dimethylpyridinium p-toluenesulfonate, 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1- Methylpyridinium halide, 2-fluoro-1-methylpyridinium p-toluenesulfonate, 2- (chloromethyl) pyridine hydrohalide, 3- (chloromethyl) pyridine hydrohalide, 4- (chloromethyl) ) Hydrogen halide salt of pyridine, 3-carbamyl-1-methylpyridinium halide, 4-carbamoyl-1-hexadecylpyridinium halide, 2-benzyloxy-1-methylpyridinium trifluoromethanesulfonate, and the like.

The above step 2 is also preferably carried out in a solvent. Examples of the solvent include amides such as N, N-dimethylformamide and N, N-dimethylacetamide, pyrrolidones such as N-methylpyrrolidone, N, N′— Examples thereof include imidazolidinone such as dimethylimidazolidinone, nitrile such as acetonitrile, ether such as tetrahydrofuran, alcohol such as methanol and ethanol, and ketone such as acetone. These solvents may be used alone or in admixture of two or more.

The reaction temperature is, for example, 20 to 70 ° C., and the reaction time is, for example, 30 minutes to 12 hours.

After completion of Step 1 or Step 2, if necessary, the reaction system can be used by appropriately combining ordinary purification means such as filtration, washing, drying, concentration, reprecipitation, centrifugation, extraction with various solvents, and chromatography. The compound can be isolated. In addition, after completion | finish of the process 1, you may use for a process 2 without isolating a target compound.
Starting from Step 1, a compound in which a sulfonic acid group is introduced into the dye compound via an alkylene group or a compound in which a sulfonimide group is introduced into the dye compound via an alkylene group can also be produced. The compound thus obtained can also be used as a colorant.

The colorant thus obtained is soluble in various organic solvents such as ketones such as cyclohexanone as shown in Examples below, and has a 5% mass reduction temperature in TG-DTA analysis. Can have excellent heat resistance of 300 ° C. or higher.

Hereinafter, the components of the colored composition of the present invention (hereinafter also simply referred to as “colored composition”) will be described.

-(A) Colorant-
The coloring composition of this invention contains this coloring agent as (A) coloring agent. This coloring agent can be used individually or in mixture of 2 or more types.
In the present invention, a colorant other than the present colorant can also be contained as the colorant (A). Such a colorant is not particularly limited as long as it has colorability, and colors and materials can be appropriately selected according to the use of the color filter. Specifically, as the colorant other than the present pigment, any of pigments, dyes and natural pigments can be used. However, since color filters are required to have high color purity, brightness, contrast, etc., A dye is preferred.

The pigment may be either an organic pigment or an inorganic pigment, and examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyer's and Colorists). . Specific examples include those with the following color index (CI) names.

C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 211;

C. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 68, C.I. I. Pigment orange 70, C.I. I. Pigment orange 71, C.I. I. Pigment orange 72, C.I. I. Pigment orange 73, C.I. I. Pigment orange 74;

C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 264, C.I. I. Pigment red 272;

C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;
C. I. Pigment blue 1, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Pigment blue 80;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58;
C. I. Pigment brown 23, C.I. I. Pigment brown 25;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

Examples of the inorganic pigment include, for example, titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine blue, bitumen, and chromium oxide. Examples include green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

In the present invention, the pigment may be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Moreover, the pigment surface may be used by modifying the particle surface with a resin if desired. Examples of the resin that modifies the pigment particle surface include a vehicle resin described in JP-A No. 2001-108817, or various commercially available resins for dispersing pigments. As a resin coating method on the carbon black surface, for example, methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969, and the like can be employed. The organic pigment is preferably used by refining primary particles by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be employed.

In addition, the dye can be appropriately selected from various oil-soluble dyes, direct dyes, acid dyes, metal complex dyes, and the like. For example, the following color index (CI) names are attached. Can be mentioned.

C. I. Solvent Yellow 4, C.I. I. Solvent Yellow 14, C.I. I. Solvent Yellow 15, C.I. I. Solvent Yellow 24, C.I. I. Solvent Yellow 82, C.I. I. Solvent Yellow 88, C.I. I. Solvent Yellow 94, C.I. I. Solvent Yellow 98, C.I. I. Solvent Yellow 162, C.I. I. Solvent yellow 179;
C. I. Solvent Red 45, C.I. I. Solvent red 49;
C. I. Solvent Orange 2, C.I. I. Solvent Orange 7, C.I. I. Solvent Orange 11, C.I. I. Solvent Orange 15, C.I. I. Solvent Orange 26, C.I. I. Solvent orange 56;
C. I. Solvent Blue 35, C.I. I. Solvent Blue 37, C.I. I. Solvent Blue 59, C.I. I. Solvent blue 67;

C. I. Acid Yellow 17, C.I. I. Acid Yellow 29, C.I. I. Acid Yellow 40, C.I. I. Acid Yellow 76;
C. I. Acid Red 91, C.I. I. Acid Red 92, C.I. I. Acid Red 97, C.I. I. Acid Red 114, C.I. I. Acid Red 138, C.I. I. Acid Red 151;
C. I. Acid Orange 51, C.I. I. Acid Orange 63;
C. I. Acid Blue 80, C.I. I. Acid Blue 83, C.I. I. Acid Blue 90;
C. I. Acid Green 9, C.I. I. Acid Green 16, C.I. I. Acid Green 25, C.I. I. Acid Green 27.

In the present invention, other colorants can be used alone or in admixture of two or more.

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

In the present invention, when a pigment is used as another colorant, it can be used together with a dispersant and a dispersion aid as desired. As the dispersing agent, for example, an appropriate dispersing agent such as a cationic type, an anionic type, or a nonionic type can be used, and a polymer dispersing agent is preferable. Specifically, urethane dispersant, polyethyleneimine dispersant, polyoxyethylene alkyl ether dispersant, polyoxyethylene alkylphenyl ether dispersant, polyethylene glycol diester dispersant, sorbitan fatty acid ester dispersant, polyester Examples thereof include an acrylic dispersant and an acrylic dispersant.

Such dispersants are commercially available. For example, acrylic dispersants such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK Corporation (BYK) And the like as urethane dispersants such as Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (Lubrisol) Etc.) as a polyethyleneimine-based dispersant, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), etc. as a polyester-based dispersant. B821, Adisper PB822, Adisper PB880, the Ajisper PB881 (Ajinomoto Fine-Techno Co., Ltd.), and the like, can be mentioned, respectively.
Examples of the dispersion aid include pigment derivatives, and specific examples include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone. The contents of the dispersant and the dispersion aid can be appropriately determined within a range that does not impair the object of the present invention.

-(B) Binder resin-
The coloring composition of the present invention contains (B) a binder resin. Thereby, alkali developability and the binding property to a board | substrate can be improved to a coloring composition. Such a binder resin is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). (B1) ") and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as" unsaturated monomer (b2) ").

Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meta ) Acrylate, p-vinylbenzoic acid and the like.
These unsaturated monomers (b1) can be used alone or in admixture of two or more.

Moreover, as said unsaturated monomer (b2), for example,
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2 To 10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) ) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate Glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[( (Meth) acrylic acid esters such as (meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane.
These unsaturated monomers (b2) can be used alone or in admixture of two or more.

In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50% by mass. More preferably, it is 10 to 40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. No. 10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Coalescence can be mentioned.

In the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-09-325494, JP-A-11-140144, As disclosed in Kaikai 2008-181095 and the like, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as a binder resin.

The binder resin in the present invention has a polystyrene-equivalent weight average molecular weight (hereinafter also referred to as “Mw”) measured by GPC (elution solvent: tetrahydrofuran), usually 1,000 to 100,000, preferably 3,000. ~ 50,000. If Mw is too small, the remaining film rate of the resulting film may be reduced, pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. On the other hand, if Mw is too large, resolution may be reduced. In addition, the pattern shape may be damaged, and dry foreign matter may be easily generated during application by the slit nozzle method.

The ratio (Mw / Mn) between the Mw of the binder resin in the present invention and the number average molecular weight in terms of polystyrene (hereinafter also referred to as “Mn”) measured by GPC (elution solvent: tetrahydrofuran) is preferably 1. 0.0 to 5.0, more preferably 1.0 to 3.0.

The binder resin in the present invention can be produced by a known method. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.

In the present invention, the binder resins can be used alone or in admixture of two or more.

In the present invention, the content of the binder resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass with respect to 100 parts by mass of the (A) colorant. If the content of the binder resin is too small, for example, the alkali developability may be decreased, or the storage stability of the resulting colored composition may be decreased. On the other hand, if the content is too large, the colorant concentration is relatively high. Therefore, it may be difficult to achieve the target color density as a thin film.

-(C) Crosslinking agent-
In the present invention, (C) a crosslinking agent refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the (C) crosslinking agent is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups.

Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, a caprolactone-modified polyfunctional ( (Meth) acrylate, alkylene oxide-modified polyfunctional (meth) acrylate, hydroxyl-functional (meth) acrylate and polyfunctional isocyanate obtained by reacting with polyfunctional isocyanate, hydroxyl-functional (meth) acrylate and acid The polyfunctional (meth) acrylate which has a carboxyl group obtained by making an anhydride react can be mentioned.

Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of trivalent or higher aliphatic polyhydroxy compounds. Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol diester. A methacrylate etc. can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

Examples of the caprolactone-modified polyfunctional (meth) acrylate include the compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include ethylene oxide of bisphenol A and / or propylene oxide modified di (meth) acrylate, ethylene oxide of isocyanuric acid and / or propylene oxide modified tri (meth) acrylate, tri Ethylene oxide and / or propylene oxide modified tri (meth) acrylate of methylolpropane, ethylene oxide and / or propylene oxide modified tri (meth) acrylate of pentaerythritol, ethylene oxide and / or propylene oxide modified tetra (meth) acrylate of pentaerythritol Dipentaerythritol ethylene oxide and / or propylene oxide modified penta (meth) acrylate, di It can be mentioned pointer ethylene oxide erythritol and / or propylene oxide-modified hexa (meth) acrylate.

Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and is a concept including melamine, benzoguanamine or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′, N Examples include '-tetra (alkoxymethyl) benzoguanamine, N, N, N', N'-tetra (alkoxymethyl) glycoluril and the like.

Of these polyfunctional monomers, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, polyfunctional (meth) acrylates modified with caprolactone, Polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′, N '-Tetra (alkoxymethyl) benzoguanamine is preferred. Among polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Erythritol hexaacrylate is a compound obtained by reacting pentaerythritol triacrylate and succinic anhydride, among polyfunctional (meth) acrylates having a carboxyl group, and obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride. The compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and background stains and film residues are hardly generated on the unexposed substrate and the light shielding layer.

In the present invention, (C) the crosslinking agent can be used alone or in admixture of two or more.

In the present invention, the content of the (C) crosslinking agent is preferably 10 to 1,000 parts by mass, particularly preferably 20 to 500 parts by mass, with respect to 100 parts by mass of the (A) colorant. In this case, if the content of the polyfunctional monomer is too small, sufficient curability may not be obtained. On the other hand, if the content of the polyfunctional monomer is too large, when the color composition of the present invention is imparted with alkali developability, the alkali developability is lowered, and on the unexposed portion of the substrate or the light shielding layer. There is a tendency that dirt, film residue, etc. are likely to occur.

-(D) Photopolymerization initiator-
The coloring composition of the present invention can contain (D) a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. The (D) photopolymerization initiator used in the present invention generates an active species capable of initiating the polymerization of the above (C) crosslinking agent by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. A compound.

Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -Diketone compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds and the like.

In the present invention, the photopolymerization initiators can be used alone or in admixture of two or more. The photopolymerization initiator is preferably at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds.

Among preferred photopolymerization initiators in the present invention, specific examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.

Specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′. -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4, 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and the like can be mentioned.

In addition, when a biimidazole compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor in terms of improving sensitivity. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like. And an amine-based hydrogen donor. In the present invention, hydrogen donors can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the sensitivity can be further improved.

Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(5-Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine compounds having a halomethyl group, such as toxistyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

Specific examples of the O-acyloxime compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3) -Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

In the present invention, when using a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound, a sensitizer can be used in combination. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass, with respect to 100 parts by mass of the (C) cross-linking agent. In this case, if the content of the photopolymerization initiator is too small, curing by exposure may be insufficient. On the other hand, if the content is too large, the formed colored layer tends to be detached from the substrate during development.

-(E) Solvent-
The colored composition of the present invention contains the above components (A) to (C) and other components optionally added, but is usually prepared as a liquid composition by blending a solvent.
As the solvent, as long as the components (A) to (C) and other components constituting the colored composition are dispersed or dissolved and do not react with these components and have appropriate volatility, the solvent is appropriately used. You can choose to use.

As such a solvent, 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 mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol;
Keto alcohols such as diacetone alcohol;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate;
Alkoxycarboxylic esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate ;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyric acid Other esters such as -propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether from the viewpoint of solubility, pigment dispersibility, coatability, etc. , Cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl acetate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate Ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.
In this invention, a solvent can be used individually or in mixture of 2 or more types.

The content of the solvent is not particularly limited, but the total concentration of each component excluding the solvent of the colored composition is 5 to 50 from the viewpoint of the coating property and stability of the obtained colored composition. An amount of mass% is preferable, and an amount of 10 to 40 mass% is particularly preferable.

-Additive-
The coloring composition of this invention can also contain a various additive as needed.

Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicon surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropro Adhesion promoters such as rutrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- Antioxidants such as t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation such as sodium polyacrylate Inhibitors: 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, 2-amino-1,3-propanediol, 4-amino-1,2-butane Such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. Examples include developability improvers.

Color filter and production method thereof The color filter of the present invention comprises a colored layer containing the present colorant.

As a method for producing a color filter, first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, for example, after applying a liquid composition of the radiation-sensitive composition of the present invention in which a red colorant is dispersed on the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which red pixel patterns are arranged in a predetermined arrangement.

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

A black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithography method. Using the radiation-sensitive composition, it can be formed in the same manner as in the case of forming the pixel.

Examples of the substrate used when forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.

In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

When the colored radiation-sensitive composition is applied to the substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, or a bar coating method may be employed. In particular, it is preferable to employ a spin coating method or a slit die coating method.

Pre-baking is usually performed by a combination of vacuum drying and heat drying. The drying under reduced pressure is usually performed until reaching 50 to 200 Pa. The conditions for heat drying are usually about 70 to 110 ° C. and about 1 to 10 minutes.

The coating thickness is usually 0.6 to 8.0 μm, preferably 1.2 to 5.0 μm, as the film thickness after drying.

Examples of radiation light sources used in forming pixels and / or black matrices include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, and low pressure mercury lamps. Examples of the light source include a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. Radiation having a wavelength in the range of 190 to 450 nm is preferable.
In general, the exposure dose of radiation is preferably 10 to 10,000 J / m ² .

Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, An aqueous solution of 5-diazabicyclo- [4.3.0] -5-nonene or the like is preferable.

An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.

As the development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

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

The film thickness of the pixel thus formed is usually 0.5 to 5.0 μm, preferably 1.0 to 3.0 μm.

Further, as a second method for producing a color filter, a method for obtaining pixels of each color by an ink jet method disclosed in Japanese Patent Laid-Open Nos. 7-318723 and 2000-310706 can be employed. . In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, after the liquid composition of the colored composition of the present invention in which, for example, a red colorant is dispersed in the formed partition wall is discharged by an ink jet apparatus, pre-baking is performed to evaporate the solvent. Next, this coating film is exposed as necessary and then cured by post-baking to form a red pixel pattern.

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

In addition, the partition has not only a light shielding function but also a function for preventing the color composition of each color discharged in the section from being mixed, so that the film is a film compared to the black matrix used in the first method described above. Thick. Therefore, a partition is normally formed using a black radiation sensitive composition.

The substrate used for forming the color filter, the light source for radiation, and the pre-baking and post-baking methods and conditions are the same as those in the first method described above. In this way, the film thickness of the pixel formed by the ink jet method is approximately the same as the height of the partition wall.

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

Since the color filter of the present invention thus obtained has extremely high luminance and color purity, it is extremely useful for color liquid crystal display elements, color imaging tube elements, color sensors, organic EL display elements, electronic paper, and the like.

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

The color liquid crystal display device having the color filter of the present invention can have an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. Further, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (indium oxide doped with tin) electrode is formed are a liquid crystal layer. It is also possible to adopt a structure that is opposed to each other. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained.

The color liquid crystal display device including the color filter of the present invention can include a cold cathode fluorescent tube (CCFL: Cold Cathode Fluorescent Lamp) and a backlight unit using a white LED as a light source. As the white LED, for example, a white LED that obtains white light by mixing red LED, green LED, and blue LED, a white LED that obtains white light by mixing blue LED, red LED, and green light emitting phosphor, blue A white LED that obtains white light by mixing colors, a white LED that obtains white light by mixing colors of a blue LED and YAG phosphor, a blue LED, an orange light emitting phosphor, and green light emission A white LED that obtains white light by color mixing by combining phosphors, a white LED that obtains white light by color mixing by combining an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor can be exemplified.

The color liquid crystal display device having the color filter of the present invention includes a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, an IPS (In-Planes Switching) type, a VA (Vertical Alignment) type, and an OCB (Optic Optical An appropriate liquid crystal mode such as a birefringence type can be applied.

Also, the organic EL display device having the color filter of the present invention can have an appropriate structure, for example, the structure disclosed in Japanese Patent Application Laid-Open No. 11-307242.

In addition, the electronic paper including the color filter of the present invention can have an appropriate structure, for example, the structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169.

Hereinafter, the embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

<Synthesis and Evaluation of the Colorant>
Example 1 (Synthesis and evaluation of compound (ix) described in the above specific example)
Sodium hydride 0.3 g, C.I. I. 1.63 g of Pigment Violet 37 (hereinafter referred to as “PV-37”) and 20 mL of dimethylformamide were mixed and stirred at room temperature for 2 hours, and further 1.45 g of 1,4-butane sultone was added and stirred for 12 hours. Thereafter, the reaction solution was filtered through Celite, and the filtrate was reprecipitated with 300 mL of acetone. The obtained solid was washed with acetone to obtain 1.5 g of a blue solid.

1.5 g of the obtained blue solid, 5 g of dimethyldioctadecyl ammonium chloride and 30 mL of acetone were mixed and stirred for 6 hours while heating under reflux. Thereafter, the reaction solution was filtered through Celite, and the solvent was removed under reduced pressure to obtain 1.5 g of a purple solid. This is designated Compound A. The compound A was confirmed to be the target compound by ¹ H-NMR (solvent: deuterated chloroform) measurement.

¹ H-NMR: δ 7.95-7.32 (m, 10H), 6.98 (S, 2H), 6.56 (S, 2H), 3.97 (t, 4H), 3.41 (t 8H), 3.30-3.10 (m, 48H), 1.98-1.02 (m, 288H)

Compound A was dissolved in 1-methoxy-2-propyl acetate to prepare a solution having a concentration of about 0.0010% by mass, and an absorption spectrum was measured. As a result, λmax = 545 nm and ε = 60000 mol ⁻¹ cm ⁻¹ L.
Compound A was dissolved in cyclohexanone by 10% by mass or more.
Further, as a result of thermogravimetric-differential thermal simultaneous measurement analysis of Compound A (hereinafter referred to as “TG-DTA”), the 5% mass reduction temperature was 315 ° C.

Example 2
In Example 1, C.I. I. A colorant was synthesized in the same manner as in Example 1 except that CI Pigment Red 254 (a compound in which both R ³ and R ⁴ in the above formula (7) are chlorine atoms) was used, and ¹ H-NMR (solvent: Deuterated chloroform) was confirmed to be the target compound.

Example 3
In Example 1, C.I. I. In place of Pigment Violet 37, C.I. I. Pigment Yellow 128 (compound represented by the following formula), 1-ethyl-pyridinium chloride in place of dimethyl dioctadecyl ammonium chloride, except for using each color are synthesized in the same manner as in Example 1, ¹ H It was confirmed by NMR (solvent: deuterated chloroform) that the compound was the objective compound.

The colorants obtained in Examples 2 to 3 were all dissolved in cyclohexanone by 10% by mass or more. Further, the 5% mass reduction temperature based on TG-DTA of the colorants obtained in Examples 2 to 3 was 250 ° C. or more.

Comparative Example 1
PV-37 was dissolved in 1-methoxy-2-propyl acetate to prepare a solution having a concentration of about 0.0010% by mass, and an absorption spectrum was measured. As a result, it was ε = 600 mol ⁻¹ cm ⁻¹ L at 562 nm.
Further, PV-37 did not dissolve even at 0.1% by mass in either 1-methoxy-2-propyl acetate or cyclohexanone.

<Preparation of pigment dispersion>
Preparation Example 1
As a coloring agent, C.I. I. 15 parts by weight of Pigment Blue 15: 6, 12.5 parts by weight of BYK-LPN21116 (produced by BYK) as a dispersant (solid content concentration = 40% by weight), 72.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent The pigment dispersion (A-1) was prepared by processing with a bead mill.

Preparation Example 2
As a coloring agent, C.I. I. Pigment Blue 15: 6 instead of C.I. I. A pigment dispersion (A-2) was prepared in the same manner as in Preparation Example 1, except that CI Pigment Violet 23 was used.

<Preparation of dye solution>
Preparation Example 3
A dye solution A was prepared by mixing 5 parts by mass of Compound A as a colorant and 95 parts by mass of propylene glycol monomethyl ether acetate as a solvent.

<Synthesis of binder resin>
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heated to 80 ° C., at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 2-ethylhexyl methacrylate 23 parts by mass, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid mono (2-acryloyloxyethyl) and 6 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) The solution was added dropwise over a period of time and polymerized for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C. and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration = 33% by mass). The obtained binder resin was Mw = 12,200 and Mn = 6,500. This binder resin is referred to as “binder resin (B1)”.

<Preparation and evaluation of coloring composition>
Example 4
13.6 parts by mass of pigment dispersion (A-1), 27.2 parts by mass of dye solution A, 16.1 parts by mass of binder resin (B1) solution as a binder resin, and M-402 manufactured by Toagosei Co., Ltd. as a crosslinking agent (Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 5.5 parts by mass and MW-30 (N, N, N ′, N ′, N ″, N ″ -hexa (methoxy) manufactured by Sanwa Chemical Co., Ltd. Methyl) melamine as a main component, weight average degree of polymerization 1.3) 2.4 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one as a photopolymerization initiator ( Ciba Specialty Chemicals, trade name IRGACURE 369) 2.2 parts by mass, and propylene glycol monomethyl ether acetate as a solvent Combined with a solid content concentration of 20 mass% of the coloring composition (CR1) was prepared.

The coloring composition (CR1) was applied on a glass substrate using a spin coater, and then pre-baked on an 80 ° C. hot plate for 10 minutes to form a coating film. Three coating films having different film thicknesses were formed by the same operation while changing the rotation speed of the spin coater.
Next, after cooling these substrates to room temperature, a high-pressure mercury lamp is used, and a radiation containing each wavelength of 365 nm, 405 nm, and 436 nm is applied to each coating film without using a photomask at an exposure dose of 2,000 J / m ² . And exposed. Then, shower development was performed for 90 seconds on these substrates by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230 ° C. for 30 minutes to form a cured film for evaluation.

The substrate on which the cured film is formed is sandwiched between two deflection plates, and the front side deflection plate is rotated while irradiating with a fluorescent lamp (wavelength range: 380 to 780 nm) from the rear side to obtain a luminance meter LS-100 (Minolta Co. The maximum value and the minimum value of the light intensity transmitted through (made by)) were measured. And about each cured film, the value which remove | divided the maximum value by the minimum value was made into the contrast ratio. From the measurement result, the contrast ratio at the chromaticity coordinate value y = 0.080 was obtained. The evaluation results are shown in Table 1.

Comparative Example 2
18.1 parts by mass of the pigment dispersion (A-1), 4.5 parts by mass of the pigment dispersion (A-2), 16.1 parts by mass of the binder resin (B1) solution as the binder resin, and Toagosei Co., Ltd. as the crosslinking agent 5.5 parts by mass of M-402 and 2.4 parts by mass of MW-30 manufactured by Sanwa Chemical Co., Ltd., 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) as a photopolymerization initiator Butane-1-one (trade name: IRGACURE 369, manufactured by Ciba Specialty Chemicals Co., Ltd.) 2.2 parts by mass and propylene glycol monomethyl ether acetate as a solvent are mixed to form a colored composition (CR2 ) Was prepared.

Evaluation was performed in the same manner as in Example 4 except that the colored composition (CR2) was used instead of the colored composition (CR1). The evaluation results are shown in Table 1.

In Table 1, “B15: 6” means C.I. I. Pigment Blue 15: 6, “V23” means C.I. I. Each means pigment violet 23;

Claims (10)

1. A colorant represented by the following formula (1).
   

   

   [In the formula (1), D represents a colorant matrix, R represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted divalent alicyclic hydrocarbon group, or a substituted Alternatively, it represents an unsubstituted arylene group, X ⁺ represents an organic ammonium ion, and m represents an integer of 1 or more. ]
2. The colorant according to claim 1, wherein R is an alkylene group, a fluorinated alkylene group or an alkenylene group.
3. The colorant according to claim 1 or 2, wherein the organic ammonium ion is represented by the following formula (2) or the following formula (3).
   

   

   

   [In the formulas (2) and (3), Q ¹ to Q ⁵ each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a phenacyl group or a heterocyclic group, and Q ⁶ represents a hydrogen atom An atom, a halo group, a substituted or unsubstituted hydrocarbon group, an alkoxycarbonyl group, a carbamoyl group, or a benzyloxy group is shown. However, at least one of Q ¹ to Q ⁴ represents a substituted or unsubstituted hydrocarbon group. ]
4. The colorant according to any one of claims 1 to 3, which has a structure represented by the following formula (4).
   

   

   [In Formula (4), R and X ⁺ are as defined above, and "*" represents a bond. ]
5. It is obtained by reacting a dye compound having active hydrogen with a compound represented by the following formula (5) in the presence of a base, and subjecting the obtained sulfonate of the dye compound to a salt exchange reaction with an organic quaternary ammonium salt. The colorant according to any one of claims 1 to 4, which is a colorant.
   

   

   [In Formula (5), R is synonymous with the above. ]
6. A coloring composition containing (A) a coloring agent, (B) a binder resin and (C) a crosslinking agent,
   A colored composition containing the colorant according to any one of claims 1 to 5 as the colorant (A).
7. The coloring composition according to claim 6, further comprising (D) a photopolymerization initiator.
8. A color filter comprising a colored layer containing the colorant according to any one of claims 1 to 5.
9. A display element comprising the color filter according to claim 8.
10. A method for producing a colorant according to any one of claims 1 to 5,
    The manufacturing method of a coloring agent including the process with which the pigment | dye compound which has active hydrogen is made to react with the compound represented by following formula (5) in presence of a base.
    

    

    [In the formula (5), R represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted divalent alicyclic hydrocarbon group, or a substituted or unsubstituted arylene group. . ]