TWI509356B - Coloring composition, color filter, and display component - Google Patents

Description

Coloring composition, color filter, and display element

The present invention relates to a coloring agent, a coloring composition, a color filter, and a display element, and more particularly, to a transmissive or reflective type color liquid crystal display element, a solid-state imaging element, an organic EL display element, an electronic paper, etc. A coloring agent for forming a color filter, a colored composition containing the coloring agent, a color filter including a coloring layer containing the coloring agent, and a display element including the color filter.

It is known that in order to manufacture a color filter using a coloring sensitizing radiation composition, a pigment dispersion type color-sensitive radiation composition is applied onto a substrate and dried, and then the dried coating film is irradiated with radiation to a desired pattern shape (hereinafter, A method of "exposure" and development to obtain pixels of respective colors (Patent Documents 1 to 2). Further, a method of forming a black matrix by using a photopolymerizable composition of dispersed carbon black is also known (Patent Document 3). Further, a method of obtaining a pixel of each color by an inkjet method using a pigment-dispersed colored resin composition is also known (Patent Document 4).

Further, in order to achieve high contrast of the liquid crystal display element or high definition of the solid-state imaging element, it is known to use a dye as a colorant. For example, Patent Document 4 proposes the use of a dye in which a sulfonic acid group directly bonded to a dye core is formed into an amine salt or a dye in which a sulfonamide group is introduced into a dye.

[Previous Technical Literature] [Patent Literature]

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

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

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

[Patent Document 4] Japanese Patent Laid-Open No. Hei 6-51115

However, as proposed in Patent Document 4, a dye in which a sulfonic acid group directly bonded to a dye core is formed into an amine salt or a dye in which a sulfonamide group is introduced into a dye can be used, and is limited to anthraquinone. A part of the pigment compound having an aromatic ring. Therefore, there is a strong demand for novel colorants which can achieve high contrast of liquid crystal display elements or high definition of solid-state photographic elements.

Therefore, an object of the present invention is to provide a novel coloring agent which is highly soluble in an organic solvent and excellent in heat resistance, and is useful for formation of a color filter or the like. Further, an object of the present invention is to provide a coloring composition containing the coloring agent, a color filter including a coloring layer containing the coloring agent, and a display element including the color filter.

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

In other words, the present invention provides a coloring agent (hereinafter also referred to as "the present coloring agent") represented by the following formula (1).

D(-R-SO ₃ ^- ) _m X ⁺ _m (1)

[In the formula (1), D represents a colorant precursor, and R represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted extended alkenyl group, a substituted or unsubstituted divalent alicyclic hydrocarbon group, or a substituted or An unsubstituted extended aryl group, X ⁺ means an organic ammonium ion, and m is an integer of 1 or more]

Further, the present invention provides a method for producing the present coloring agent 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 the formula (5), the R system 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 provides a colored composition containing the above coloring agent as the coloring agent (A). A color filter including the coloring layer of the coloring agent and a display element including the color filter. Here, the term "colored layer" means a color pixel, a black matrix, a black spacer, or the like used for a color filter.

The coloring agent of the present invention has high solubility in an organic solvent and is excellent in heat resistance. Further, when a coloring composition containing the coloring agent of the present invention is used, a color filter having pixels of high contrast can be obtained.

Therefore, the coloring agent of the present invention can be suitably used for, for example, color filters for color liquid crystal display elements, color filters for color separation of solid-state imaging elements, color filters for organic EL display elements, and electronic paper. The production of various color filters, including color filters. Further, the coloring agent of the present invention can also be suitably used for an electrophoretic display element. Further, the coloring agent of the present invention can also be used as a pigment derivative type pigment dispersing agent.

[Formation for implementing the invention]

The invention will be described in detail below.

Colorant

First, the definition of the symbols in the formula (1) will be explained.

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. Specific examples thereof include an exoethyl group, a propyl group, a trimethylene group, a tetramethylene group, a butyl-1,3-diyl group, a pentamethylene group, a pentane-1,3-diyl group, and a pentane-1. ,4-diyl, hexa-1,4-diyl, hex-1,5-diyl, 4,4-dimethylpentan-1,3-diyl, dodecane-1,4-diyl Wait. The alkylene group may have a substituent, and examples of the substituent include a halogen group, and among them, a fluorine group is preferred.

In R of the above formula (1), the alkenyl group may be linear or branched, and examples thereof include an alkenyl group having 3 to 6 carbon atoms. Specific examples thereof include 1-propene-1,3-diyl, but-1-ene-1,3-diyl, pent-1-ene-1,3-diyl, and hex-1-ene- 1,3-diyl and the like. The alkenyl group may have a substituent, and examples of the substituent include a halogen group.

In the R of the above formula (1), the divalent alicyclic hydrocarbon group may, for example, be 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 extended aryl group include a naphthalene-1,8-diyl group. The aryl group may have a substituent, and examples of the substituent include an alkoxy group, a halogen group, a nitro group, a cyano group, and a trifluoromethyl group.

In the present invention, R is preferably an alkylene group, a fluorinated alkyl group or an alkenyl group, particularly an alkylene group having 2 to 5 carbon atoms, a fluorinated alkyl group having 2 to 5 carbon atoms or a carbon number of 3~. The alkenyl group of 6 is preferred.

D is a colorant precursor, but in terms of D, it is preferable to have -NHCO-, -CONHCO-, -OH, -NH ₂ , -NH-, - from the viewpoint of ease of production of the colorant. A residue of one or more active hydrogens is removed from a dye compound having a base of active hydrogen such as COCH ₂ CO-, -COOH or -SH.

When m is an integer of 1 or more, it may be appropriately selected depending on the type of the coloring agent. However, from the viewpoint of easiness of production of the coloring agent, it is preferably an integer of 1 to 6, more preferably an integer of 2 to 4.

The dye compound having a group having an active hydrogen, for example, 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 compounds of the compound groups a to k described below.

In the formulae (6) and (7), R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen group, an alkyl group, an alkoxy group, an alkyl-substituted amine 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 halogen group, an alkyl group, an alkoxy group, an alkyl-substituted amine group, a trifluoromethyl group or a nitro group, but among these, It is preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

Further, in the above formula (7), R ³ to R ⁴ each independently represent a hydrogen atom, a halogen group, an alkyl group, an alkoxy group, an alkyl-substituted amine group, a trifluoromethyl group or a nitro group, but these Among them, a halogen group is preferred. The halogen group is exemplified by fluorine, chlorine, bromine or iodine, and among them, chlorine is preferred.

The number of carbon atoms of the alkyl group constituting the alkyl group and the alkyl group-substituted amino group in R ¹ to R ⁴ is preferably from 1 to 20, more preferably from 1 to 12. Further, the alkyl-substituted amine group may be one-substituted or two-substituted. Further, the alkoxy group in R ¹ to R ⁴ preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Further, the alkyl group and the alkoxy group may be linear or branched.

In the present invention, it is preferable that one or more of the dye compounds having -NHCO-, -CONHCO-, and especially -NHCO- are removed from the viewpoint of solubility in an organic solvent and heat resistance. Residue of active hydrogen. That is, in the case of the present colorant, it is preferred to have a structure represented by the following formula (4).

[In the formula (4), R and X ⁺ are synonymous with R and X ⁺ in the above formula (1), and "*" means a linkage]

X ⁺ is not particularly limited as long as it is an organic ammonium ion, but it 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 formulae (2) and (3), Q ¹ to Q ⁵ each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a benzamidine methyl group or a heterocyclic group, and Q ⁶ represents a hydrogen atom or a halogen. A hydrocarbyl group, a substituted or unsubstituted hydrocarbyl group, an alkoxycarbonyl group, an amine carbenyl group or a benzyloxy group. However, at least one of Q ¹ to Q ⁴ represents a substituted or unsubstituted hydrocarbon group]

Q, Q ¹ to ^6, in terms of hydrocarbon, carbon atoms, for example, include an aliphatic hydrocarbon group of 1 to 20, 3 to 20 carbon atoms of the aliphatic cyclic hydrocarbon group having 6 to 20 carbon atoms, an aryl group of carbon number 7 to 20 aralkyl and the like. 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. Further, the alkyl group, the alkenyl group and the alkynyl group may be linear or branched, and the alkenyl group and the alkynyl group may have an unsaturated bond in either the molecule or the terminal. Further, examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, and a biphenyl group. Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group, a phenethyl group, a trityl group, an alkylene group (preferably a C _1-6 alkylene group)-phenylene-alkylene group. a base (preferably a C _1-6 alkylene group), an alkylene group (preferably a C _1-6 alkylene group)-extended biphenyl-alkylene group (preferably a C _1-6 alkylene group) ) base. Here, the term "C _1-6 " in the present specification means that the number of carbon atoms is 1 to 6.

The hydrocarbon group may have a substituent, and examples of the substituent include a hydroxyl group, an alkoxy group, a halogen group, a nitro group, a cyano group, a decylamino group, a sulfonic acid group, and an alkyl group. It is a C _1-6 alkyl)-carbonyl group, an aryl group (preferably a C _6-14 aryl group)-carbonyl group or the like. Further, the positions and the number of the substituents are arbitrary, and when there are two or more substituents, the substituents may be the same or different. Here, "C _6-14 " in the present specification means that the number of carbon atoms is 6 to 14.

Further, in the examples of Q ¹ to Q ⁵ , the heterocyclic group may be a single ring formed by combining at least one atom selected from a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom (preferably 3~). The base of the 8-member ring, more preferably the 5- to 6-member ring. Specific examples include pyrrolidinyl, imidazolidinyl, pyrazolyl, piperidinyl, N-hexahydropyridyl, and hexahydropyridyl. Hexahydropyrrolidine base, Olinyl group, sulfur Alicyclic heterocyclic group, pyridyl group, pyridyl group Base, pyrimidinyl, oxime Base, quinolyl, isoquinolyl, anthracene Base, naphthyridinyl, quin Lolinyl, thienyl, furyl, pyranyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, An aromatic heterocyclic group such as an azolyl group, a fluorenyl group, a carbazolyl group, a benzimidazolyl group or a fluorenyl group.

Among them, in the case of Q ¹ to Q ⁵ , a hydrogen atom or a substituted or unsubstituted hydrocarbon group is preferred. The hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms or a cycloalkane having 3 to 8 carbon atoms. The base is particularly preferably an alkyl group having 1 to 20 carbon atoms. Further, at least one of Q ¹ to Q ⁴ represents a substituted or unsubstituted hydrocarbon group, but in the hydrocarbon group, an aliphatic hydrocarbon group having 1 to 20 carbon atoms and an alicyclic carbon having 3 to 20 carbon atoms are preferable. The hydrocarbon group is more preferably an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 20 carbon atoms.

Further, the alkoxy group in the alkoxycarbonyl group in Q ⁶ may be linear or branched, but the carbon number is preferably from 1 to 6.

Among them, in the case of Q ⁶ , a hydrogen atom, a substituted or unsubstituted hydrocarbon group is preferred, and a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is preferred.

Among these, X ⁺ represented by the above formula (2) is preferably a mono-, di-, tri- or tetraalkylammonium ion, particularly a tetraalkylammonium ion. Specific examples thereof include tetraethylammonium ion, tetrabutylammonium ion, dimethyl(di-octadecyl)ammonium ion, tetrahexylammonium ion, tributyl(methyl)ammonium ion, and tetra- Dodecyl ammonium ion, tetraoctyl ammonium ion, trimethyl (hexadecyl) ammonium ion, trioctyl (methyl) ammonium ion, tetraisoamyl ammonium ion, and the like.

Further, X ⁺ represented by the above formula (3) includes, for example, a pyridinium, an alkyl-substituted pyridyl cation, a 1-alkylpyridinium cation, a 1-alkyl-halo-substituted pyridyl cation, 1-alkyl-alkoxycarbonyl-substituted pyridinium cation, 1-benzylidenemethylpyridinium cation, 1-alkyl-amine-methylindenyl-substituted pyridyl cation, 1-alkyl-benzyloxy-substituted pyridyl cation. Specific examples thereof include 2,4,6-trimethylpyridine cation, 1-methylpyridine cation, 1-dodecylpyridine cation, 1-butyl-3-methylpyridine cation, and 2-bromo. 1-ethylpyridinium cation, 1-ethyl-3-(hydroxymethyl)pyridine cation, 1-ethyl-4-(methoxycarbonyl)pyridine cation, 4-aminomethylcarbonyl-1-hexa Alkylpyridine cation, 2-benzyloxy-1-methylpyridine cation, and the like.

Suitable 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 coloring agent can be obtained by, for example, supplying a dye compound having active hydrogen to a compound which is reacted with a compound represented by the following formula (5) in the presence of a base (hereinafter also referred to as "step 1"). The sulfonate of the pigment compound is produced by a step of performing a base exchange reaction with an organic quaternary ammonium salt (hereinafter also referred to as "step 2").

[In the formula (5), the R system is synonymous with the above]

The dye compound having active hydrogen used in the step 1 may be a compound which is synthesized by a known method or may be a commercially available product. In the case of a commercially available product, for example, a compound of the Z-based ethoxy group and a R ¹ and R ² -based hydrogen atom in the compound represented by the above formula (6) (CI Pigment Violet 37), or the above formula (7) Among the compounds represented by the compounds, R ³ and R ⁴ are chlorine atoms (CI Pigment Red 254), which are available from Ciba Specialty Chemicals.

Further, examples of the base used in the step 1 include potassium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, sodium methoxide, tertiary potassium butoxide, triethylamine, DBU, sodium hydride, and the like.

In the above formula (5), R is preferably an alkylene group, a fluorinated alkyl group or an extended alkenyl group. Examples of such a compound include the following formula (5-1). Compound.

[In the formula (5-1), R ^a represents a methylene group or an alkyl group which may have a halogen group, or an alkenyl group, an R ² group represents a hydrogen atom, an alkyl group or a halogen group which may have a halogen group, R ^c is a hydrogen atom or a halogen group]

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

Specific examples of the compound represented by the above formula (5) include 1,2-ethanesulfonate, 1,3-propane lactone, 1,4-butene lactone, and 2,4-. Butiprolactone, 1,5-pentane lactone, 2,5-pentane lactone, 3,5-pentane lactone, 3,6-hexanone, 2,6-hexansulone, 2,2-Dimethyl-3,5-pentane sultone, 9,12-dodecanone, 1,3-propene sultone, perfluoro-1,2-ethane sultone, perfluoro -2,3-propane lactone, perfluoro-3,4-butane lactone, 1,8-naphthalene lactone, 5-hydroxy-2,6-bicyclo[2.2.1]heptane lactone ( 5-hydroxy-3- -2-Thiotricyclo[4.2.1.0 ^4,8 ]壬-2,2-dione).

The compound represented by the above formula (5) can be produced by a known method, for example, in the method disclosed in JP-A-H05-43572, JP-A-2007-31355, or the like. Product.

Further, the above step 1 is preferably carried out in a solvent, and examples of the solvent include decylamine such as N,N-dimethylformamide and N,N-dimethylacetamide. An imidazolidone such as N-methylpyrrolidone or an imidazole ketone such as N,N'-dimethylimidazolidinone, a nitrile such as acetonitrile or an 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.

The organic quaternary ammonium salt used in the step 2 may, for example, be tetraethylammonium halide, tetrabutylammonium halide, dimethyl(di-octadecyl)ammonium halide, tetrahexammonium halide, halogenated. Tributyl (methyl) ammonium, tetra-dodecyl ammonium halide, tetraoctyl ammonium halide, trimethyl (hexadecyl) ammonium halide, trioctyl (methyl) ammonium halide, tetraisoammonium halide , 1-butyl-3-methylpyridinium halide, 1-butyl-4-methylpyridinium halide, 1-butylpyridinium halide, 1-dodecylpyridinium halide, 1-ethyl- 3-(hydroxymethyl)pyridinium ethyl sulfate, 1-ethyl-3-methylpyridinium bis(trifluoromethanesulfonyl) fluorene imide, 1-ethylpyridinium halide, halogenated 1-methyl Pyridinium chloride, 1-benzylformamidine pyridinium halide, 1-propylpyridinium halide, 1-ethyl-4-(methoxycarbonyl)pyridinium halide, 2,4,6-trimethylpyridine鎓p-toluenesulfonate, 2,6-dimethylpyridinium p-toluenesulfonate, 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1-methylpyridinium halide, 2- Fluoro-1-methylpyridinium p-toluenesulfonate, hydrogen halide of 2-(chloromethyl)pyridine, hydrogen halide of 3-(chloromethyl)pyridine, 4-( Hydrogen halide of chloromethyl)pyridine, 3-aminoformamido-1-methylpyridinium halide, 4-aminemethylamino-1-hexadecylpyridinium halide, 2-benzyloxy-1- Methylpyridinium trifluoromethanesulfonate and the like.

The above step 2 is also preferably carried out in a solvent, and examples of the solvent include decylamine such as N,N-dimethylformamide and N,N-dimethylacetamide. - pyrrolidone such as methylpyrrolidone, imidazolidinone such as N,N'-dimethylimidazolidinone, nitrile such as acetonitrile, ether such as tetrahydrofuran, alcohol such as methanol or ethanol, or ketone such as acetone . These solvents may be used singly or in combination 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 the end of step 1 or step 2, if necessary, a combination of filtration, washing, drying, concentration, re-sinking, centrifugation, extraction with various solvents, chromatography, etc., and the purpose of the reaction system The compounds were isolated separately. Further, after the end of the step 1, the step compound 2 may be supplied without separately separating the objective compound.

Further, starting from the first step, a compound in which a sulfonic acid group is introduced into a dye compound via an alkylene group or a compound in which a sulfonimide group is introduced into a dye compound via an alkylene group can also be produced. The compound thus obtained can also be used as a coloring agent.

The coloring agent thus obtained is soluble in various organic solvents including ketones such as cyclohexanone as shown in the examples described later, and has a temperature of 5% by mass in the TG-DTA analysis at 300. Excellent heat resistance such as above °C.

Coloring composition

Hereinafter, the constituent components of the coloring composition of the present invention (hereinafter referred to as "coloring composition") will be described.

- (A) colorant -

The coloring composition of the present invention contains the present coloring agent as (A) a coloring agent. These coloring agents can be used singly or in combination of two or more.

In the present invention, a coloring agent other than the coloring agent may be contained as (A) a coloring agent. The coloring property of the coloring agent is not particularly limited, and the color or material can be appropriately selected depending on the use of the color filter. Specifically, any of a pigment, a dye, and a natural pigment may be used as a coloring agent other than the coloring matter. However, since the color filter requires high color purity, brightness, contrast, etc., it is preferably a pigment and/or dye.

Any of the above-mentioned pigments may be any of an organic pigment and an inorganic pigment, and examples of the organic pigment include compounds classified as pigments in a pigment index (C.I.; The Society of Dyers and Colourists). Specifically, the name of the pigment index (C.I.) as described below is attached.

CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 180, CI Pigment Yellow 211; CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI pigment orange 43, CI pigment orange 46, CI pigment orange 49, CI pigment orange 61, CI pigment orange 64, CI pigment orange 68, CI pigment orange 70, CI pigment orange 71, CI pigment orange 72, CI pigment orange 73, CI Pigment Orange 74; CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 5, CI Pigment Red 17, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 41, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170 CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 209, CI Pigment Red 214, CI Pigment Red 220, CI Pigment Red 221, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 254, CI pigment red 255, CI pigment red 262, CI pigment red 264, CI pigment red 272; CI pigment violet 1, CI pigment violet 19, CI pigment violet 23, CI pigment violet 29, CI pigment violet 32, CI pigment violet 36, CI Pigment Violet 38; CI Pigment Blue 1, CI Pigment Blue 15, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 60, CI Pigment Blue 80; CI Pigment Green 7 , CI Pigment Green 36, CI Pigment Green 58; CI Pigment Brown 23, CI Pigment Brown 25; CI Pigment Black 1, CI Pigment Black 7.

Further, examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, lead chromate, zinc chrome yellow, iron oxide (red iron oxide (III)), and cadmium red. Ultramarine, Prussian blue, chrome oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black, etc.

In the present invention, the pigment may also be purified by recrystallization, re-sinking, solvent washing, sublimation, vacuum heating or a combination thereof. Further, the pigment may be used by modifying the surface of the particles with a resin as needed. The resin for modifying the surface of the pigment particles may, for example, be a carrier resin described in JP-A-2001-108817 or a commercially available resin for dispersion of various pigments. For the resin coating method of the surface of the carbon black, for example, a method such as those described in JP-A-H09-71733, JP-A-H09-95625, JP-A-9-124969, and the like can be used. Further, the organic pigment is preferably used by refining primary particles by so-called salt milling. For the method of salt milling, for example, a method disclosed in Japanese Laid-Open Patent Publication No. Hei 08-179111 can be employed.

In addition, the dye may be appropriately selected from various oil-soluble dyes, direct dyes, acid dyes, metal complex dyes, and the like, and for example, a pigment index (CI) name as described below may be attached. .

CI Solvent Yellow 4, CI Solvent Yellow 14, CI Solvent Yellow 15, CI Solvent Yellow 24, CI Solvent Yellow 82, CI Solvent Yellow 88, CI Solvent Yellow 94, CI Solvent Yellow 98, CI Solvent Yellow 162, CI Solvent Yellow 179; CI solvent red 45, CI solvent red 49; CI solvent orange 2, CI solvent orange 7, CI solvent orange 11, CI solvent orange 15, CI solvent orange 26, CI solvent orange 56; CI solvent blue 35, CI solvent blue 37, CI Solvent Blue 59, CI Solvent Blue 67; CI Acid Yellow 17, CI Acid Yellow 29, CI Acid Yellow 40, CI Acid Yellow 76; CI Acid Red 91, CI Acid Red 92, CI Acid Red 97, CI Acid Red 114, CI acid red 138, CI acid red 151; CI acid orange 51, CI acid orange 63; CI acid blue 80, CI acid blue 83, CI acid blue 90; CI acid green 9, CI acid green 16, CI acid green 25, CI acid green 27.

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

(A) The content ratio of the coloring agent is usually from 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. Good is 5~60% by mass. The solid component referred to herein is a component other than the solvent described later.

When the pigment is used as another coloring agent in the present invention, it can be used together with a dispersing agent or a dispersing aid as needed. As the dispersing agent, for example, a suitable dispersing agent such as a cationic system, an anionic system or a nonionic system can be used, but a polymer dispersant is preferred. Specific examples thereof include an urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene alkyl phenyl ether dispersant, and a polyethylene glycol II. An ester-based dispersant, a sorbitan fatty acid ester-based dispersant, a polyester-based dispersant, an acrylic dispersant, and the like.

Such dispersing agents are commercially available, and for example, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above BYK Chemie (BYK)), etc. Acrylic dispersant, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above BYK Chemie (BYK)), Solsperse 76500 (manufactured by Lubrizol Co., Ltd.) As a urethane dispersant, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), etc., as a polyethyleneimine dispersant, Ajisper PB821, Ajisper PB822, Ajisper PB880, Ajisper PB881 (Ajinomoto Fine-Techno limited stock) Co., Ltd.) is used as a polyester dispersant.

Further, examples of the dispersing aid include a pigment derivative, specifically, a copper phthalocyanine, a diketopyrrolopyrrole, a sulfonic acid derivative of quinacridone, and the like. In addition, the content of the dispersing agent and the dispersing aid can be appropriately determined within the range not inhibiting the object of the present invention.

- (B) Adhesive Resin -

The coloring composition of the present invention contains (B) a binder resin. Thereby, the alkali developability or the adhesion to the substrate can be improved in the colored composition. The 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 a "carboxyl group-containing polymer") is preferable, and for example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated single") may be mentioned. A copolymer of the body (b1)") with another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (b2)").

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

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

Further, the above unsaturated monomer (b2) may, for example, be an N-position substituted cis-butene such as N-phenylbutyleneimine or N-cyclohexylmethyleneimine. An enediamine imine; such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, an aromatic vinyl compound of ruthenium; Methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, ( Benzyl methacrylate, 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, isodecyl (meth) acrylate, ( Methyl)acrylic acid tricyclo[5.2.1.0 ^2,6 ]癸-8-yl ester, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxybenzene (meth)acrylate Ethylene oxide modified (meth)acrylic acid of ester and p-cumylphenol , (Meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl-ylmethyl ester, 3 - [(meth) Bing Xixi oxymethyl] Bismuth, 3-[(methyl)acryloxymethyl]-3-ethyl (Meth) acrylate; such as cyclohexyl vinyl ether, isodecyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] 癸-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3- (vinyloxymethyl)-3-ethyl a vinyl ether of hydrazine; such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polyoxy siloxane, having a mono (meth) acrylonitrile at the end of the polymer molecular chain Base of macromonomers, etc.

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

Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) are disclosed in, for example, JP-A-7-140654, JP-A-8-259876, and Japan. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A copolymer such as No.

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

In the binder resin of the present invention, the polystyrene-equivalent weight average molecular weight (hereinafter also referred to as "Mw") measured by GPC (solution solvent: tetrahydrofuran) is generally 1,000 to 100,000, preferably 3,000 to 50,000. When the Mw is too small, the residual film ratio of the obtained film is lowered, the pattern shape, heat resistance, and the like are impaired, and the electrical characteristics are deteriorated. On the other hand, if the thickness is too large, the resolution is lowered, the pattern shape is impaired, and the shape is narrow. When the nozzle nozzle method is applied, it is easy to cause dry foreign matter.

In addition, the ratio of Mw of the binder resin in the present invention to the number average molecular weight (hereinafter also referred to as "Mn") in terms of polystyrene measured by GPC (solution solvent: tetrahydrofuran) is compared with (Mw/Mn). Good is 1.0~5.0, better is 1.0~3.0.

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

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

In the present invention, the content of the binder resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. When the content of the binder resin is too small, for example, the alkali developability is lowered, and the storage stability of the obtained colored composition is lowered. On the other hand, if the amount of the colorant is relatively large, the concentration of the colorant is relatively lowered, so that it is difficult to achieve The color density of the film for the purpose.

-(C) Crosslinker -

In the present invention, the (C) crosslinking agent is a compound having two or more polymerizable groups. The polymerizable group may, for example, be an ethylenically unsaturated group. base, Mercapto group, N-alkoxymethylamino group and the like. In the present invention, the (C) crosslinking agent is preferably a compound having two or more (meth)acryl fluorenyl groups or a compound having two or more N-alkoxymethylamino groups. .

Specific examples of the compound having two or more (meth) acrylonitrile groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid, A polyfunctional (meth) acrylate modified with caprolactone, a polyfunctional (meth) acrylate modified with an oxyalkylene, and a reaction between a (meth) acrylate having a hydroxyl group and a polyfunctional isocyanate A functional urethane (meth) acrylate, a polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group and an acid anhydride, or the like.

Here, the aliphatic polyhydroxy compound may, for example, be a divalent aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol or polypropylene glycol, glycerin, trimethylolpropane or neopentyl An aliphatic polyhydroxy compound having a trivalent or higher valence of tetraol or dipentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, and pentaerythritol. Acrylate, dipentaerythritol penta (meth) acrylate, glyceryl dimethacrylate, and the like. The polyfunctional isocyanate may, for example, be toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate or isophorone diisocyanate. Examples of the acid anhydride include, for example, succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, a dibasic acid anhydride, pyromellitic anhydride, and biphenyl tetra Tetraacid dianhydride of formic acid dianhydride and diphenyl ketone tetracarboxylic dianhydride.

In addition, the polyfunctional (meth) acrylate which is modified by the above-mentioned caprolactone is, for example, a compound described in paragraphs [0015] to [0018] of JP-A-11-44955. The polyfunctional (meth) acrylate modified by the above oxyalkylene may be exemplified by oxidation of ethylene oxide and/or propylene oxide modified di(meth)acrylate of bisphenol A or isocyanuric acid. Ethylene and/or propylene oxide modified tri(meth)acrylate, trimethylolpropane ethylene oxide and/or propylene oxide modified tri(meth)acrylate, neopentyl alcohol ethylene oxide and/or oxidation Propylene-modified tris(meth)acrylate, neopentyl alcohol ethylene oxide and/or propylene oxide modified tetra(meth)acrylate, dipentaerythritol ethylene oxide and/or propylene oxide modified five ( Methyl) acrylate, ethylene oxide of dipentaerythritol and/or propylene oxide modified hexa(meth) acrylate.

In addition, the compound having two or more N-alkoxymethylamino groups may, for example, be a compound having a melamine structure, a benzoguanamine structure or a urea structure. In addition, the melamine structure and the benzoguanamine structure mean that there are one or more Ring or phenyl substituted three The ring serves as the chemical structure of the basic skeleton and also contains the concept of melamine, benzoguanamine or the like. Specific examples of the compound having two or more N-alkoxymethylamino groups include N,N,N',N',N",N"-hexa(alkoxymethyl) Melamine, N,N,N',N'-tetrakis(alkoxymethyl)benzoguanamine, N,N,N',N'-tetrakis(alkoxymethyl)glycolil, and the like.

Among these polyfunctional monomers, a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound having three or more valences with (meth)acrylic acid, and a modified by caprolactone are preferred. Polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate having carboxyl group, N, N, N', N', N", N"- Hexa(alkoxymethyl)melamine, N,N,N',N'-tetrakis(alkoxymethyl)benzoguanamine. Among the polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound having a trivalent or higher value with (meth)acrylic acid, trimethylolpropane triacrylate, neopentyl alcohol triacrylate , dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate; in a polyfunctional (meth) acrylate having a carboxyl group, which is obtained by reacting pentaerythritol triacrylate with succinic anhydride The compound obtained by reacting the compound, dipentaerythritol pentaacrylate and succinic anhydride has high strength in the colored layer, excellent surface smoothness of the colored layer, and difficulty in floating on the substrate on the unexposed portion and on the light shielding layer. Scumming, residual film and the like are particularly good.

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

The content of the (C) crosslinking agent in the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) coloring agent. In this case, if the content of the polyfunctional monomer is too small, sufficient curability may not be obtained. On the other hand, when the content of the polyfunctional monomer is too large, the alkali developability of the colored composition of the present invention is lowered, and the alkali developability is lowered, and the substrate is easily formed on the unexposed portion or on the light shielding layer. There is a tendency to produce dross, residual film, and the like.

-(D) Photopolymerization Initiator -

The coloring composition of the present invention may contain (D) a photopolymerization initiator. Thereby, the coloring composition can be imparted with radiation linearity. The (D) photopolymerization initiator used in the present invention is a compound which produces an active species which can be caused by exposure of radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays or the like (C). Polymerization of the crosslinking agent.

Examples of such a photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a biimidazole compound, and the like. Compound, O-mercapto oxime compound, sulfonium salt compound, benzoin compound, diphenyl ketone compound, α-diketone compound, polynuclear oxime compound, diazo compound, sulfimine sulfonate An acid ester compound or the like.

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

Among the preferable photopolymerization initiators in the present invention, specific examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2- Isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2, 4-diisopropylthioxanthone and the like.

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

Further, specific examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'- Biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2 , 4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and the like.

Further, when a biimidazole-based compound is used as the photopolymerization initiator, it is preferred to use a hydrogen donor in combination to improve the sensitivity. The term "hydrogen donor" as used herein means a compound which can supply a hydrogen atom to a radical derived from a biimidazole-based compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzoene. An amine-based hydrogen such as a thiol-based hydrogen donor such as oxazole, 4,4'-bis(dimethylamino)diphenyl ketone or 4,4'-bis(diethylamino)diphenyl ketone Subject. In the present invention, the hydrogen-providing system may be used alone or in combination of two or more. However, one or more thiol-based hydrogen donors may be used in combination with one or more amine-based hydrogen donors, and the sensitivity may be further improved. Preferably.

In addition, with the above three Specific examples of the compound include 2,4,6-para(trichloromethyl)-s-three. 2-methyl-4,6-bis(trichloromethyl)-s-three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-three ,2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-three Three of the halomethyl groups a compound.

Further, specific examples of the O-indenyl lanthanide compound include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzylidene).肟), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylindenyl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), ethyl ketone ,1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzyl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl) Ethylketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-di) Methoxybenzylhydrazinyl}-9H-indazol-3-yl]-, 1-(O-ethylindenylhydrazine) and the like.

In the present invention, when a photopolymerization initiator other than the biimidazole compound such as an acetophenone-based compound is used, a sensitizer may be used in combination. Examples of such a sensitizer include 4,4'-bis(dimethylamino)diphenyl ketone and 4,4'-bis(diethylamino)diphenyl ketone, and 4 2-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2, 5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzylidene) coumarin, 4-(2-B Amino group) Chalcone and the like.

In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass, per 100 parts by mass of the (C) crosslinking agent. In this case, if the content of the photopolymerization initiator is too small, the curing due to exposure becomes insufficient. On the other hand, if the amount is too large, the formed coloring layer is likely to be detached from the substrate during development. tendency.

- (E) Solvent -

The colored composition of the present invention contains the above components (A) to (C) and other components which can be arbitrarily added. However, it is usually prepared by mixing a solvent and using a liquid composition.

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

Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, and diethylene glycol monomethyl ether. , diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. (poly)alkylene glycol monoalkyl ethers; alkyl lactate such as methyl lactate or ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tertiary butanol, (cyclo)alkyl alcohols such as 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 a (poly)alkylene glycol monoalkyl ether acetate such as 3-methoxybutyl acetate or 3-methyl-3-methoxybutyl acetate; diethylene glycol dimethyl ether; Other ethers such as diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; propylene glycol diacetate, 1, 3 - diacetate such as butanediol diacetate or 1,6-hexanediol diacetate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethyl Alkoxycarboxylates such as methyl oxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate; Ethyl ester, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, Isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetate, 2-ethyloxybutyrate, etc. Other esters; aromatic hydrocarbons such as toluene and xylene; N,N-dimethylformamide, N,N-dimethyl A guanamine or an indoleamine such as a ketamine or an N-methylpyrrolidone.

Among these solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, and 3-methoxybutyl are preferable from the viewpoints of solubility, pigment dispersibility, and coatability. Acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butanediol diacetate, 1,6- Hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methyl Oxybutyl butyl propionate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate , ethyl pyruvate and the like.

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

The content of the solvent is not particularly limited, but the total concentration of each component other than the solvent of the colored composition is preferably from 5 to 50% by mass from the viewpoints of coatability and stability of the colored composition obtained. The amount is preferably from 10 to 40% by mass.

-additive-

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

Examples of the additive include a filler such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); a fluorine-based surfactant; a fluorene-based surfactant; Surfactant; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, N-(2-aminoethyl)-3-aminopropyl Methyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyl Trimethoxy decane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldi a adhesion promoter such as methoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane; 2,2- An antioxidant such as thiobis(4-methyl-6-tertiary butyl phenol) or 2,6-di-tertiary butyl phenol; 2-(3-tert-butyl-5-methyl-2) -hydroxyphenyl)-5-chlorobenzotriene , ultraviolet absorbers such as alkoxydiphenyl ketones; deflocculants such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2- Aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino group a residue improving agent of -1,2-butanediol or the like; succinic acid mono [2-(methyl) propylene methoxyethyl], fumaric acid mono [2-(methyl) propylene oxiranyl ethyl] A developability improving agent such as ω-carboxypolycaprolactone mono(meth)acrylate.

Color filter and manufacturing method thereof

The color filter of the present invention is provided with a color layer containing the coloring agent.

For the method of manufacturing a color filter, the first method is as follows. First, on the surface of the substrate, a light shielding layer (black matrix) is formed as needed to form a portion of the pixel. Next, a liquid composition of the radiation sensitive composition of the present invention, for example, a red coloring agent is applied onto the substrate, and then prebaked and the solvent is evaporated to form a coating film. Next, after the coating film was exposed through a reticle, it was developed using an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Thereafter, by performing post-baking, a pixel array in which red pixel patterns are arranged in a predetermined arrangement is formed.

Next, using each of the green or blue colored radiation-linear composition, the coating, prebaking, exposure, development, and post-baking of each coloring radiation composition are performed in the same manner as described above, and green is sequentially formed on the same substrate. A pixel array and a blue pixel array. Thereby, a color filter configured by arranging pixel arrays of three primary colors of red, green and blue on the substrate can be obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above.

Further, the black matrix can be formed by forming a desired pattern by a lithography method using a metal film such as chromium formed by sputtering or vapor deposition, but it is also possible to use a color-developing linear composition of a dispersed black colorant. The object is formed in the same manner as in the case of forming the above-described pixels.

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

Further, in the substrate system, an appropriate pretreatment such as a drug treatment, a plasma treatment, an ion plating, a sputtering, a gas phase reaction method, or a vacuum vapor deposition by a decane coupling agent or the like may be applied in advance. .

When the coloring sensitizing radiation composition is applied to the substrate, a suitable 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. However, a spin coating method or a slit coating method is preferred.

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

The coating thickness is usually 0.6 to 8.0 μm, preferably 1.2 to 5.0 μm, in terms of film thickness after drying.

Examples of the light source for forming radiation used in the pixel and/or black matrix include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, and a low pressure. A light source such as a mercury lamp or a laser source such as an argon ion laser, a YAG laser, a XeCl excimer laser, or a nitrogen laser, but a radiation having a wavelength in the range of 190 to 450 nm is preferred.

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

Further, in the above alkali developing solution, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diguanidine-[5.4.0]-7 is preferred. An aqueous solution of undecene, 1,5-difluorenebicyclo-[4.3.0]-5-decene or the like.

A water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkali developing solution in an appropriate amount. Further, after alkali development, it is usually washed with water.

In the development treatment method, a shower development method, a spray development method, a dipping (impregnation) development method, an immersion (liquid pool) development method, or the like can be employed. The development conditions are preferably at room temperature, 5 to 300 seconds.

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

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

In addition, in the second method of producing a color filter, a method of obtaining pixels of respective colors by an inkjet method, which is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. 7-318723, No. 2000-310706, and the like. In this method, first, a partition wall having a light shielding function is formed on the surface of the substrate. Next, a liquid composition of the colored composition of the present invention in which a red coloring agent is dispersed is discharged by an inkjet device in the formed partition wall, and then prebaked to evaporate the solvent. Next, the coating film is exposed as needed, and then cured by post-baking to form a red pixel pattern.

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

Further, the partition wall has a function of not only a light-shielding function but also a coloring composition for each color extruded in the division, so that the film thickness is thicker than that of the black matrix used in the first method described above. . Thus, the partition walls are usually formed using a black sensitizing radioactive composition.

The substrate or the radiation source used in forming the color filter, and the method or condition of prebaking or post-baking is the same as the first method described above. In this way, the film thickness of the pixel formed by the ink jet method is the same as the height of the partition wall.

On the pixel pattern thus obtained, a protective film is formed as needed, and then a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer may be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but may be a spacer having a light-shielding property (black spacer). In this case, a color-developing radiation-linear composition of a disperse black coloring agent can be used, but the coloring composition of the present invention can also be suitably used for the formation of a black spacer such as a black spacer.

The color filter of the present invention thus obtained is extremely useful in color liquid crystal display elements, color image sensor elements, color sensors, organic EL display elements, electronic paper, and the like because of extremely high luminance and color purity.

Display component

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

The color liquid crystal display element having the color filter of the present invention can adopt a suitable structure. For example, a color filter may be formed on a substrate different from a substrate for driving a thin film transistor (TFT), and a structure in which a substrate on which the driving substrate and the color filter are formed is opposed to each other via a liquid crystal layer, and further It is also possible to adopt a structure in which a substrate on which a color filter is formed on a surface of a substrate for driving a thin film transistor (TFT) and a substrate on which an ITO (tin-doped indium oxide) electrode is formed are opposed to each other via a liquid crystal layer. The latter structure allows the aperture ratio to be remarkably improved, and has the advantage of providing a bright and high-definition liquid crystal display element.

The color liquid crystal display element including the color filter of the present invention may be provided with a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL: Cold Cathode Fluorescent Lamp). The white LED may be, for example, a white LED in which a red LED is combined with a green LED and a blue LED to obtain white light by color mixing, and a blue LED and a red LED and a green light-emitting phosphor are combined to be mixed. A white LED with white light is obtained, a blue LED is combined with a red illuminating phosphor and a green illuminating phosphor, and a white LED is obtained by color mixing, and a white color is obtained by mixing a blue LED and a YAG phosphor. Light white LED, blue LED combined with orange illuminating phosphor and green illuminating phosphor to obtain white light white LED by mixing color, ultraviolet LED and red luminescent phosphor and green luminescent phosphor and blue A color light-emitting phosphor is combined to obtain a white light white LED or the like by color mixing.

For the color liquid crystal display element having the color filter of the present invention, TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, IPS (In-Planes Switching) type, VA (Vertical Alignment) type, OCB can be used. Appropriate liquid crystal mode (Optically Compensated Birefringence) type.

In addition, the organic EL display element having the color filter of the present invention can be suitably configured, and for example, it can be configured as disclosed in Japanese Laid-Open Patent Publication No. Hei 11-307242.

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

[Examples]

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

<Synthesis and evaluation of this coloring agent>

Example 1 (Synthesis and evaluation of the compound (ix) described in the above specific example)

0.3 g of sodium hydride, CI Pigment Violet 37 (hereinafter also referred to as "PV-37") and 20 mL of dimethylformamide were mixed and stirred at room temperature for 2 hours, and further added thereto. 4-butene sultone 1.45 g and stirred for 12 hours. Thereafter, the reaction liquid was filtered through celite, and the filtrate was reprecipitated with 300 mL of acetone. The obtained solid was washed with acetone to give 1.5 g of a blue solid.

1.5 g of the obtained blue solid, 5 g of dimethyldi-octadecyl ammonium chloride and 30 mL of acetone were mixed, and the mixture was stirred for 6 hours while heating under reflux. Thereafter, the reaction liquid was filtered through celite, and the solvent was removed under reduced pressure, whereby 1.5 g of a purple solid was obtained. This was taken as Compound A. The compound of the desired compound was confirmed by ¹ H-NMR (solvent: heavy hydrogen chloroform) of Compound A.

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 the absorption spectrum was measured. As a result, λmax = 545 nm and ε = 60,000 mol ^-1 cm ^-1 L.

Further, the compound A is dissolved in cyclohexanone at 10% by mass or more.

Further, as a result of the thermal weight-differential heat simultaneous measurement analysis of Compound A (hereinafter referred to as "TG-DTA"), the temperature at which the 5% mass was reduced was 315 °C.

Example 2

In Example 1 except that CI Pigment Red 254 (the above compounds R ³ and R ⁴ are both chlorine atoms based formula (7)) other than a substituted-based Example PV-37 Synthesis of a toner in the same manner, by ^a H-NMR (solvent: heavy hydrogen chloroform) was measured to confirm the desired compound.

Example 3

In Example 1, except that CI Pigment Yellow 128 (a compound represented by the following formula) was used instead of CI Pigment Violet 37, and 1-ethylpyridinium chloride was used instead of dimethyldi-octadecylammonium chloride. The synthetic coloring agent was synthesized in the same manner as in Example 1, and the compound was identified by ¹ H-NMR (solvent: hydrogen chloroform).

Any of the color formers obtained in Examples 2 to 3 was dissolved in cyclohexanone at 10% by mass or more. Further, the TG-DTA-based 5% mass reduction temperature of the coloring agents obtained in Examples 2 to 3 was 250 ° C or higher.

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 the absorption spectrum was measured. As a result, ε = 600 mol ^-1 cm ^-1 L at 562 nm.

Further, PV-37 is not dissolved in any of 1-methoxy-2-propyl acetate and cyclohexanone even at 0.1% by mass.

<Preparation of Pigment Dispersion>

Modulation example 1

15 parts by mass of CI Pigment Blue 15:6 was used as a coloring agent, and 12.5 parts by mass (solid content concentration = 40% by mass) BYK-LPN21116 (manufactured by BYK Chemie (BYK) Co., Ltd.) was used as a dispersing agent, and 72.5 parts by mass of propylene glycol was used. Monomethyl ether acetate was used as a solvent and treated by bead milling to prepare a pigment dispersion (A-1).

Modulation example 2

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

<Modulation of Dye Solution>

Modulation example 3

The dye solution A was prepared by mixing 5 parts by mass of the compound A as a coloring agent and 95 parts by mass of propylene glycol monomethyl ether acetate as a solvent.

<Synthesis of Adhesive Resin>

In a flask equipped with a cooling tube and a stirrer, 100 parts by mass of propylene glycol monomethyl ether acetate was charged and nitrogen substitution was carried out. The mixture was heated to 80 ° C, and 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, and methacrylic acid 2 were added dropwise at the same temperature for 1 hour. 15 parts by mass of hydroxyethyl ester, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenyl maleimide, and succinic acid mono(2-propenyloxyethyl) 15 A mixed solution of 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and polymerized at this temperature for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and further polymerization was carried out for 1 hour to obtain a binder resin solution (solid content concentration = 33% by mass). The obtained binder resin was Mw = 12,200 and Mn = 6,500. The binder resin was referred to as "binder resin (B1)".

<Modulation and evaluation of coloring composition>

Example 4

13.6 parts by mass of the pigment dispersion liquid (A-1), 27.2 parts by mass of the dye solution A, 16.1 parts by mass of a binder resin (B1) solution as a binder resin, and M manufactured by Toagosei Co., Ltd. as a crosslinking agent -402 (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 5.5 parts by mass with MW-30 (N, N, N', N', N" manufactured by Sanwa Chemical Co., Ltd. N-hexyl(methoxymethyl)melamine as a main component, weight average degree of polymerization 1.3) 2.4 parts by mass, 2-benzyl-2-dimethylamino-1-(4) as a photopolymerization initiator - 2.2 parts by mass of morphylphenyl)butan-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name IRGACURE 369), and propylene glycol monomethyl ether acetate mixed as a solvent to prepare a color composition having a solid concentration of 20% by mass (CR1).

The colored composition (CR1) was applied onto a glass substrate by a spin coater, and then prebaked by a hot plate at 80 ° C for 10 minutes to form a coating film. The number of rotations of the spin coater was changed to form three coating films having different film thicknesses by the same operation.

Then, after the substrates were cooled to room temperature, the radiation containing the respective wavelengths of 365 nm, 405 nm, and 436 nm was exposed to an exposure amount of 2,000 J/m ² for each coating film without using a high-pressure mercury lamp. Thereafter, the developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C was sprayed at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm) on the substrates, and development was carried out for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and further baked in a cleaning 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 by two deflecting plates, and is irradiated with a fluorescent lamp (wavelength range of 380 to 780 nm) from the back side while rotating the deflecting plate on the front side by a luminance meter LS-100 (Minolta) The maximum and minimum values of the transmitted light intensity are determined. Then, for each of the cured films, the value of dividing the maximum value by the minimum value is regarded as a comparison ratio. From the measurement results, 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 liquid (A-1), 4.5 parts by mass of the pigment dispersion liquid (A-2), 16.1 parts by mass of the binder resin (B1) solution as a binder resin, and 5.5 parts by mass as a crosslinking agent. M-402 manufactured by Toagosei Co., Ltd. and 2.4 parts by mass of MW-30 manufactured by Sanwa Chemical Co., Ltd., 2-benzyl-2-dimethylamino-1-(4-) as photoinitiator 2.2 parts by mass of morphylphenyl)butan-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name IRGACURE 369), and propylene glycol monomethyl ether acetate mixed as a solvent to prepare a color composition having a solid concentration of 20% by mass (CR2).

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

In Table 1, "B15:6" means C.I. Pigment Blue 15:6, and "V23" means C.I. Pigment Violet 23.

Claims (10)

A coloring composition comprising a coloring composition of (A) a coloring agent, (B) a binder resin, and (C) a crosslinking agent, wherein the coloring agent (A) contains a formula (1) represented by the following formula (1) Dyeing agent; D(-R-SO ₃ ^- ) _m X ⁺ _m (1) [In the formula (1), D is represented by having -NHCO-, -CONHCO-, -OH, -NH ₂ , -NH a residue of one or more active hydrogens removed from a dye compound of -COCH ₂ CO-, -COOH or -SH, and R represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylene group. A divalent alicyclic hydrocarbon group or a substituted or unsubstituted aryl group, X ⁺ means an organic ammonium ion, and m means an integer of 1 or more. The colored composition of claim 1, wherein the R is an alkyl group, a fluorinated alkyl group or an alkenyl group. The coloring composition of the first aspect of the invention, wherein the organic ammonium ion is represented by the following formula (2) or the following formula (3); In the formulae (2) and (3), Q ¹ to Q ⁵ each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a benzamidine methyl group or a heterocyclic group, and the Q ⁶ group represents a hydrogen atom or a halogen. a hydrocarbyl group, a substituted or unsubstituted hydrocarbon group, an alkoxycarbonyl group, an amine carbenyl group or a benzyloxy group; but at least one of Q ¹ to Q ⁴ represents a substituted or unsubstituted hydrocarbon group]. The colored composition of claim 1, which has a structure represented by the following formula (4); [In the formula (4), R and X ⁺ are synonymous with the above, and "*" means a linkage]. The colored composition of claim 1, wherein the dye compound having 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 pigment compound is The organic 4-grade ammonium salt is obtained by a base exchange reaction; [In the formula (5), the R system is synonymous with the above]. The colored composition of claim 1, wherein the pigment compound is a pigment. The colored composition of the first aspect of the invention, wherein the pigment compound is a compound represented by the following formula (6) or a compound represented by the following formula (7): In the formulae (6) and (7), R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen group, an alkyl group, an alkoxy group, an alkyl-substituted amine group, a trifluoromethyl group or a nitro group, and Z represents Ethoxy]. The colored composition of claim 1, further comprising (D) a photopolymerization initiator. A color filter comprising a coloring layer formed using the colored composition according to any one of claims 1 to 8. A display element comprising the color filter of item 9 of the patent application.