KR20130094771A - Coloring agent, coloring composition, color filter and display element - Google Patents

Abstract

The present invention provides a novel colorant having high solubility in organic solvents, excellent heat resistance, and useful for forming color filters and the like. The coloring agent of this invention is represented by following General 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 or unsubstituted arylene. Group, X ⁺ represents an organic ammonium ion, m represents an integer of 1 or more]

Description

Colorants, coloring compositions, color filters and display elements {COLORING AGENT, COLORING COMPOSITION, COLOR FILTER AND DISPLAY ELEMENT}

This invention relates to a coloring agent, a coloring composition, a color filter, and a display element, More specifically, it is preferable for formation of color filters, such as a transmissive or reflective color liquid crystal display element, a solid-state image sensor, an organic EL display element, and an electronic paper. It relates to a colorant, a color filter comprising the colorant containing the colorant, a color layer containing the colorant, and a display element comprising the color filter.

In manufacturing a color filter using a colored radiation sensitive composition, after apply | coating a pigment dispersion type colored radiation sensitive composition on a board | substrate, and drying it, radiation of a dry coating film to a desired pattern shape (hereinafter, "exposure" And developing to obtain pixels of each color (Patent Documents 1 to 2). Moreover, the method (patent document 3) which forms a black matrix using the photopolymerizable composition which disperse | distributed carbon black is also known. Moreover, the method (patent document 4) which obtains the pixel of each color by the inkjet system using the pigment dispersion type colored resin composition is also known.

By the way, in order to implement | achieve high contrast of a liquid crystal display element, and high definition of a solid-state image sensor, it is known that it is effective to use dye as a coloring agent. For example, Patent Literature 4 proposes the use of a dye in which a sulfonic acid group directly bonded to the dye mother nucleus is in the form of an amine salt or a dye in which a sulfonamide group is introduced into a dye.

Japanese Patent Application Laid-Open No. 2-144502 Japanese Patent Laid-Open Publication No. 3-53201 Japanese Patent Application Laid-Open No. 6-35188 Japanese Patent Laid-Open No. 6-51115

However, the dyes in which the sulfonic acid group directly bonded to the dye mother nucleus as a amine salt or a dye in which a sulfonamide group is introduced into the dye as proposed in Patent Literature 4 can be used as some pigments having an aromatic ring such as phthalocyanine. It is limited to a compound. Therefore, there is a strong demand for the development of a novel colorant capable of realizing high contrast of liquid crystal display elements and high definition of solid-state imaging elements.

Therefore, the subject of this invention is providing the novel coloring agent which is high in solubility with respect to an organic solvent, is excellent also in heat resistance, and is useful for formation of a color filter. Moreover, the subject of this invention is providing the display element provided with the coloring composition containing the said coloring agent, the color filter provided with the coloring layer containing the said coloring agent, and the said color filter.

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

That is, this invention provides the coloring agent (henceforth a "main coloring agent") represented by following General 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 or unsubstituted arylene. Group, X ⁺ represents an organic ammonium ion, m represents an integer of 1 or more]

Moreover, this invention provides the manufacturing method of this coloring agent containing the process of making the dye compound which has active hydrogen react with the compound represented by following General formula (5) in presence of a base.

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

Moreover, this invention is a coloring composition containing (A) coloring agent, (B) binder resin, and (C) crosslinking agent, The coloring composition containing the said coloring agent as (A) coloring agent, and the coloring layer containing this coloring agent. The present invention provides a color filter provided and a display element including the color filter. Here, "colored layer" means each color pixel used for a color filter, a black matrix, a black spacer, etc.

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

Therefore, the coloring agent of this invention is very suitable for preparation of various color filters, including the color filter for color liquid crystal display elements, the color filter for color separation of a solid-state image sensor, the color filter for organic electroluminescent display elements, and the color filter for electronic paper, for example. Can be used. In addition, the coloring agent of this invention can be used suitably also for an electrophoretic display element. Moreover, the coloring agent of this invention can be used also as a pigment dispersant of a pigment derivative type.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Pattern colorant

First, the definition of the symbol in General formula (1) is demonstrated.

In R of the said General formula (1), an alkylene group may be linear or branched chain, For example, a C2-C20 alkylene group is mentioned. Specifically, an ethylene group, a 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- dimethyl pentane- 1, 3- diyl group, a dodecane-1, 4- diyl group, etc. are mentioned. The alkylene group may have a substituent, As a substituent, a halo group is mentioned, for example, A fluoro group is especially preferable.

In R of the said General formula (1), an alkenylene group may be linear or branched chain, For example, a C3-6 alkenylene group is mentioned. Specifically, 1-propene-1,3-diyl group, buta-1-ene-1,3-diyl group, penta-1-ene-1,3-diyl group, hexa-1-ene-1,3 -Diyl group etc. are mentioned. The alkenylene group may have a substituent and a halo group is mentioned as said substituent, for example.

As a bivalent alicyclic hydrocarbon group in R of the said General formula (1), a bicyclo [2.2.1] heptane-2, 6- diyl group is mentioned, for example. The divalent alicyclic hydrocarbon group may have a substituent, and a hydroxyl group is mentioned as said substituent, for example.

As an arylene group in R of the said General formula (1), naphthalene-1, 8- diyl group is mentioned, for example. The arylene group may have a substituent and an alkoxy group, a halo group, a nitro group, a cyano group, and a trifluoromethyl group are mentioned as said substituent, for example.

In the present invention, R is preferably an alkylene group, a fluorinated alkylene group or an alkenylene group, and particularly 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.

D represents a colorant matrix, and as D, activities such as -NHCO-, -CONHCO-, -OH, -NH ₂ , -NH-, -COCH ₂ CO-, -COOH, -SH, etc. It is preferable that it is a residue remove | excluding one or more active hydrogens from the pigment | dye compound provided with group which has hydrogen.

If m is an integer greater than or equal to 1, it is possible to select suitably according to the kind of this coloring agent, The integer of 1-6 is preferable from the point of the ease of manufacture of this coloring agent, and the integer of 2-4 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 groups a to k. The compound shown can be mentioned.

[In Formulas (6) and (7), R ¹ to R ⁴ 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.]

[Compound Group a]

[Compound Group b]

[Compound Group c]

[Compound Group d]

Compound Group e

Compound Group f

[Compound Group g]

[Compound Group h]

[Compound Group i]

[Compound Group j]

[Compound Group k]

In Formula (6), R ¹ to R ² 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, among which a hydrogen atom and an alkyl group are preferable. Especially a hydrogen atom is preferable.

In the 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 which halo groups are preferred. Examples of the halo group include fluorine, chlorine, bromine and iodine, and chlorine is particularly preferred.

1-20 are preferable and, as for carbon number of the alkyl group which comprises the alkyl group in R <^1> -R <^4> and an alkyl substituted amino group, 1-12 are more preferable. In addition, the alkyl substituted amino group may be 1 substitution or 2 substitutions. In addition, the carbon number of the alkoxy group in R ¹ to R ⁴ are preferable, and a 1 to 8, more preferably 1-4. In addition, the alkyl group and the alkoxy group may be linear or branched.

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

[In the formula (4), R and X ⁺ is R, and X ⁺ and agreed in the above formula (1), "*" denotes a bond hand;

Although it will not specifically limit if X <^{+> is an} organic ammonium ion, What is represented by following General formula (2) or following General formula (3) from a viewpoint of the solubility and heat resistance with respect to an organic solvent is preferable.

[Formula (2) and Formula (3), Q ¹ to Q ⁵ 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, a halo group, or a substituent Or an unsubstituted hydrocarbon group, an alkoxycarbonyl group, a carbamoyl group, or a benzyloxy group, provided that at least one of Q ¹ to Q ⁴ represents a substituted or unsubstituted hydrocarbon group.]

In Q ¹ to Q ⁶ , examples of the hydrocarbon group include 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, an aralkyl group having 7 to 20 carbon atoms, and the like. Can be mentioned. As a C1-C20 aliphatic hydrocarbon group, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, etc. are mentioned. As a C3-C20 alicyclic hydrocarbon group, a C3-C8 cycloalkyl group, a C3-C8 cycloalkenyl group, etc. are mentioned. In addition, the alkyl group, alkenyl group and alkynyl group may be linear or branched chain, and the alkenyl group and alkynyl group may have an unsaturated bond in the molecule | numerator and terminal. Moreover, as a C6-C20 aryl group, a phenyl group, a naphthyl group, anthryl group, a phenanthryl group, a biphenylene group, etc. are mentioned. 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, alkyl A lene (preferably C _1-6 alkylene) -biphenylene-alkylene (preferably C _1-6 alkylene) group and the like. Here, in this specification, " _C1-6 " means that carbon number is _1-6 .

These hydrocarbon groups may have a substituent, and 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, an alkyl (preferably C _1-6 alkyl) -carbonyl group, Aryl (preferably C _6-14 aryl) _-carbonyl group etc. are mentioned. In addition, the position and number of these substituents are arbitrary, and when it has two or more substituents, the said substituent may be same or different. Here, in this specification, " _C6-14 " means that carbon number is _6-14 .

In Q ¹ to Q ⁵ , the heterocyclic group is a monocyclic ring (preferably a 3 to 8 membered ring, more preferably formed by bonding a carbon atom and at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom); The group derived from a 5-6 membered ring) is mentioned. Specific examples include alicyclic groups such as pyrrolidinyl group, imidazolidinyl group, pyrazolidinyl group, piperidyl group, piperidino group, piperazinyl group, homopiperazinyl group, morpholinyl group and theomorpholinyl group Heterocyclic group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, quinolyl group, isoquinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, thienyl group, furyl group, pyran Aromatic heterocyclic groups, such as a silyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, a tetrazolyl group, a thiazolyl group, an oxazolyl group, an indolyl group, an indazolyl group, a benzoimidazolyl group, and a furinyl group Can be mentioned.

Especially, as Q <^1> -Q <^5> , a hydrogen atom or a substituted or unsubstituted hydrocarbon group is preferable. As said hydrocarbon group, a C1-C20 aliphatic hydrocarbon group and a C3-C20 alicyclic hydrocarbon group are preferable, A C1-C20 alkyl group and a C3-C8 cycloalkyl group are more preferable, Especially C1-C20 Alkyl groups are preferred. In addition, at least one of Q ¹ to Q ⁴ represents a substituted or unsubstituted hydrocarbon group, and the hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms and an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and preferably having 1 to 20 carbon atoms. An alkyl group and a C3-C8 cycloalkyl group are more preferable, and a C1-C20 alkyl group is especially preferable.

Moreover, although alkoxy in an alkoxycarbonyl group in Q <^6> may be linear or branched chain, 1-6 are preferable as carbon number.

Especially, as Q <^6> , a hydrogen atom, a substituted or unsubstituted hydrocarbon group is preferable, and a hydrogen atom and a C1-C6 alkyl group are especially preferable.

Among these, as X <^+> represented by the said General formula (2), a mono, di, tri, or tetraalkylammonium ion is preferable, and tetraalkylammonium ion is especially preferable. Specifically, tetraethylammonium ion, tetrabutylammonium 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, etc. are mentioned.

Moreover, as X <^+> represented by the said General formula (3), for example, pyridinium ion, alkyl substituted pyridinium ion, 1-alkylpyridinium ion, 1-alkyl-halo substituted pyridinium ion, 1-alkyl-alkoxycarbonyl Substituted pyridinium ions, 1-phenacylpyridinium ions, 1-alkyl-carbamoyl substituted pyridinium ions, and 1-alkyl-benzyloxy substituted pyridinium ions. Specifically, 2,4,6-trimethylpyridinium ion, 1-methylpyridinium ion, 1-dodecylpyridinium ion, 1-butyl-3-methylpyridinium ion, 2-bromo-1-ethylpyridinium ion Ion, 1-ethyl-3- (hydroxymethyl) pyridinium ion, 1-ethyl-4- (methoxycarbonyl) pyridinium ion, 4-carbamoyl-1-hexadecylpyridinium ion, 2- Benzyloxy-1-methylpyridinium ion etc. are mentioned.

Although the preferable specific example of a compound represented by the said General formula (1) is shown to the following compound groups l-p, it is not limited to these.

[Compound Group l]

[Compound Group m]

[Compound Group n]

[Compound group o]

[Compound Group p]

This coloring agent organically reacts the sulfonate of the obtained pigment compound with the process of reacting the pigment compound which has active hydrogen, for example in presence of a base with the compound represented by following General formula (5) (henceforth "process 1"). It can manufacture from what is provided to the process of carrying out the salt exchange reaction with a quaternary ammonium salt (henceforth "process 2").

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

The pigment compound which has active hydrogen used at the process 1 may be synthesize | combined by a well-known method, and may be a commercial item. As a commercial item, For example, in the compound represented by the said General formula (6), Z is an ethoxy group, R <^1> and R <^2> are hydrogen atoms (CI pigment violet 37), and are represented by the said General formula (7) The compound (CI Pigment Red 254) whose R <^3> and R <^4> is a chlorine atom in a compound can be obtained from Ciba specialty chemical company.

Moreover, as a base used at the process 1, potassium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, sodium methylate, potassium t-butoxide, triethylamine, DBU, sodium hydride, etc. are mentioned, for example.

In said Formula (5), as R, an alkylene group, a fluorinated alkylene group, or an alkenylene group is preferable, As such a compound, the compound represented by following General formula (5-1) is mentioned, for example.

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

R ^a alkylene group having a carbon number is preferably from 2 to 4, The alkenylene group preferably having a carbon number is 2, and the alkyl group in R ^b in R ^a in is preferably a carbon number of 1 to 3 . As for the sum total carbon number of R ^<a> and R <^b> , 1-5 are preferable.

Specific examples of the compound represented by the formula (5) include 1,2-ethanesultone, 1,3-propanesultone, 1,4-butanesultone, 2,4-butanesultone, 1,5-pentanesultone, 2, 5-pentanesultone, 3,5-pentanesultone, 3,6-hexanesultone, 2,6-hexanesultone, 2,2-dimethyl-3,5-pentanesultone, 9,12-dodecanesultone, 1,3 -Propenesultone, perfluoro-1,2-ethanesultone, perfluoro-2,3-propanesultone, perfluoro-3,4-butanesultone, 1,8-naphthosultone, 5-hydroxy -2,6-bicyclo [2.2.1] heptanesultone (5-hydroxy-3-oxa-2-thiatricyclo [4.2.1.0 ^4,8 ] nonane-2,2-dione), etc. are mentioned. .

The compound represented by the formula (5) can be produced by a known method, for example, the method described in JP-A-5-43572, JP-A-2007-31355, and the like, and are commercially available products. You can also use

In addition, it is preferable to perform the said process 1 in a solvent, As said solvent, For example, amides, such as N, N- dimethylformamide, N, N- dimethylacetamide, pyrrolidone, such as N-methylpyrrolidone, And nitriles such as imidazolidinone and acetonitrile, such as N, N'-dimethylimidazolidinone, and ethers such as tetrahydrofuran.

Reaction temperature is 20-150 degreeC, for example, and reaction time is 30 minutes-48 hours, for example.

Examples of the organic quaternary ammonium salt used in Step 2 include tetraethylammonium halide, tetrabutylammonium halide, dimethyl (dioctadecyl) ammonium halide, tetrahexyl ammonium halide, tributyl (methyl) ammonium halide and tetradodecyl ammonium halide. , Tetraoctyl ammonium halide, trimethyl (hexadecyl) ammonium halide, trioctyl (methyl) ammonium halide, tetraisopentylammonium halide, 1-butyl-3-methylpyridinium halide, 1-butyl-4-methylpyridinium halide, 1-butylpyridinium halide, 1-dodecylpyridinium halide, 1-ethyl-3- (hydroxymethyl) pyridinium ethyl sulfite, 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, tetrafluoroboric acid 2-bromo-1-ethylpyridinium, 2-chloro-1- Methylpyridinium halide, 2-fluoro-1-methylpyridinium p-toluenesulfonate, halogenated hydrogen salt of 2- (chloromethyl) pyridine, halogenated hydrogen salt of 3- (chloromethyl) pyridine, 4- (chloromethyl Hydrogen halide salt of pyridine, 3-carbamyl-1-methylpyridinium halide, 4-carbamoyl-1-hexadecylpyridinium halide, 2-benzyloxy-1-methylpyridinium trifluoromethanesulfonate Etc. can be mentioned.

It is preferable to perform the said process 2 also in a solvent, As said solvent, For example, amides, such as N, N- dimethylformamide, N, N- dimethylacetamide, pyrrolidone, such as N-methylpyrrolidone, N, Nitriles such as imidazolidinone, such as N'-dimethylimidazolidinone, acetonitrile, ethers such as tetrahydrofuran, alcohols such as methanol and ethanol, ketones such as acetone, and the like. These solvents may be used alone or in combination of two or more thereof.

Reaction temperature is 20-70 degreeC, for example, and reaction time is 30 minutes-12 hours, for example.

After the completion of step 1 or step 2, if necessary, appropriate purification methods such as filtration, washing, drying, concentration, reprecipitation, centrifugation, extraction with various solvents, chromatography, etc. are appropriately combined to obtain the target compound from the reaction system. I can isolate it. In addition, after the completion of step 1, the target compound may be provided to step 2 without isolation.

Moreover, the compound which introduce | transduced the sulfonic acid group through the alkylene group to the pigment compound through the alkylene group, and the compound which introduce | transduced the sulfonimide group via the alkylene group into the pigment compound can also be manufactured starting from process 1 as a starting point. The compound thus obtained can also be used as a colorant.

The colorant thus obtained is soluble in various organic solvents, including ketones such as cyclohexanone, as shown in the examples posted later, and the excellent 5% mass reduction temperature in TG-DTA analysis is 300 ° C or higher. It may have heat resistance.

Coloring composition

Hereinafter, the structural component of the coloring composition (henceforth simply a "coloring composition") of this invention is demonstrated.

- (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 this invention, coloring agents other than this coloring agent can be contained as (A) coloring agent. As such a coloring agent, if it has coloring property, it will not specifically limit, A color and a material can be selected suitably according to the use of a color filter. Specifically, any of pigments, dyes, and natural dyes may be used as colorants other than the present dyes, and pigments and / or dyes are preferable from the point that high color purity, brightness, contrast, and the like are required for the color filter.

The pigment may be either an organic pigment or an inorganic pigment, and examples of the organic pigment include compounds classified as pigments in a color index (C.I .; issued by The Society of Dyers and Colorists). Specific examples include those having the following color index (C.I.) names.

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

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

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

C.I. Pigment Violet 1, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment Violet 32, C.I. Pigment Violet 36, C.I. Pigment Violet 38;

C.I. Pigment Blue 1, C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 60, C.I. Pigment Blue 80;

C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment green 58;

C.I. Pigment Brown 23, C.I. Pigment Brown 25;

C.I. Pigment Black 1, C.I. Pigment Black 7.

Examples of the inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zincated, lead sulfate, yellow lead, zinc sulfur, bengal (red iron oxide (III)), cadmium red, ultramarine blue, blue wire, chromium oxide rust, and cobalt. Rust, amber, titanium black, synthetic iron black, carbon black and the like.

In the present invention, the pigment may be purified by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or a combination thereof. In addition, a pigment can also be used, modifying the particle surface with resin as needed. As resin which modifies the particle surface of a pigment, the vehicle resin of Unexamined-Japanese-Patent No. 2001-108817, or commercially available various pigment dispersion resin is mentioned, for example. As a resin coating method of the carbon black surface, the method as described in Unexamined-Japanese-Patent No. 9-71733, Unexamined-Japanese-Patent No. 9-95625, Unexamined-Japanese-Patent No. 9-124969, etc. are mentioned, for example. Can be adopted. In addition, it is preferable to use an organic pigment to refine | miniaturize a primary particle by what is called salt milling. As a method of salt milling, the method disclosed by Unexamined-Japanese-Patent No. 08-179111 can be employ | adopted, for example.

Moreover, as said dye, it can select suitably from various oil-soluble dyes, a direct dye, an acid dye, a metal complex dye, etc., For example, the thing with the following color index (C.I.) names is mentioned.

C.I. Solvent Yellow 4, C.I. Solvent Yellow 14, C.I. Solvent Yellow 15, C.I. Solvent Yellow 24, C.I. Solvent Yellow 82, C.I. Solvent Yellow 88, C.I. Solvent Yellow 94, C.I. Solvent Yellow 98, C.I. Solvent Yellow 162, C.I. Solvent yellow 179;

C.I. Solvent Red 45, C.I. Solvent red 49;

C.I. Solvent Orange 2, C.I. Solvent Orange 7, C.I. Solvent Orange 11, C.I. Solvent Orange 15, C.I. Solvent Orange 26, C.I. Solvent orange 56;

C.I. Solvent Blue 35, C.I. Solvent Blue 37, C.I. Solvent Blue 59, C.I. Solvent blue 67;

C.I. Acid yellow 17, C.I. Acid yellow 29, C.I. Acid yellow 40, C.I. Acid yellow 76;

C.I. Acid red 91, C.I. Acid Red 92, C.I. Acid red 97, C.I. Acid red 114, C.I. Acid red 138, C.I. Acid red 151;

C.I. Acid orange 51, C.I. Acid orange 63;

C.I. Acid blue 80, C.I. Acid Blue 83, C.I. Acid blue 90;

C.I. Acid Green 9, C.I. Acid Green 16, C.I. Acid Green 25, C.I. Acid Green 27.

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

(A) The content rate of a coloring agent is 5-70 mass% in solid content of a coloring composition normally from the point which forms the pixel which has high brightness | luminance and excellent color purity or excellent light-shielding property, Preferably it is 5-60 mass%. . Solid content here is components other than the solvent mentioned later.

When using a pigment as another coloring agent in this invention, it can be used together with a dispersing agent and a dispersion adjuvant as needed. As the dispersant, for example, suitable dispersants such as cationic, anionic and nonionic systems can be used. A polymer dispersant is preferable. Specific examples thereof include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene alkyl phenyl ether-based dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants, polyester dispersants, .

Such dispersants are commercially available, and are, for example, disperbyk-2000, dispervic-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK) as acrylic dispersants Dispervic -161, dispervic -162, dispervic -167, dispervic -170, dispervic -182 (above, manufactured by BYK Corporation), Solsper's 76500 (Lubric) Solspur 24000 (Lubric Sol Co., Ltd.) and the like are used as a polyethylene imine dispersant, and azisper PB821, azisper PB822, azisper PB880 and azisper are used as a polyester dispersant. PB881 (made by Ajinomoto Fine Techno Co., Ltd.) etc. is mentioned, respectively.

Moreover, a pigment derivative is mentioned as said dispersion adjuvant, For example, copper phthalocyanine, diketopyrrolopyrrole, the sulfonic acid derivative of quinophthalone, etc. are mentioned. In addition, content of a dispersing agent and a dispersal auxiliary agent can be suitably determined within the range which does not impair the objective of this invention.

- (B) Binder Resin -

The coloring composition of this invention contains (B) binder resin. Thereby, alkali developability and binding property to a board | substrate can be improved to a coloring composition. Although it does not specifically limit as such binder resin, It is preferable that it is resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Especially, the polymer which has a carboxyl group (henceforth a "carboxyl group-containing polymer") is preferable, for example, copolymerization different from the ethylenically unsaturated monomer which has one or more carboxyl groups (henceforth "unsaturated monomer (b1)"). The copolymer of possible ethylenically unsaturated monomer (henceforth "unsaturated monomer (b2)") is mentioned.

Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, monosuccinic acid [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, p-vinyl benzoic acid etc. are mentioned.

These unsaturated monomers (b1) can be used individually or in mixture of 2 or more types.

Moreover, as said unsaturated monomer (b2), for example

N-substituted maleimide such as N-phenylmaleimide, N-cyclohexylmaleimide;

Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether and acenaphthylene;

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

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decane-8-ylvinyl ether, pentacyclopentadedecaneylvinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane Vinyl ethers such as;

Macro monomers having a mono (meth) acryloyl group at the ends of polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane

And the like.

These unsaturated monomers (b2) can be used individually or in mixture of 2 or more types.

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

As a specific example of the copolymer of an unsaturated monomer (b1) and an unsaturated monomer (b2), For example, Unexamined-Japanese-Patent No. 7-140654, Unexamined-Japanese-Patent No. 8-259876, Unexamined-Japanese-Patent No. 10-31308, Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-174224, Japanese Patent Laid-Open No. 11-258415, Japanese Patent Laid-Open No. 2000-56118 The copolymer disclosed in Unexamined-Japanese-Patent No. 2004-101728, etc. are mentioned.

Moreover, in this invention, for example, Unexamined-Japanese-Patent No. 5-19467, Unexamined-Japanese-Patent No. 6-230212, Unexamined-Japanese-Patent No. 7-207211, Unexamined-Japanese-Patent As disclosed in Japanese Patent Application Laid-Open No. 09-325494, Japanese Patent Application Laid-Open No. Hei 11-140144, Japanese Patent Application Laid-Open No. 2008-181095, and the like, a polymerizable unsaturated bond such as a (meth) acryloyl group is added to a side chain thereof. The carboxyl group-containing polymer which has can also be used as binder resin.

The binder resin in this invention has a weight average molecular weight (henceforth "Mw" hereafter) of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran) normally 1,000-100,000, Preferably it is 3,000-50,000. If the Mw is too small, the remaining film ratio or the like of the resulting film may be lowered, the pattern shape, heat resistance, or the like may be impaired, or the electrical properties may be deteriorated. On the other hand, if the Mw is too large, the resolution may be lowered or the pattern shape may be damaged. There exists a possibility that a dry foreign material may generate easily at the time of application | coating by the.

Moreover, the ratio (Mw / Mn) of the number average molecular weight (henceforth "Mn") of polystyrene conversion measured by Mw of binder resin in this invention and GPC (elution solvent: tetrahydrofuran) is preferable. 1.0-5.0, More preferably, it is 1.0-3.0.

The binder resin in this invention can be manufactured by a well-known method, For example, Unexamined-Japanese-Patent No. 2003-222717, Unexamined-Japanese-Patent No. 2006-259680, International Publication No. 07/029871, etc. By the method disclosed, the structure, Mw, and Mw / Mn can also be controlled.

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

In this invention, content of binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts. When there is too little content of binder resin, alkali developability may fall, for example, there exists a possibility that the storage stability of the coloring composition obtained may fall, and when too large, since the coloring agent concentration will fall comparatively, the target color density as a thin film will be. There is a fear that it will be difficult to achieve.

-(C) crosslinking agent-

In the present invention, (C) crosslinking agent refers to a compound having two or more polymerizable groups. As a group which can superpose | polymerize, an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, an N-alkoxy methylamino group, etc. are mentioned, for example. In the present invention, as the (C) crosslinking agent, a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups is preferable.

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 polyfunctional (meth) acrylate modified with caprolactone, The polyfunctional urethane (meth) acrylate obtained by making alkylene oxide modified polyfunctional (meth) acrylate, the (meth) acrylate which has a hydroxyl group, and polyfunctional isocyanate, the (meth) acrylate which has a hydroxyl group, and an acid anhydride The polyfunctional (meth) acrylate which has a carboxyl group obtained by making it react, etc. are mentioned.

Here, as the aliphatic polyhydroxy compound, for example, a divalent aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, trivalent such as glycerin, trimethylolpropane, pentaerythritol, or dipentaerythritol The above aliphatic polyhydroxy compound is mentioned. As (meth) acrylate which has the said hydroxyl group, 2-hydroxyethyl (meth) acrylate, trimethylol propanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth), for example Acrylate, glycerol dimethacrylate, etc. are mentioned. As said polyfunctional isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, etc. are mentioned, for example. As the acid anhydride, for example, anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic dianhydride And tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

Moreover, as said caprolactone modified polyfunctional (meth) acrylate, the compound described in Paragraph [0015]-[0018] of Unexamined-Japanese-Patent No. 11-44955 is mentioned, for example. Examples of the alkylene oxide modified polyfunctional (meth) acrylates include ethylene oxide and / or propylene oxide modified di (meth) acrylates of bisphenol A, ethylene oxide and / or propylene oxide modified tri (meth) acrylates of isocyanuric acid. Ethylene oxide and / or propylene oxide modified tri (meth) acrylate of trimethylolpropane, ethylene oxide and / or propylene oxide modified tri (meth) acrylate of pentaerythritol, ethylene oxide and / or propylene oxide modification of pentaerythritol Tetra (meth) acrylate, ethylene oxide and / or propylene oxide modified penta (meth) acrylate of dipentaerythritol, ethylene oxide and / or propylene oxide modified hexa (meth) acrylate of dipentaerythritol, and the like.

Moreover, as a compound which has the said 2 or more N-alkoxymethylamino group, the compound etc. which have a melamine structure, a benzoguanamine structure, a urea structure are mentioned, for example. In addition, a melamine structure and the benzoguanamine structure are the chemical structures which have one or more triazine ring or a phenyl substituted triazine ring as a basic skeleton, and are a concept including melamine, benzoguanamine, or 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'-tetra (alkoxy Methyl) benzoguanamine, N, N, N ', N'- tetra (alkoxy methyl) glycoluril, etc. are mentioned.

Among these polyfunctional monomers, a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth) acrylic acid, a caprolactone modified polyfunctional (meth) acrylate, and a 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. In the polyfunctional (meth) acrylate obtained by making a trivalent or more aliphatic polyhydroxy compound and (meth) acrylic acid react, trimethylol propane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexa In the polyfunctional (meth) acrylate which an acrylate has a carboxyl group, the compound obtained by making pentaerythritol triacrylate and succinic anhydride react, and the compound obtained by making dipentaerythritol pentaacrylate and succinic anhydride react the intensity of a colored layer It is especially preferable at the point that it is high, it is excellent in the surface smoothness of a colored layer, and it is hard to produce background contamination, film | membrane remainder, etc. on the board | substrate and the light shielding layer of an unexposed part.

In this invention, (C) crosslinking agent can be used individually or in mixture of 2 or more types.

As for content of (C) crosslinking agent in this invention, 10-1,000 mass parts is preferable with respect to 100 mass parts of (A) coloring agents, and 20-500 mass parts is especially preferable. In this case, when there is too little content of a polyfunctional monomer, there exists a possibility that sufficient sclerosis | hardenability may not be obtained. On the other hand, when there is too much content of a polyfunctional monomer, alkali developability will fall when alkali developability is provided to the coloring composition of this invention, and background contamination, a film | membrane residue, etc. generate | occur | produce on the board | substrate or the light shielding layer of an unexposed part. It tends to be easy.

- (D) Photopolymerization initiator -

(D) a photopolymerization initiator may be contained in the coloring composition of the present invention. Thereby, radiation sensitivity can be provided to a coloring composition. The (D) photoinitiator used for this invention is a compound which generate | occur | produces the active species which can start superposition | polymerization of the said (C) crosslinking agent by exposure of radiation, such as visible light, an ultraviolet-ray, an ultraviolet-ray, an electron beam, and X-rays. .

As such a photoinitiator, a thioxanthone type compound, an acetophenone type compound, a biimidazole type compound, a triazine type compound, an O-acyl oxime type compound, an onium salt type compound, a benzoin type compound, a benzophenone type compound, (alpha)-diketone type compound, a polynuclear quinone type compound, a diazo type compound, an imide sulfonate type compound, etc. are mentioned.

In the present invention, the photopolymerization initiator may be used alone or in combination of two or more. As the photopolymerization initiator, at least one member selected from the group consisting of a thioxanone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, and an O-acyloxime compound is preferable.

Specific examples of the thioxanone compound in the photopolymerization initiator of the present invention include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like.

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

Moreover, as a specific example of the said biimidazole type compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl- 1,2'-biimidazole, 2,2' -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'- tetraphenyl-1,2'-biimidazole, etc. are mentioned.

When a non-imidazole-based compound is used as the photopolymerization initiator, it is preferable to use a hydrogen donor in view of improving the sensitivity. As used herein, the term &quot; hydrogen donor &quot; means a compound capable of donating a hydrogen atom to a radical generated from a nonimidazole compound by exposure. Examples of the hydrogen donors include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4'-bis (dimethylamino) benzophenone, and 4,4'-bis (di Amine hydrogen donors, such as ethylamino) benzophenone, are mentioned. In the present invention, the hydrogen donors may be used alone or in combination of two or more thereof. In the sense of using a combination of one or more mercaptan-based hydrogen donors and one or more amine-based hydrogen donors, the sensitivity may be improved. More preferred.

In addition, specific examples of the triazine-based 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 (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4 Triazine type compounds which have halomethyl groups, such as a 6-bis (trichloromethyl) -s-triazine, are mentioned.

In addition, specific examples of the O-acyl oxime compound 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-tetrahydro Furanylmethoxybenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2- Dimethyl-1,3-dioxoranyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

In the present invention, when a photopolymerization initiator other than a non-imidazole-based compound such as an acetophenone-based compound is used, a sensitizer may be used in combination. As such a sensitizer, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylamino acetophenone, 4-dimethylamino propiophenone, for example. Ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoic acid, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl ) Coumarin, 4- (diethylamino) chalcone, and the like.

In this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (C) crosslinking agents, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. In this case, when there is too little content of a photoinitiator, there exists a possibility that hardening by exposure may become inadequate, and when too large, there exists a tendency for the formed colored layer to fall off from a board | substrate at the time of image development.

-(E) solvent-

The coloring composition of this invention contains the said (A)-(C) component and the other component added arbitrarily, Usually, a solvent is mix | blended and it is prepared as a liquid composition.

The solvent may be appropriately selected and used as long as it disperses or dissolves the components (A) to (C) and the other components constituting the coloring composition, and does not react with these components and has appropriate volatility.

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, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tri (Poly) alkyls such as propylene glycol monomethyl ether and tripropylene glycol monoethyl ether Glycol monomethyl 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 and 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 (Poly) alkylene glycol monoalkyl ether acetates such as acetate, 3-methoxybutyl acetate and 3-methyl-3-methoxybutyl acetate;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate;

Alkoxycarboxylates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate and 3-methyl- Acid esters;

Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate Other esters such as n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate;

Aromatic hydrocarbons such as toluene and xylene;

Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone, or lactams

And the like.

Propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol from the viewpoint of solubility, pigment dispersibility, coating properties, etc. in these solvents Methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methoxypropionate, 3-e Methyl oxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, butyric acid Ethyl, butyric acid i-propyl, n-butyl butyrate, ethyl pyruvate and the like are preferred.

In this invention, a solvent can be used individually or in mixture of 2 or more types.

Although content of a solvent is not specifically limited, From the viewpoint of the applicability | paintability, stability, etc. of the coloring composition obtained, the quantity by which the total concentration of each component except the solvent of the said coloring composition becomes 5-50 mass% is preferable, Especially it is 10-10. The amount which becomes 40 mass% is preferable.

-additive-

The coloring composition of this invention may contain various additives as needed.

As an additive, For example, fillers, such as glass and an alumina; High molecular compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); Surfactants such as fluorine-based surfactants and silicone-based surfactants; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Adhesion promoter; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; An anti-aggregation 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-propane Residue improvers such as diol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol; (Meth) acryloyloxyethyl] phthalate mono [2- (meth) acryloyloxyethyl], and omega -carboxypolycaprolactone mono (meth) .

Color filter and its manufacturing method

The color filter of this invention is equipped with the coloring layer containing this coloring agent.

As a method of manufacturing a color filter, the first following method is mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to partition a portion for forming a pixel as necessary. Subsequently, after apply | coating the liquid composition of the radiation sensitive composition of this invention which the red coloring agent disperse | distributed, for example on this board | substrate, prebaking is performed and the solvent is evaporated and a coating film is formed. Subsequently, after exposing through a photomask to this coating film, it develops using alkaline developing solution, and removes and removes the unexposed part of a coating film. Thereafter, by postbaking, a pixel array in which red pixel patterns are arranged in a predetermined arrangement is formed.

Subsequently, using each colored radiation-sensitive composition of green or blue, applying, prebaking, exposure, developing and post-baking of each colored radiation-sensitive composition are carried out in the same manner as described above, and the green pixel array and the blue pixel Arrays are sequentially formed on the same substrate. As a result, a color filter in which pixel arrays of three primary colors of red, green, and blue are arranged on a substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

In addition, the 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, and using the colored radiation-sensitive composition in which black colorant is dispersed, the pixel is used. It can also be formed in the same manner as in the case of forming.

As a board | substrate used when forming a color filter, glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. are mentioned, for example.

If necessary, 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, vacuum deposition, or the like.

When the colored radiation-sensitive composition is applied to the substrate, suitable coating methods such as spraying, roll coating, rotary coating (spin coating), slit die coating, and bar coating can be adopted. It is preferable to adopt the slit die coating method.

Prebaking is normally performed combining pressure reduction drying and heat drying. The reduced-pressure drying is usually carried out until 50 to 200 Pa is reached. The conditions for heating and drying are usually about 70 to 110 DEG C for about 1 to 10 minutes.

Coating thickness is 0.6-8.0 micrometers normally as a film thickness after drying, Preferably it is 1.2-5.0 micrometers.

As a light source for radiation used when forming a pixel and / or a black matrix, for example, a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, or an argon ion Laser light sources, such as a laser, a YAG laser, an XeCl excimer laser, and a nitrogen laser, etc. are mentioned, The radiation in which a wavelength exists in the range of 190-450 nm is preferable.

In general, the exposure dose of the radiation is preferably 10 to 10,000 J / m ² .

As the alkaline developer, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydrooxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabi Aqueous solutions, such as cyclo- [4.3.0] -5-nonene, are preferable.

A suitable amount of water-soluble organic solvents such as methanol and ethanol, surfactants, and the like may be added to the alkaline developer. After the alkali development, it is usually washed with water.

As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (liquid pooling) developing method, and the like can be applied. The developing conditions are preferably 5 to 300 seconds at room temperature.

Post-baking conditions are about 10 to 60 minutes at 180-280 degreeC normally.

The film thickness of the pixel formed in this way is 0.5-5.0 micrometers normally, Preferably it is 1.0-3.0 micrometers.

As a second method of manufacturing the color filter, a method of obtaining various pixels by the inkjet method disclosed in Japanese Patent Laid-Open No. 7-318723, Japanese Patent Laid-Open No. 2000-310706, or the like can be adopted. have. In this method, the partition which also serves as the light shielding function is first formed on the surface of the substrate. Subsequently, after discharging the liquid composition of the coloring composition of this invention in which the red coloring agent was disperse | distributed, for example in the formed partition by inkjet apparatus, prebaking is performed and the solvent is evaporated. Subsequently, after exposing this coating film as needed, it hardens | cures by post-baking and a red pixel pattern is formed.

Subsequently, using the green or blue coloring composition, a green pixel pattern and a blue pixel pattern are sequentially formed on the same board | substrate similarly to the above. Thereby, the color filter by which the pixel pattern of three primary colors of red, green, and blue is arrange | positioned on a board | substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

In addition, the partition wall has a function of preventing the mixing of the coloring composition of each color discharged in the compartment as well as the light shielding function, and thus has a thicker film thickness than the black matrix used in the first method described above. Therefore, a partition is normally formed using a black radiation sensitive composition.

The substrate and the light source of the radiation used in forming the color filter, the prebaking and postbaking methods and conditions are the same as those of the first method described above. Thus, the film thickness of the pixel formed by the inkjet system is about the same as the height of a partition.

After forming a protective film on the pixel pattern obtained in this way as needed, a transparent conductive film is formed by sputtering. After a transparent conductive film is formed, a spacer may be further formed to form a color filter. Although a spacer is normally formed using a radiation sensitive composition, it can also be set as the spacer (black spacer) which has light shielding property. In this case, a coloring and radiation-sensitive composition in which a black coloring agent is dispersed is used, and the coloring composition of the present invention can be preferably used for forming such a black spacer.

Since the color filter of this invention obtained in this way is extremely high in brightness | luminance and color purity, it is very useful for a color liquid crystal display element, a color image tube element, a color sensor, an organic EL display element, an electronic paper, etc.

Display element

The display element of this invention is equipped with the color filter of this invention. As a display element, a color liquid crystal display element, an organic electroluminescent display element, an electronic paper, etc. are mentioned.

The color liquid crystal display device having the color filter of the present invention can take an appropriate structure. For example, the color filter may be formed on a substrate separate 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 have an opposite structure via the liquid crystal layer. In addition, the substrate on which the color filter is formed on the surface of the driving substrate on which the thin film transistor (TFT) is disposed and the substrate on which the ITO (indium oxide doped tin) electrode is formed have a structure opposite to each other via the liquid crystal layer. It may be. The latter structure can particularly improve the aperture ratio and has the advantage that a bright and high definition liquid crystal display element is obtained.

The color liquid crystal display device having the color filter of the present invention may include a backlight unit having a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As a white LED, for example, a white LED which combines a red LED, a green LED, and a blue LED to obtain white light by mixing, and a white LED and a blue LED that combines a blue LED, a red LED and a green light emitting phosphor to obtain white light by mixing White LED that obtains white light by mixing color by combining red light emitting phosphor and green light emitting phosphor, white LED which obtains white light by mixing blue LED and YAG-based phosphor, and combination of green light emitting phosphor and green light emitting phosphor The white LED which obtains white light, the ultraviolet-ray LED, the red light emitting fluorescent substance, the green light emitting fluorescent substance, and the blue light emitting fluorescent substance are combined, and the white LED etc. which obtain white light by mixing are mentioned.

The color liquid crystal display device including the color filter of the present invention includes a twisted nematic (TN) type, a super twisted nematic (STN) type, an in-plane switching switching (IPS) type, a vertical alignment (VA) type, and an optically compensated beirefringence (OCB) type. Appropriate liquid crystal modes such as a mold can be applied.

In addition, the organic electroluminescent display element provided with the color filter of this invention can take a suitable structure, for example, can take the structure disclosed by Unexamined-Japanese-Patent No. 11-307242.

Moreover, the electronic paper provided with the color filter of this invention can take a suitable structure, for example, can take the structure disclosed by Unexamined-Japanese-Patent No. 2007-41169.

<Examples>

Hereinafter, an Example is given and embodiment of this invention is described further more concretely. However, this invention is not limited to the following Example.

<Synthesis and evaluation of this colorant>

Example 1 (Synthesis and Evaluation of Compound (VII) Described in Specific Examples)

0.3 g of sodium hydride, the C.I. made by Ciba specialty chemical company. 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, 1.45 g of 1,4-butanesultone was further added, followed by stirring 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 dimethyl dioctadecyl ammonium chloride, and 30 mL of acetone were mixed and stirred for 6 hours while heating to 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. Let this be compound A. It was confirmed by ¹ H-NMR (solvent: deuterated chloroform) measurement of compound A that it was a desired compound.

¹ H-NMR: δ7.95-7.32 (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, a solution having a concentration of about 0.0010% by mass was prepared, and the absorption spectrum was measured. As a result, the ^{λmax = 545nm, ε = 60000mol -1} cm -1 L.

In addition, compound A was melt | dissolved 10 mass% or more in cyclohexanone.

Moreover, the 5% mass reduction temperature was 315 degreeC as a result of the thermogravimetry-differential heat simultaneous measurement analysis (henceforth "TG-DTA") of compound A.

Example 2

A colorant was synthesized in the same manner as in Example 1 except for using CI Pigment Red 254 (a compound in which both R ³ and R ⁴ are chlorine atoms in Chemical Formula (7)) instead of PV-37. , ¹ H-NMR (solvent: deuterated chloroform) was confirmed to be the desired compound.

Example 3

Example 1 and 1 except that CI pigment yellow 128 (compound represented by the following formula) was used instead of CI pigment violet 37 and 1-ethylpyridinium chloride was used instead of dimethyldioctadecylammonium chloride, respectively. Similarly, the coloring agent was synthesize | combined and it confirmed that it was a desired compound by ¹ H-NMR (solvent: deuterated chloroform) measurement.

All the coloring agents obtained in Examples 2-3 were dissolved in cyclohexanone by 10 mass% or more. In addition, the 5% mass reduction temperature based on TG-DTA of the coloring agent obtained in Examples 2-3 was all 250 degreeC or more.

Comparative Example 1

PV-37 was dissolved in 1-methoxy-2-propyl acetate, a solution having a concentration of about 0.0010% by mass was prepared, and the absorption spectrum was measured. As a result, the ε = 600mol ^-1 cm ^-1 L according to 562nm.

In addition, even 0.1 mass% of PV-37 was not dissolved in any of 1-methoxy-2-propyl acetate and cyclohexanone.

&Lt; Production of Pigment Dispersion >

Production Example 1

As a colorant, C.I. 15 parts by mass of Pigment Blue 15: 6, 12.5 parts by mass of BYK-LPN21116 (manufactured by BYK Corporation) as a dispersant (solid content concentration = 40% by mass), and 72.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent. Treatment with a beads mill yielded a pigment dispersion (A-1).

Production Example 2

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

<Production of Dye Solution>

Production Example 3

5 mass parts of compound A as a coloring agent and 95 mass parts of propylene glycol monomethyl ether acetates were mixed as a solvent, and the dye solution A was prepared.

&Lt; Synthesis of binder resin >

100 parts by mass of propylene glycol monomethyl ether acetate was charged into a flask equipped with a cooling tube and a stirrer and purged with nitrogen. Heated to 80 DEG C, 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, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of mono (2-acryloyloxyethyl) succinate and 2,2'-azobis (2,4-dimethylvalero Nitrile) 6 mass parts of mixed solution was dripped over 1 hour, and it maintained this temperature and superposed | polymerized for 2 hours. Then, the binder solution (solid content concentration = 33 mass%) was obtained by heating up the temperature of reaction solution at 100 degreeC, and superposing | polymerizing for 1 hour. Obtained binder resin was Mw = 12,200 and Mn = 6,500. This binder resin is referred to as "binder resin (B1)".

&Lt; Preparation and evaluation of colored composition >

Example 4

13.6 mass parts of pigment dispersion liquid (A-1), 27.2 mass parts of dye solution A, 16.1 mass part of binder resin (B1) solution as a binder resin, M-402 (Dipentaerythritol hexaacrylate and di pentaerythritol hexaacrylate) as a crosslinking agent 5.5 parts by mass of a mixture of pentaerythritol pentaacrylate) and MW-30 (N, N, N ', N', N ", N" -hexa (methoxymethyl) melamine manufactured by Sanwa Chemical Co., Ltd. are the main components and the weight average polymerization degree 1.3 ) 2.4 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (manufactured by Ciba Specialty Chemical Co., Ltd., brand name Irgacure) as a photopolymerization initiator Propylene glycol monomethyl ether acetate was mixed as 2.2 mass parts and a solvent, and the coloring composition (CR1) of 20 mass% of solid content concentration was prepared.

After apply | coating a coloring composition (CR1) on a glass substrate using a spin coater, it prebaked for 10 minutes on the 80 degreeC hotplate, and formed the coating film. The rotation speed of a spin coater was changed and the three coating films from which a film thickness differs were formed by the same operation.

Subsequently, after cooling these board | substrates to room temperature, the radiation which contains each wavelength of 365 nm, 405 nm, and 436 nm in each coating film is exposed to the exposure amount of 2,000 J / m <^2> using a high pressure mercury lamp, without a photomask. It was. Thereafter, the developer was discharged at a developing pressure of 1 kgf / cm ² (nozzle diameter of 1 mm) at a developing pressure of 23 ° C. containing 0.04% by mass of potassium hydroxide aqueous solution, and a shower development was performed for 90 seconds. Then, after wash | cleaning this board | substrate with ultrapure water and air drying, the cured film for evaluation was formed by performing post-baking further for 30 minutes in a 230 degreeC clean oven.

The substrate on which the cured film was formed was sandwiched by two deflection plates, the deflection plate on the front side was rotated while irradiating with a fluorescent lamp (wavelength range of 380 to 780 nm) from the rear side, and the luminance meter LS-100 (manufactured by Minolta Co., Ltd.) The maximum value and minimum value of the light intensity transmitted by the same were measured. Then, for each of the cured films, a value obtained by dividing the maximum value by the minimum value was defined as a 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 a binder resin, 5.5 parts by mass of Toagosei Co., Ltd. M-402 2.4 parts by mass of Sanwa Chemical Co., Ltd. MW-30 and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Shiba Specialty Chemical Co., Ltd. make, brand name) as a photoinitiator Propylene glycol monomethyl ether acetate was mixed as 2.2 mass parts and solvents, and the coloring composition (CR2) of 20 mass% of solid content concentration was prepared.

It evaluated like Example 4 except having used coloring composition (CR2) instead of coloring composition (CR1). The evaluation results are shown in Table 1.

In Table 1, "B15: 6" means C.I. Pigment Blue 15: 6 refers to C.I. Pigment violet 23 means each.

Claims (10)

The coloring agent represented by following General 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 or unsubstituted arylene. Group, X ⁺ represents an organic ammonium ion, m represents an integer of 1 or more] The coloring agent of Claim 1 whose R is an alkylene group, a fluorinated alkylene group, or an alkenylene group. The coloring agent of Claim 1 or 2 in which the said organic ammonium ion is represented by following General formula (2) or following General formula (3).

[Formula (2) and Formula (3), Q ¹ to Q ⁵ 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, a halo group, or a substituent Or an unsubstituted hydrocarbon group, an alkoxycarbonyl group, a carbamoyl group, or a benzyloxy group, provided that at least one of Q ¹ to Q ⁴ represents a substituted or unsubstituted hydrocarbon group.] The coloring agent in any one of Claims 1-3 which has a structure represented by following General formula (4).

[In Formula (4), R and X <^+> are synonymous with the above, "*" shows a bond.] The dye compound having an active hydrogen is reacted with a compound represented by the following formula (5) in the presence of a base, and the sulfonate of the obtained dye compound is reacted with an organic quaternary ammonium salt according to any one of claims 1 to 4. The coloring agent obtained by salt exchange reaction.

[In Formula (5), R is synonymous with the above.] It is a coloring composition containing (A) a coloring agent, (B) binder resin, and (C) crosslinking agent,
The coloring composition containing the coloring agent of any one of Claims 1-5 as said (A) coloring agent. The coloring composition of Claim 6 which further contains (D) photoinitiator. The color filter provided with the coloring layer containing the coloring agent of any one of Claims 1-5. A display element comprising the color filter of claim 8. It is a manufacturing method of the coloring agent in any one of Claims 1-5.
The manufacturing method of the coloring agent containing the process of making the pigment compound which has active hydrogen react with the compound represented by following General formula (5) in presence of a base.

[In 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.]