JP2020055990A - Azo pigment, colorant for color filter, colored composition and color filter - Google Patents

Abstract

To provide a colored composition for a color filter, which not only has excellent fastness such as heat resistance and light resistance, few foreign matters in a coating film, and good storage stability or transferability, but also gives high brightness and a reduced film thickness when exhibiting the same color.SOLUTION: The colored composition for a color filter contains an azo pigment comprising a compound represented by the formula below. In the formula, Rrepresents a halogen atom, a substituted/unsubstituted alkyl group, a substituted/unsubstituted alkoxy group, or a substituted/unsubstituted aryloxy group; and Rand Reach independently represent a hydrogen atom, a substituted/unsubstituted alkyl group, or a substituted/unsubstituted phenyl group.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a colorant for a color filter, a coloring composition used for manufacturing a color filter used for a color liquid crystal display device, a color solid-state imaging device, and the like, and a color filter formed using the same.

  In a liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the degree of polarization of light passing through the first polarizing plate and controls the amount of light passing through the second polarizing plate. , And a type using a twisted nematic (TN) type liquid crystal is mainly used. Other typical liquid crystal display systems include an in-plane switching (IPS) system in which a pair of electrodes are provided on one substrate and an electrolysis is applied in a direction parallel to the substrate, and a negative dielectric anisotropy. Vertical alignment (VA) method for vertically aligning nematic liquid crystal having a vertical axis, and optically convenient bend (OCB) method for optically compensating by making the optical axes of uniaxial retardation films orthogonal to each other. Etc., each of which has been put to practical use.

  A liquid crystal display device can display a color by providing a color filter between two polarizing plates. In recent years, the liquid crystal display device has been used for a television, a personal computer monitor, and the like. There is a growing demand for higher brightness.

  The color filter is a filter in which two or more kinds of fine band (stripe) filter segments of different hues are arranged in parallel or intersecting on the surface of a transparent substrate such as glass, or the fine filter segments are arranged in a constant vertical and horizontal direction. It consists of those arranged in. The filter segments are as fine as several microns to several hundred microns, and are arranged in a predetermined arrangement for each hue.

  Generally, in a color liquid crystal display device, a transparent electrode for driving liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. I have. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to form them generally at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a coloring agent is mainly used as a method for producing a color filter.

  The quality items required for the color filter include luminance and contrast ratio. When a color filter having a low contrast ratio is used, the liquid crystal disturbs the controlled degree of polarization, and when light must be blocked (OFF state), light leaks or light must be transmitted (ON state). Since the transmitted light is attenuated in (state), the screen becomes blurred. Therefore, in order to realize a high-quality liquid crystal display device, high contrast is indispensable.

  In addition, when a color filter with low luminance is used, the light transmittance is low, so that a dark screen is obtained. In order to obtain a bright screen, it is necessary to increase the number of backlights as light sources. For this reason, from the viewpoint of suppressing an increase in power consumption, increasing the luminance of a color filter has become a trend. Further, as described above, since the color liquid crystal device has been used for a television, a personal computer monitor, and the like, the color filter has been required to have high luminance and high contrast and high reliability.

  In the red filter segment, which is one of the three primary colors (red, green, blue; RGB) of the color filter substrate, a pigment having excellent light resistance and heat resistance such as a diketopyrrolopyrrole pigment, an anthraquinone pigment or a perylene pigment as a colorant. It is common to use singly or in combination.

  Among the above pigment types, from the viewpoint of luminance, C.I. I. Pigment Red 254 is an anthraquinone pigment from the viewpoint of contrast ratio. I. Pigment Red 177 is used as the main pigment. Among them, C.I. I. Pigment Red 177 has a spectral transmittance of C.I. I. Pigment Red 254 and a poor spectral shape. I. As Pigment Red 177 was added, there was a disadvantage that the luminance was reduced. Therefore, C.I. I. There is a need for the development of Pigment Red 177 alternative material.

  In recent years, in order to realize high brightness and high coloring power, C.I. I. The use of an azo pigment represented by CI Pigment Red 269 or a disazo pigment described in Patent Document 3 as a main pigment has been proposed. However, the affinity of the pigment to a solvent, the acidity of the pigment surface, and the like are C.I. I. Pigment Red 254 and C.I. I. Pigment Red 177, etc., have the disadvantages of being inferior in dispersibility, fluidity, and storage stability, and are also inferior in heat resistance and light resistance, and a practical color filter has not been obtained. C.I. I. In the case of azo pigments such as Pigment Red 269, a decrease in luminance due to color transfer to an adjacent other color filter segment may be a problem, and there is a high demand for transferability.

  Patent Documents 1 to 3 disclose C.I. in order to further improve the luminance of the red filter segment. I. Pigment Red 177, C.I. I. Pigment Red 269 and the disazo pigment described in Patent Document 3 have been proposed as main pigments, but sufficient luminance cannot be obtained, and further improvement has been demanded.

  In the production of the red filter segment, a red pigment and C.I. I. Generally, a yellow pigment such as CI Pigment Yellow 138, 139, or 185 is used in combination as a colorant (Patent Documents 4 to 6). However, in the conventional combination of a red pigment and a yellow pigment, there is no material satisfying both the luminance and the coloring power, and a coloring material having a high coloring power has been required.

JP 2008-304521 A JP-T 2007-533802 JP 2014-160160 A JP 2007-133131A JP 2011095491 A JP 2008-81566 A

  An object of the present invention is to provide a film having excellent heat resistance, light fastness, excellent fastness such as light resistance, less foreign matter in a coating film, good storage stability and good transferability, high brightness, and the same color. An object of the present invention is to provide a color filter coloring composition having a reduced thickness.

As a result of intensive studies, the present inventors have found that the above problems can be solved by using an azo pigment having a specific structure as a colorant for a color filter, and have reached the present invention.

That is, an embodiment of the present invention relates to an azo pigment comprising a compound represented by the following general formula (1).

General formula (1)




[In the general formula (1), R ₁ represents a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent. . R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent. ]

Further, an embodiment of the present invention relates to the azo pigment, comprising a compound represented by the following general formula (2).

General formula (2)


[In the general formula (2), R ₄ represents a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent. . R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent. ]

  Further, an embodiment of the present invention relates to a colorant for a color filter containing the azo pigment.

An embodiment of the present invention is a coloring composition for a color filter comprising at least a coloring agent and a binder resin, wherein the coloring agent contains the coloring agent for a color filter. About things.

  Further, an embodiment of the present invention relates to a coloring composition for a color filter, further comprising a resin-type dispersant having an acidic substituent.

  Further, an embodiment of the present invention relates to a coloring composition for a color filter, wherein the resin-type dispersant having an acidic substituent is a resin-type dispersant having an aromatic carboxyl group.

  Further, an embodiment of the present invention relates to a coloring composition for a color filter, further comprising a dye derivative, wherein the dye derivative contains a dye derivative having a basic substituent.

Further, in the embodiment of the present invention, the coloring agent may further include C.I. I. Pigment Red 254, C.I. I. Pigment Red 242, C.I. I. Pigment yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 185, C.I. I. Pigment yellow 150, at least one selected from the group consisting of a yellow pigment represented by the following general formula (3) and a brominated diketopyrrolopyrrole pigment.

General formula (3)


[In the general formula (3), Z _{1 to} Z ₁₃ each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and a substituent. It may have an aryl group, -SO ₃ H, -COOH, and monovalent to trivalent metal salt thereof acidic groups, alkylammonium salt, an optionally substituted phthalimidomethyl group, or a substituent The following shows a sulfamoyl group which may be possessed.
Adjacent groups of Z _{1 to} Z ₄ and / or Z _{10 to} Z ₁₃ may combine to form an aromatic ring which may have a substituent. ]

  Further, an embodiment of the present invention relates to the coloring composition for a color filter, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

  Further, an embodiment of the present invention relates to a color filter comprising a filter segment formed on the substrate from the coloring composition for a color filter.

Further, an embodiment of the present invention relates to a liquid crystal display device including the color filter.

Further, an embodiment of the present invention relates to a solid-state imaging device including the color filter.

Further, an embodiment of the present invention relates to an organic EL display device including the color filter.

  According to the present invention, heat resistance, excellent fastness such as light resistance, less coating film foreign matter, good storage stability, as well as high brightness and contrast, the film thickness when expressing the same color There is an excellent effect that a coloring composition for a color filter and a color filter which can be thinned can be provided.

FIG. 1 is a schematic sectional view of the liquid crystal display device. FIG. 2 is an example of the emission spectrum of a white organic EL light source (EL-1). The horizontal axis indicates the wavelength, and the vertical axis indicates the emission intensity.

  Hereinafter, the present invention will be described in detail. In the present specification, when “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” is used, Unless otherwise specified, “acryloyl and / or methacryloyl”, “acryl and / or methacryl”, “acrylic and / or methacrylic”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. ]. In addition, “CI” described in this specification means a color index (CI).

<Azo pigment>
First, the azo pigment represented by formula (1) or (2) of the present invention will be described. In the present specification, "azo pigments represented by the general formula (1) or (2)" are abbreviated as "pigments" and "colorants for color filters" are abbreviated as "colorants", respectively. There is.

General formula (1)

  In the general formula (1), parentheses indicate that any two of the hydrogen atoms on anthraquinone are replaced by two nitrogen atoms of the amide.

In the general formula (1), R ₁ represents a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.

In R ₁ "halogen atom", fluorine, bromine, chlorine, mention may be made of iodine, chlorine is preferred among them.

Examples of the “optionally substituted alkyl group” for R ₁ include a methyl group, an ethyl group and n
-Propyl, isopropyl, n-butyl, tert-butyl, isobutyl, tert-amyl, 2-ethylhexyl, stearyl, chloromethyl, trichloromethyl, trifluoromethyl, 2-methoxyethyl Groups, 2-chloroethyl group, 2-nitroethyl group, cyclopentyl group, cyclohexyl group, dimethylcyclohexyl group and the like. Of these, a methyl group and a trifluoromethyl group are preferable.

Examples of the “optionally substituted alkoxyl group” in R ₁ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an n-octyloxy group, a 2-ethylhexyloxy group, Examples thereof include a trifluoromethoxy group, a cyclohexyloxy group, a stearyloxy group, and a 2- (diethylamino) ethoxy group. Among them, a methoxy group and a trifluoromethoxy group are preferable, and a methoxy group is particularly preferable.

Examples of the “aryloxy group optionally having substituent (s)” for R ₁ include a phenoxy group, a naphthyloxy group, a 4-methylphenyloxy group, a 3,5-chlorophenyloxy group, and a 4-chloro-2-methylphenyloxy Groups, 4-tert-butylphenyloxy group, 4-methoxyphenyloxy group, 4-diethylaminophenyloxy group, 4-nitrophenyloxy group, and the like. Of these, a phenoxy group is preferable.

In R ₂ and R ₃ , the “optionally substituted alkyl group” includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an isobutyl group, a tert group -Amyl group, 2-ethylhexyl group, stearyl group, chloromethyl group, trichloromethyl group, trifluoromethyl group, 2-methoxyethyl group, 2-hydroxyethyl group, 2-chloroethyl group, 2-nitroethyl group, cyclopentyl group, Examples thereof include a cyclohexyl group and a dimethylcyclohexyl group, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an isobutyl group, and a 2-hydroxyethyl group are preferred.

In R ₂ and R ₃ , the substituent of the “phenyl group optionally having substituent (s)” is R ₁
A halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and an aryloxy group which may have a substituent, in addition to these, a hydroxyl group, amino group, -NR ₇ R _8, a sulfo _{group, -SO 2 NR 9 R 10,} -COOR 11, -CONR 12 R 13, a nitro group, a cyano group.

R _{7 to} R ₁₃ each independently represent a hydrogen atom or an alkyl group which may have a substituent,
As the “alkyl group optionally having a substituent”, an alkyl group substituted with an amino group, a monoalkylamino group, or a dialkylamino group is preferable.

General formula (2)

In the general formula (2), R ₄ represents a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent. R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.

In R ₄ , "halogen atom", "optionally substituted alkyl group", "optionally substituted alkoxyl group", and "optionally substituted aryloxy group" Is as defined for R ₁ .

In R ₅ and R ₆ , the “alkyl group optionally having substituent (s)” and “phenyl group optionally having substituent (s)” are the same as those in R ₂ and R ₃ .

<Colorant for color filter>
The colorant for a color filter of the present invention contains an azo pigment comprising a compound represented by the general formula (1) or (2). The colorant for a color filter of the present invention includes a pigment other than the pigment containing the compound represented by the general formula (1) or (2) as long as the effects of the present invention are not impaired, for example, for adjusting chromaticity. Alternatively, another colorant such as a dye may be used in combination. These pigments / dyes can be used alone or as a mixture of two or more at any ratio as needed.

  As other coloring agents, for example, C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 269, 270, 272, 273, 274, 276, 277, Red pigments such as 278, 279, 280, 281, 282, 283, 284, 285, 286, or 287. Examples of the red dye include a xanthene dye, an azo (pyridone type, barbituric acid type, etc.) dye, a disazo dye, an anthraquinone dye, and a methine dye. In addition, lake pigments obtained by laking these dyes, inorganic salts of acidic dyes having an acidic group such as sulfonic acid and carboxylic acid, salt-forming compounds of acidic dyes with nitrogen-containing compounds, and sulfonic acid amide compounds of acidic dyes It may be.

C.I. I. Orange pigments such as CI Pigment Orange 43, 71 or 73 and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 1
5, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 21 It can be used in combination with yellow pigment represented by the 214,218,219,220,221 or the following general formula (3). Examples of the orange dye and / or yellow dye include quinoline-based, azo-based (pyridone-based, barbituric acid-based, and metal complex-based), disazo-based, and methine-based dyes.

Preferred among the colorants used in combination are azo, isoindoline, diketopyrrolopyrrole, anthraquinone, quinophthalone, and perylene dyes from the viewpoints of heat resistance, light fastness and chromaticity range. Is mentioned. Specifically, C.I. I. Pigment Red 269, 177, 254, 242, C.I. I. Pigment Yellow 138, 139, 185, 150, a yellow pigment represented by the following general formula (3), and a brominated diketopyrrolopyrrole pigment.
In particular, from the viewpoints of luminance and coloring power, C.I. I. Pigment Red 254, 242, C.I. I. Pigment Yellow 138, 139, 185, 150, a yellow pigment represented by the following general formula (3), and a brominated diketopyrrolopyrrole pigment are more preferred.

General formula (3)


[In the general formula (3), Z _{1 to} Z ₁₃ each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and a substituent. It may have an aryl group, -SO ₃ H, -COOH, and monovalent to trivalent metal salt thereof acidic groups, alkylammonium salt, an optionally substituted phthalimidomethyl group, or a substituent The following shows a sulfamoyl group which may be possessed.
Adjacent groups of Z _{1 to} Z ₄ and / or Z _{10 to} Z ₁₃ may combine to form an aromatic ring which may have a substituent.

  Here, examples of the halogen atom include fluorine, chlorine, bromine and iodine.

  Examples of the alkyl group which may have a substituent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl, and n-octyl. Group, stearyl group, linear or branched alkyl group such as 2-ethylhexyl group, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4- Examples include an alkyl group having a substituent such as a methoxybenzyl group, a 4-nitrobenzyl group, and a 2,4-dichlorobenzyl group.

  Examples of the alkoxyl group which may have a substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutyloxy group, a tert-butyloxy group, a neopentyloxy group, and a 2,3. Linear or branched alkoxyl groups such as -dimethyl-3-pentoxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy And an alkoxyl group having a substituent such as a benzyloxy group.

  Examples of the aryl group which may have a substituent include an aryl group such as a phenyl group, a naphthyl group and an anthranyl group, a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, and a p-methylphenyl group. Methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4 , 5,8-trichloro-2-naphthyl group, anthraquinonyl group, and an aryl group having a substituent such as a 2-aminoanthraquinonyl group.

As the acidic _group, -SO 3 H, -COOH and the like, monovalent these acidic groups to 3
Examples of the valent metal salt include a sodium salt, a potassium salt, a magnesium salt, a calcium salt, an iron salt, an aluminum salt and the like. Examples of the alkylammonium salt of an acidic group include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine and stearylamine, and quaternary alkyls such as palmityltrimethylammonium, dilauryldimethylammonium and distearyldimethylammonium salts. Ammonium salts.

“Substituent in a phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N—CH ₂ —) which may have a substituent and a sulfamoyl group (H ₂ NSO ₂ —) which may have a substituent Examples of the above "include the above-mentioned halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and an aryl group which may have a substituent.

The groups adjacent to Z _{1 to} Z ₄ and / or Z _{10 to} Z _{13 in} the general formula (3) may be combined to form an aromatic ring which may have a substituent. As used herein, the aromatic ring includes a hydrocarbon aromatic ring and a heteroaromatic ring. Examples of the hydrocarbon aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Ring, pyrazine ring, pyrrole ring, quinoline ring, quinoxaline ring, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, oxazole ring, thiazole ring, imidazole ring, pyrazole ring, indole ring, carbazole ring and the like.

  Specific examples of the yellow pigment represented by the general formula (3) used in the colorant for a color filter of the present invention include the following quinophthalone compounds (a) to (ad). It is not limited. The quinophthalone compound used in the present invention can be produced, for example, by the method described in Japanese Patent Publication No. 2930774, but the present invention is not limited to these.

Dyes which can be used in combination are those exhibiting red and purple colors, and preferably have any form of oil-soluble dyes, acid dyes, direct dyes and basic dyes.
Among these, it is preferable to use a xanthene-based oil-soluble dye, a xanthene-based basic dye, and a xanthene-based acid dye because of excellent hue. In addition, lake pigments obtained by laking these dyes, inorganic salts of acidic dyes having an acidic group such as sulfonic acid and carboxylic acid, salt-forming compounds of acidic dyes with nitrogen-containing compounds, and sulfonic acid amide compounds of acidic dyes It may be.

Xanthene-based oil-soluble dyes include C.I. I. Solvent Red 35, C.I. I. Solvent Red 36, C.I. I. Solvent Red 42, C.I. I. Solvent Red 43, C.I. I. Solvent Red 44, C.I. I. Solvent Red 45, C.I. I. Solvent Red 46, C.I. I. Solvent Red 47, C.I. I. Solvent Red 48, C.I. I. Solvent Red 49, C.I. I. Solvent Red 72, C.I. I. Solven Red 73, C.I. I. Solvent Red 109, C.I. I. Solvent Red 140, C.I. I. Solvent Red 141, C.I. I. Solvent Red 237, C.I. I. Solvent Red 246, C.I. I. Solvent Violet 2, C.I. I. Solvent Violet 10 and the like. Among them, C.I. I. Solvent Red 35, C.I. I. Solvent Red 36, C.I. I. Solvent Red 49, C.I. I. Solvent Red 109, C.I. I. Solvent Red 237, C.I. I. Solvent Red 246, C.I. I. Solvent Violet 2 is more preferred.
Xanthene-based basic dyes include C.I. I. Basic Red 1 (rhodamine 6GCP), 8 (rhodamine G), C.I. I. Basic Violet 10 (rhodamine B) and the like. Among them, C.I. I. Basic Red 1, C.I. I. It is preferable to use the basic violet 10.
Xanthene-based acid dyes include C.I. I. Acid Red 51 (erythrosine (edible red No. 3)), C.I. I. Acid red 52 (acid rhodamine), C.I. I. Acid Red 87 (Eosin G (edible red No. 103)), C.I. I. Acid Red 92 (Acid Phloxine PB (edible red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (edible red No. 5), Acid Rhodamine G, C.I. I. Acid violet 9 is preferably used.
Above all, in terms of heat resistance and light resistance, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388 or C.I. I. Acid red 52 (acid rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. It is more preferable to use Acid Violet 9.
Among these dyes, C.I. which is a rhodamine-based acid dye is particularly preferred in that it is excellent in coloring property, heat resistance and light resistance. I. It is most preferable to use Acid Red 52.

  When used in combination with the above-mentioned red pigment, yellow pigment, orange pigment, or dye, the content of the pigment containing the compound represented by the general formula (1) or (2) is 10% by mass in the total of 100% by mass of the coloring agent. ９０90% by mass, preferably 20-80% by mass. When the content of the pigment containing the compound represented by the general formula (1) or (2) is less than 10% by mass, the excellent effects of luminance and coloring power cannot be sufficiently exhibited.

<Average primary particle diameter of pigment>
The average primary particle diameter of the pigment was measured (calculated) by the following method.
Propylene glycol monomethyl ether acetate was added to the pigment powder, a small amount of Disperbyk-161 was added as a resin-type dispersant, and the mixture was dispersed with an ultrasonic cleaner for 1 minute to prepare a measurement sample. Using a transmission electron microscope (“JEM-1200EX” manufactured by JEOL Ltd.), three photographs (for three visual fields) in which primary particles of 100 or more pigments can be confirmed were taken of this sample, and 100 photographs were taken in order from the upper left in each case. Was measured for the size of primary particles. Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment are measured in units of nm, the average is defined as the primary particle diameter of the pigment, and a distribution of a total of 300 particles is created at intervals of 5 nm. The median of the steps (for example, 8 nm in the case of 6 nm or more and 10 nm or less) was approximated as the particle diameter of those particles, and the number average particle diameter was calculated by calculating based on each particle diameter and the number thereof.

<Refinement of colorant>
The pigment used in the present invention can be used after being refined. The pigment containing the compound represented by the general formula (1) or (2) is also preferably used in a finely divided form, but the method for making finer is not particularly limited. For example, wet grinding, dry grinding Any of the dissolution and precipitation methods can be used, and a salt milling treatment by a kneader method, which is one type of wet grinding, can be performed as exemplified in the present invention.

The primary particle size of the finely divided pigment is preferably 20 nm or more, since dispersion in the colorant carrier is good. Further, the thickness is preferably 100 nm or less because a filter segment having a high contrast ratio can be formed. A particularly preferred range is 25 to 85 nm
Range.

  Salt milling treatment is to heat a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent using a kneader such as a kneader, a trimix, a two-roll mill, a three-roll mill, a ball mill, an attritor, and a sand mill. This is a process of removing water-soluble inorganic salts and water-soluble organic solvents by washing with water after mechanically kneading. The water-soluble inorganic salt functions as a crushing aid, and the pigment is crushed by utilizing the hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution range, and a sharp particle size distribution.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used in terms of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2,000 parts by mass, and most preferably 300 to 1,000 parts by mass, based on 100 parts by mass of the coloring agent, from both the processing efficiency and the production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) with water and does not substantially dissolve the inorganic salt to be used. However, since the temperature rises during salt milling and the solvent is likely to evaporate, a high boiling solvent having a boiling point of 120 ° C. or higher is preferred from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by mass, and most preferably 50 to 500 parts by mass, based on 100 parts by mass of the colorant.

  When the pigment is subjected to the salt milling treatment, a resin may be added as necessary. The type of the resin used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin used is preferably solid at room temperature, insoluble in water, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by mass with respect to 100 parts by mass of the colorant.

  Further, when the pigment is subjected to the salt milling treatment, a dye derivative described later may be added as necessary. The structure of the dye derivative used is not particularly limited, and examples thereof include compounds in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent is introduced into an organic pigment, anthraquinone, acridone or triazine. Can be These can be used alone or in combination of two or more.

  The use amount of these dye derivatives is preferably 2 to 30 parts by mass, and most preferably 5 to 20 parts by mass, based on 100 parts by mass of the coloring agent.

<Coloring composition for color filter>
The coloring composition for a color filter of the present invention comprises a binder resin in addition to the coloring agent described above.

<Binder resin>
The binder resin disperses, dyes, or penetrates the colorant, and includes a thermoplastic resin and the like. When used in the form of an alkali-developed colored resist material, it is preferable to use an alkali-soluble vinyl resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can be used.

  In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain for an alkali-developing colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. By doing so, the colorant is fixed, the heat resistance is improved, and fading (deterioration of spectral characteristics) due to heat of the colorant can be suppressed. Also, in the developing step, there is an effect of suppressing aggregation and precipitation of the colorant component.

  The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, and more preferably in the range of 10,000 to 80,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When the binder resin is used as a photosensitive coloring composition for a color filter, a carboxyl group serving as a colorant-adsorbing group and an alkali-soluble group during development, an aliphatic group serving as an affinity group for a colorant carrier and a solvent, and The balance of the aromatic group is important for the dispersibility, penetrability, developability, and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in a developer is poor, and it is difficult to form a fine pattern. If it exceeds 300 mgKOH / g, no fine pattern remains.

  The binder resin of the general formula (1) is preferably used in an amount of 20 parts by mass or more with respect to the total mass of 100 parts by mass of the colorant, since the binder resin has good film formability and various resistances. Since good color characteristics can be exhibited, it is preferable to use the compound in an amount of 1000 parts by mass or less.

  As the thermoplastic resin used for the binder resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate , Polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. . Among them, it is preferable to use an acrylic resin.

Examples of the vinyl-based alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include a resin having an acidic group such as a carboxyl group and a sulfone group.
Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydride) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Isobutylene / (anhydride) maleic acid copolymer; Above all, an acrylic resin having an acidic group and at least one resin selected from styrene / styrenesulfonic acid copolymers, particularly an acrylic resin having an acidic group, are preferably used because of their high heat resistance and high transparency.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include a resin into which an unsaturated ethylenic double bond has been introduced by the following method (i) or (ii).

[Method (i)]
In the method (i), for example, the side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers is used. The carboxyl group of an unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and further, the generated hydroxyl group is reacted with a polybasic acid anhydride to form an unsaturated ethylenic double bond and a carboxyl group. There is a way to introduce it.

  Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4 epoxybutyl (meth) acrylate, And 3,4 epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more. Glycidyl (meth) acrylate is preferred from the viewpoint of reactivity with the unsaturated monobasic acid in the next step.

  Examples of the unsaturated monobasic acid include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl (meth) acrylic acid, alkoxyl, halogen, nitro and cyano-substituted products. Monocarboxylic acids may be used, and these may be used alone or in combination of two or more.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, and these may be used alone or in combination of two or more. I don't care. Increasing the number of carboxyl groups, etc., if necessary, using a tricarboxylic anhydride such as trimellitic anhydride, or using a tetracarboxylic dianhydride such as pyromellitic dianhydride, the remaining anhydride Hydrolysis of the group is also possible. When tetrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be further increased.

  As a similar method to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group with one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is subjected to an addition reaction to a part of the carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

[Method (ii)]
In the method (ii), an unsaturated ethylenic monomer having a hydroxyl group is used, and another unsaturated monobasic acid monomer having a carboxyl group or another monomer is copolymerized. There is a method in which an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group is reacted with a side chain hydroxyl group of the obtained copolymer.

Examples of the unsaturated ethylenic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate and cyclohexanedimethanol mono (meth) acrylate, which may be used alone or in combination of two or more. Further, a polyether mono (meth) acrylate obtained by addition-polymerizing ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) ester mono (meth) acrylate to which (poly) 12-hydroxystearic acid or the like has been added. From the viewpoint of suppressing paint film foreign matter, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferred.

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, but are not limited thereto. Instead, two or more types can be used in combination.

<Organic solvent>
In the coloring composition of the present invention, a coloring agent is sufficiently dispersed and penetrated in a coloring agent carrier, and applied on a substrate such as a glass substrate so that a dry film thickness is 0.2 to 5 μm to form a filter segment. An organic solvent can be included to facilitate formation. The organic solvent is selected in consideration of not only good coating properties of the coloring composition but also solubility of each component of the coloring composition and further safety.

Examples of the organic solvent include 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, , 4-Dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 3-ethoxypropionic acid Ethyl, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide , N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene , P-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl Ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether Teracetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether , Diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipro Len glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol Phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether pro Onato, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters. These solvents can be used alone or as a mixture of two or more kinds in an optional ratio as needed.

  The solvent can be used in an amount of 100 to 10000 parts by mass, preferably 500 to 5000 parts by mass, based on 100 parts by mass of the coloring agent in the coloring composition.

<Photopolymerizable monomer>
The photopolymerizable monomer that may be added to the coloring composition of the present invention includes a monomer or an oligomer that is cured by ultraviolet light or heat to form a transparent resin.

  Examples of monomers and oligomers which are cured by ultraviolet light or heat to produce a transparent resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycine Di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, (meth) acrylate of methylolated melamine, epoxy (meth) acrylate, urethane acrylate and other acrylates and methacrylates, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (Meth) acrylamide, N-vinylformamide, acrylonitrile and the like, but are not necessarily limited thereto. These photopolymerizable compounds can be used singly or as a mixture of two or more at any ratio as needed.

  The content of the photopolymerizable monomer is preferably from 5 to 500 parts by mass, more preferably from 10 to 400 parts by mass from the viewpoint of photocurability and developability, based on 100 parts by mass of the colorant. .

<Photopolymerization initiator>
The coloring composition of the present invention is prepared by curing the composition by ultraviolet irradiation and adding a photopolymerization initiator to form a filter segment by a photolithography method. Can be prepared.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Is a benzoin-based compound such as benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenylsulfide, or 3,3 ′, Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone Thioxanthones such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy) Enyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, -(4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] Or an oxime ester compound such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; An imidazole compound; or a titanocene compound or the like is used. One of these photopolymerization initiators may be used alone, or two or more of them may be used in an optional ratio as needed.

  The content of the photopolymerization initiator is preferably from 1 to 500 parts by mass, more preferably from 5 to 400 parts by mass, from the viewpoint of photocurability and developability based on 100 parts by mass of the coloring agent.

<Sensitizer>
Further, the coloring composition for a color filter of the present invention may contain a sensitizer.
Examples of the sensitizer include unsaturated ketones such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxanol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivative, azulhenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, Trapyrazino porphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxaliloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyllin derivative, annulene derivative, spiropyran derivative, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, Michler's ketone derivatives and the like. One of these sensitizers can be used alone, or two or more of them can be used in an optional ratio as needed.

Further examples include Shin Okawara et al., “Dye Handbook” (1986, Kodansha), Shin Okawara et al., “Chemistry of Functional Dyes” (1981, CMC), Chusaburo Ikemori et al.,
Sensitizers described in "Specially Functional Materials" (1986, CMC), but are not limited thereto. In addition, a sensitizer that absorbs light in the ultraviolet to near infrared region can be contained.
Among the above sensitizers, particularly suitable sensitizers include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.

  The content of the sensitizer is preferably 3 to 60 parts by mass with respect to 100 parts by mass of the photopolymerization initiator contained in the coloring composition, and from the viewpoint of photocurability and developability, 5 to 50 parts by mass. Is more preferable.

<Polyfunctional thiol>
The coloring composition for a color filter of the present invention can contain a polyfunctional thiol. A polyfunctional thiol is a compound having two or more thiol (SH) groups. By using the polyfunctional thiol together with the above-mentioned photopolymerization initiator, it acts as a chain transfer agent in the radical polymerization process after light irradiation, and generates thiyl radicals that are less susceptible to polymerization inhibition by oxygen. The composition becomes highly sensitive. Particularly, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as a methylene or ethylene group is preferable.

  Examples of the polyfunctional thiol include hexane dithiol, decane dithiol, 1,4-butanediol bisthioglycolate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropiolate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolethanetris (3-mercaptobutyrate), trimethylolpropanetris (3-mercaptobutyrate), trimethylolpropanetris (3- Mercaptopropionate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropione) G), dipentaerythritol hexakis (3-mercaptopropionate), tris (2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s- Triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine and the like. These polyfunctional thiols can be used alone or as a mixture of two or more at any ratio as needed.

The content of the polyfunctional thiol is preferably 0.05 to 100 parts by mass, more preferably 1.0 to 50.0 parts by mass, based on 100 parts by mass of the coloring agent.
By using 0.05 parts by mass or more of the polyfunctional thiol, better development resistance can be obtained. When a monofunctional thiol having one thiol (SH) group is used, such improvement in development resistance cannot be obtained.

<Leveling agent>
It is preferable to add a leveling agent to the coloring composition of the present invention in order to improve the leveling property of the composition on the transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray Co., Ltd.
And BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. Usually, the content of the leveling agent is preferably 0.003 to 1.0 part by mass based on 100 parts by mass of the total mass of the coloring composition.

  Particularly preferred as a leveling agent is a kind of a so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a low solubility in water while having a hydrophilic group, and when added to a coloring composition, It has the feature that surface tension lowering ability is low, and even though the surface tension lowering ability is low, it is useful that the wettability to the glass plate is good, and at the amount of addition that does not cause defects in the coating film due to foaming Those which can sufficiently suppress the charging property can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes a polyethylene oxide unit and a polypropylene oxide unit, and the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  The bonding form of the polyalkylene oxide unit with dimethylpolysiloxane is a pendant type in which the polyalkylene oxide unit is bonded in a repeating unit of dimethylpolysiloxane, a terminal-modified type in which the polyalkylene oxide unit is bonded to a terminal of dimethylpolysiloxane, and dimethylpolysiloxane. Any of a linear block copolymer type alternately and repeatedly bonded may be used. Dimethyl polysiloxane having a polyalkylene oxide unit is commercially available from Dow Corning Toray Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ -2207, but is not limited thereto.

  Anionic, cationic, nonionic, or amphoteric surfactants can be added to the leveling agent in an auxiliary manner. Two or more surfactants may be used as a mixture. Examples of anionic surfactants to be added to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, alkyldiphenyletherdisulfonate Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, styrene-acrylic acid copolymer monoethanolamine, polyoxyethylene alkyl ether phosphate Esters and the like.

  Examples of the chaotic surfactant supplementally added to the leveling agent include an alkyl quaternary ammonium salt and an ethylene oxide adduct thereof. Nonionic surfactants to be added to the leveling agent supplementally include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate And polyethylene glycol monolaurate. Examples of the amphoteric surfactant to be added to the leveling agent include alkyl betaines such as alkyldimethylaminoacetate betaine and amphoteric surfactants such as alkylimidazoline.

<Ultraviolet absorber, polymerization inhibitor>
The coloring composition for a color filter of the present invention may contain an ultraviolet absorber or a polymerization inhibitor. By containing an ultraviolet absorber or a polymerization inhibitor, the shape and resolution of the pattern can be controlled.

  Examples of the ultraviolet absorbent include 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl). -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine and the like Hydroxyphenyltriazine, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, Benzotriazoles such as 2- (3-tbutyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole; Benzophenones such as droxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, and salicylates such as phenyl salicylate and p-tert-butylphenyl salicylate. , Cyanoacrylates such as ethyl-2-cyano-3,3'-diphenylacrylate, 2,2,6,6-tetramethylpiperidine-1-oxyl (triacetone-amine-N-oxyl), bis (2 , 2,6,6-tetramethyl-4-piperidyl) -sebacate, poly [[6-[(1,1,3,3-tetrabutyl) amino] -1,3,5-triazine-2,4-diyl ] ((2,2,6,6-tetramethyl-4-piperidinyl) imino] and the like. These ultraviolet absorbers can be used alone or as a mixture of two or more at any ratio as needed.

  Examples of the polymerization inhibitor include hydroquinones such as methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol. Derivatives and phenolic compounds, amine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, copper such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, and manganese diphenyldithiocarbamate And manganese salt compounds, such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine Toroso compounds and their ammonium salts or aluminum salts and the like. One of these polymerization inhibitors may be used alone, or two or more thereof may be used in an optional ratio as needed.

The ultraviolet absorber and the polymerization inhibitor can be used in an amount of 0.01 to 20 parts by mass, preferably 0.05 to 10 parts by mass, based on 100 parts by mass of the coloring agent in the coloring composition.
Better resolution can be obtained by using 0.01 parts by mass or more of the ultraviolet absorber or the polymerization inhibitor.

<Antioxidant>
The coloring composition for a color filter of the present invention can contain an antioxidant in order to increase the transmittance of the coating film. The antioxidant prevents the photopolymerization initiator contained in the coloring composition for a color filter from being oxidized and yellowed by a heat process at the time of heat curing or ITO annealing. it can. Therefore, by containing an antioxidant, yellowing due to oxidation during the heating step can be prevented, and high transmittance of the coating film can be obtained.

  Preferred examples of the antioxidant include a hindered phenol-based antioxidant, a hindered amine-based antioxidant, a phosphorus-based antioxidant, and a sulfide-based antioxidant. Further, more preferred are a hindered phenol-based antioxidant, a hindered amine-based antioxidant, and a phosphorus-based antioxidant. These antioxidants can be used alone or as a mixture of two or more at any ratio as needed.

  Hindered phenolic antioxidants include 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) and 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5- Di-t-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and the like.

  Hindered amine antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N , N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4- Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3,4 -Butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} (2,2,6,6- Tetramethyl-4-piperidyl) Mino {hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl)} (2,2 , 6,6-tetramethyl-4-piperidyl) imino {hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl) -4 Polycondensate with N-hydroxy-2,2,6,6-tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2, 6,6-pentamethyl-4-piperidyl) amino {-1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine and the like.

  Phosphorus antioxidants include tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphepin- 6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-2- Yl) oxy] ethyl] amine, and ethyl bis (2,4-ditert-butyl-6-methylphenyl) phosphite.

  Examples of sulfide antioxidants include 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like.

  The content of the antioxidant is preferably 0.1 to 5 parts by mass based on 100 parts by mass of the total solid content of the coloring composition for a color filter. When the amount of the antioxidant is less than 0.1 part by mass, the effect of increasing the transmittance is small, and when the amount is more than 5 parts by mass, the hardness is largely reduced and the sensitivity of the coloring composition for a color filter is greatly reduced.

<Other ingredients>
The coloring composition for a color filter of the present invention contains an adhesion improver such as a silane coupling agent or the like, or an amine compound having a function of reducing dissolved oxygen, in order to enhance the adhesion with the transparent substrate. Can be done.

Examples of the silane coupling agent include vinyl silanes such as vinyl tris (β-methoxyethoxy) silane, vinyl ethoxy silane and vinyl trimethoxy silane, (meth) acryl silanes such as γ-methacryloxypropyl trimethoxy silane, and β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxy Epoxysilanes such as cyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (Aminoethyl) γ-ami Propyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, Examples include aminosilanes such as N-phenyl-γ-aminopropyltriethoxysilane and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

  The silane coupling agent can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the coloring agent in the coloring composition.

  Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl-dimethylaminobenzoate, N, N-dimethylparatoluidine and the like.

<Production method of coloring composition for color filter>
The coloring composition for a color filter of the present invention comprises a kneader, a two-roll mill, a three-roll mill, a ball mill, and a colorant in a colorant carrier such as a resin and / or a solvent, if necessary, together with a dispersing aid. It can be finely dispersed using various dispersing means such as a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). At this time, two or more kinds of colorants or the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. The epoxy compound may be added at the stage of preparing the colorant dispersion, and the same effect can be obtained by adding the epoxy compound later to the prepared colorant dispersion. When the solubility of a coloring agent such as a dye is high, specifically, the solubility in a solvent to be used is high, and the mixture is dissolved by stirring, if the foreign matter is not confirmed, the fine dispersion as described above is produced. No need.

  When used as a photosensitive coloring composition (resist material) for a color filter, it can be prepared as a solvent developing type or alkali developing type coloring composition. The solvent-developable or alkali-developable coloring composition comprises the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent and other pigment dispersants and additives. And the like can be mixed. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

<Dispersion aid>
When dispersing the colorant in the colorant carrier, it is preferable to appropriately include a dispersing aid such as a resin-type dispersant, a dye derivative, and a surfactant. Since the dispersing aid has a large effect of preventing the re-aggregation of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersing aid has a luminance and storage stability. Become good.

<Resin type dispersant>
The resin-type dispersant has a colorant affinity site having a property of adsorbing to the colorant, and a site compatible with the colorant carrier, and adsorbs on the colorant to disperse the colorant into the colorant carrier. It works to stabilize. Specific examples of the resin-type dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, and polycarboxylic acid alkylamine salt. , Polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylic esters, modified products thereof, amides and salts thereof formed by the reaction of poly (lower alkyleneimine) with a polyester having a free carboxyl group Such as oil-based dispersants, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Resins, water-soluble polymer compounds, polyesters, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan. , 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -P104, P104S, 220S, 6919, or LACTIMON, LACTIMON-WS or Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 160 manufactured by Lubrizol Japan, Ltd. 0, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320 , 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554 1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

Further, as the resin-type dispersant used in the present invention, those having an acidic substituent are preferable, and among them, those having an aromatic carboxyl group are particularly preferable because the effect of preventing re-aggregation of the colorant after dispersion is particularly large. . As the resin-type dispersant having an aromatic carboxyl group, one containing the following (S1) or (S2) is preferable.
(S1) A resin-type dispersant which is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride and / or a tetracarboxylic dianhydride.
(S2) A polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride and / or a tetracarboxylic dianhydride. Resin-type dispersant which is united.

[Resin type dispersant (S1)]
The resin-type dispersant (S1) can be produced by a known method such as WO 2008/007776, JP-A-2008-029901, JP-A-2009-155406. The polymer having a hydroxyl group (p) is preferably a polymer having a hydroxyl group at a terminal. For example, an ethylenically unsaturated monomer (r) was polymerized in the presence of a compound having a hydroxyl group (q). It can be obtained as a polymer. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Since the terminal hydroxyl group is preferably plural, a compound (q1) having two hydroxyl groups and one thiol group in the molecule is particularly preferably used.

  That is, a polymer having two hydroxyl groups at one end, which is a more preferable example, is obtained by preparing a monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. Can be obtained as a polymer (p1) obtained by polymerizing the ethylenically unsaturated monomer (r). The hydroxyl group of the polymer (p) having a hydroxyl group reacts with an acid anhydride group of a tricarboxylic anhydride and / or a tetracarboxylic dianhydride to form an ester bond, while the anhydride ring opens to form a carboxylic acid. Is generated.

[Resin type dispersant (S2)]
The resin-type dispersant (S2) can be produced by a known method such as JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, and for example, a compound having a hydroxyl group. By polymerizing the ethylenically unsaturated monomer (r) in the presence of a reaction product of the hydroxyl group of (q) and an acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride. can get. Above all, in the presence of a reaction product of a hydroxyl group of a compound (q1) having two hydroxyl groups and one thiol group in a molecule, and an acid anhydride group of a tricarboxylic anhydride and / or a tetracarboxylic dianhydride. And a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) containing a monomer (r1).

  The difference between (S1) and (S2) is whether the introduction of the polymer site obtained by polymerizing the ethylenically unsaturated monomer (r) is performed first or later. Although the molecular weight and the like may be slightly different depending on various conditions, if the raw materials and the reaction conditions are the same, theoretically the same can be obtained.

  The resin-type dispersant is preferably used in an amount of about 5 to 200 parts by weight, more preferably about 5 to 100 parts by weight, from the viewpoint of film forming properties.

<Dye derivative>
It is preferable that the coloring composition for a color filter of the present invention further contains a dye derivative. The dye derivative may be contained in the azo pigment.
As the dye derivative used in the present invention, a known dye derivative having an acidic dye, a basic group, a neutral group, or the like in an organic dye residue can be used. For example, compounds having an acidic functional group such as a sulfo group, a carboxy group, and a phosphoric acid group and amine salts thereof, compounds having a basic functional group such as a sulfonamide group or a tertiary amino group at a terminal, a phenyl group or a phthalimide Compounds having a neutral functional group such as an alkyl group are mentioned. Examples of the organic dye include phthalocyanine pigments such as diketopyrrolopyrrole pigments, copper phthalocyanine, zinc phthalocyanine, aluminum phthalocyanine, copper phthalocyanine halide, zinc phthalocyanine halide, aluminum phthalocyanine halide, and metal-free phthalocyanine, aminoanthraquinone, and diamino. Anthraquinone pigments such as dianthraquinone, anthrapyrimidine, flavanthrone, anthantrone, indanthrone, pyranthrone, biolanthrone, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, Benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinoff Ron pigments, naphthol pigments, threne pigments, metal complex pigments, azo, disazo, azo pigments such as polyazo, and the like.
More specifically, JP-A-61-246261, JP-A-63-26467, JP-A-09-272812, JP-A-10-245501, JP-A-10-265597, JP-A-11-199796, JP-A-2001-172520, JP-A-2001-220520, JP-A-2002-201377, JP-A-2003-165922, JP-A-2003-168208, JP-A-2003-2003 JP-A-171594, JP-A-2004-217842, JP-A-2005-213404, JP-A-2006-291194, JP-A-2007-079094, JP-A-2007-226161, JP-A-2007-314681 JP, JP-A-2007-314785, JP-A-2008-3 No. 281, JP-A-2009-57478, WO2009 / 025325, WO2009 / 081930, JP2011-162662, WO2011 / 052617, JP2012-172092, JP2012 JP-A-208329, JP-A-2012-226110, WO2012 / 102399, JP-A-2014-5439, WO2016 / 163351, JP-A-2017-156397, and JP-A-5575266. And these can be used alone or in combination of two or more. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a pigment dispersant, or simply a compound, and the like, but the above-described organic dye residue includes an acidic group, a basic group, and a neutral group. The compound having the functional group is synonymous with the dye derivative.

  Among the dye derivatives used in the present invention, a dye derivative having a basic substituent is preferable because the effect of suppressing aggregation between pigments is remarkable. Further, those derived from diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, quinophthalone-based pigments and azo-based pigments as organic dye residues are preferred from the viewpoint of hue and contrast.

<Surfactant>
As the surfactant, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate Anionic surfactants such as monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphate, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; Chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkyl betaines such as betaine acetate and alkyl imidazolines. These can be used alone or as a mixture of two or more, but are not necessarily limited thereto.

  When a surfactant is added, the amount is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass, per 100 parts by mass of the colorant. When the content of the surfactant is less than 0.1 part by mass, it is difficult to obtain the added effect, and when the content is more than 55 parts by mass, the dispersion may be affected by an excessive dispersant. .

<Removal of coarse particles>
The colored composition of the present invention is obtained by means of centrifugation, filtration using a sintered filter or a membrane filter, or the like, and coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more. It is preferable to remove the mixed dust. As described above, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention includes a red filter segment, a green filter segment, and a blue filter segment on a base material, and further includes a magenta filter segment, a cyan filter segment, or a yellow filter segment. And the at least one filter segment is formed from the coloring composition of the present invention.

<Production method of color filter>
The color filter of the present invention can be manufactured by a printing method or a photolithography method. Since the formation of the filter segment by the printing method can be performed by repeating the printing and drying of the coloring composition prepared as the printing ink, the patterning can be performed at low cost and excellent in mass productivity as a color filter manufacturing method. Further, fine patterns having high dimensional accuracy and smoothness can be printed by the development of printing technology. In order to perform printing, it is preferable that the composition be such that the ink does not dry and solidify on a printing plate or on a blanket. It is also important to control the fluidity of the ink on the printing press, and the viscosity of the ink can be adjusted by a dispersant or extender.

  When the filter segment is formed by a photolithography method, the coloring composition prepared as the solvent-developable or alkali-developable colored resist material is coated on a transparent substrate by spray coating, spin coating, slit coating, roll coating, or the like. According to the method, coating is performed so that the dry film thickness becomes 0.2 to 5 μm. The film dried as required is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like to remove an uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Further, in order to promote the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the printing method can be manufactured.

In the development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as an alkali developing solution, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developer.
In order to increase the UV exposure sensitivity, the above-mentioned colored resist material is applied and dried, and then a water-soluble or alkali-water-soluble resin, such as polyvinyl alcohol or a water-soluble acrylic resin, is applied and dried to form a film for preventing polymerization inhibition by oxygen. After that, ultraviolet exposure can be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink-jet method or the like in addition to the above-mentioned methods, and the coloring composition of the present invention can be used in any method. The electrodeposition method is a method of producing a color filter by forming each color filter segment on a transparent conductive film by electrophoresis of colloid particles using a transparent conductive film formed on a substrate. . The transfer method is a method in which a filter segment is previously formed on the surface of a peelable transfer base sheet, and the filter segment is transferred to a desired substrate.

  Before forming each color filter segment on a substrate such as a transparent substrate or a reflective substrate, a black matrix can be formed in advance. As the black matrix, a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. Alternatively, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. On the color filter of the present invention, an overcoat film, a transparent conductive film or the like is formed as necessary.

The dry film thickness of the filter segment and the black matrix is preferably from 0.2 to 10 μm, more preferably from 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

  The color filter is adhered to the counter substrate using a sealant, the liquid crystal is injected from the injection port provided in the seal section, and then the injection port is sealed.If necessary, a polarizing film or a retardation film is formed on the outside of the substrate. By laminating, a liquid crystal display panel is manufactured.

  Such liquid crystal display panels include Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertically Alignment (VA), Optically Convenient Bend (OCB). It can be used in a liquid crystal display mode for performing colorization using a color filter such as.

  As the transparent substrate, a glass plate such as soda lime glass, low alkali borosilicate glass, and alkali-free aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used. Further, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate for driving the liquid crystal after paneling.

<Liquid crystal display device>
A liquid crystal display device including the color filter of the present invention will be described.
A liquid crystal display device of the present invention includes the color filter of the present invention and a light source. Examples of the light source include a cold cathode fluorescent lamp (CCFL) and a white LED. However, in the present invention, it is preferable to use a white LED from the viewpoint that the red reproduction region is widened. FIG. 1 is a schematic sectional view of a liquid crystal display device 10 including the color filter of the present invention. The device 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 arranged so as to face each other, and a liquid crystal LC is sealed between them.

The liquid crystal LC is aligned according to a driving mode such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane switching), VA (Vertical Alignment), OCB (Optically Compensated Birefringence), and the like. On the inner surface of the first transparent substrate 11,
A TFT (thin film transistor) array 12 is formed, on which a transparent electrode layer 13 made of, for example, ITO is formed. An alignment layer 14 is provided on the transparent electrode layer 13. Further, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

  On the other hand, the color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. The red, green and blue filter segments constituting the color filter 22 are separated by a black matrix (not shown).

  A transparent protective film (not shown) is formed as needed to cover the color filter 22, and a transparent electrode layer 23 made of, for example, ITO is further formed thereon. Is provided.

  A polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Note that a backlight unit 30 is provided below the polarizing plate 15.

Examples of the white LED light source include a light source in which a fluorescent filter is formed on the surface of a blue LED, and a light source in which a phosphor is contained in a resin package of a blue LED, and a wavelength at which the emission intensity is maximized within a range of 430 nm to 485 nm ( λ3), has a wavelength (λ4) at which the emission intensity is maximum in the range of 530 nm to 580 nm, has a wavelength (λ5) at which the emission intensity is maximum within the range of 600 nm to 650 nm, and has a wavelength. The ratio (I4 / I3) of the emission intensity I3 at λ3 to the emission intensity I4 at the wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio of the emission intensity I3 at the wavelength λ3 to the emission intensity I5 at the wavelength λ5 (I5 / I3 ) Having a spectral characteristic of 0.1 or more and 1.3 or less and a wavelength (λ1) at which the emission intensity becomes maximum within a range of 430 nm to 485 nm. And has a second emission intensity peak wavelength (λ2) in the range of 530 nm to 580 nm, and the ratio (I2 / I1) of the emission intensity I1 at the wavelength λ1 to the emission intensity I2 at the wavelength λ2 is 0.2 to 0. A white LED light source (LED2) having a spectral characteristic of 0.7 or less is preferable.

  Specific examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation) and NSSW304D-HG-V1 (manufactured by Nichia Corporation).

  Specific examples of the LED 2 include NSSW440 (manufactured by Nichia), NSSW304D (manufactured by Nichia), and the like.

<Organic EL display device>
The organic EL display device according to the present invention includes a color filter formed of a coloring composition containing an azo pigment characterized by comprising a compound represented by the general formula (1), and a white light-emitting organic EL element (hereinafter, referred to as a color filter). It is preferable that the display device has an organic EL element) as a light source.

(Organic EL device (white light emitting organic EL device))
The organic EL element used in the present invention has peak wavelengths λ1 and λ2 at which the light emission intensity is maximized in at least a wavelength range of 430 nm to 485 nm and a wavelength range of 560 nm to 620 nm. It is preferable that a ratio (I2 / I1) of the emission intensity I2 at the wavelength λ2 has an emission spectrum of 0.4 or more and 0.9 or less, and more preferably 0.5 or more and 0.8 or less. . Especially preferably, it is 0.5 or more and 0.7 or less.
It is preferable to have an emission spectrum in which the ratio of the emission intensity I2 (I2 / I1) is 0.4 or more and 0.9 or less, because high brightness and wide color reproducibility can be obtained.

Further, it preferably has a maximum value of the emission intensity or a shoulder in a wavelength range of 530 nm to 650 nm.
The wavelength range of 430 nm to 485 nm is preferable when a color display device including the color filter displays blue with good color reproducibility. More preferably, it is in the range of 430 nm to 475 nm.
By using an organic EL element satisfying these configurations and the color filter, a color display device having a wide color reproduction region and high brightness can be obtained.

  The organic EL device is constituted by a device in which one or more organic layers are formed between an anode and a cathode. Here, a single-layer organic EL element refers to an element including only a light-emitting layer between an anode and a cathode. On the other hand, a multilayer organic EL element refers to, in addition to the light-emitting layer, holes or holes in the light-emitting layer. A hole injection layer, a hole transport layer, a hole blocking layer, and an electron injection for the purpose of facilitating the injection of electrons and facilitating recombination of holes and electrons in the light emitting layer. Refers to a stack of layers. Therefore, typical element configurations of the multilayer organic EL device include (1) anode / hole injection layer / light emitting layer / cathode, and (2) anode / hole injection layer / hole transport layer / light emitting layer / cathode. (3) anode / hole injection layer / light emitting layer / electron injection layer / cathode, (4) anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode, (5) anode / positive (6) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron injection layer / cathode; (7) anode / hole injection layer / hole blocking layer / electron injection layer / cathode An element configuration in which the anode / light-emitting layer / hole blocking layer / electron injection layer / cathode and (8) anode / light-emitting layer / electron injection layer / cathode are stacked in a multilayer structure is exemplified. However, the organic EL device used in the present invention is not limited to these.

  In addition, each of the above-described organic layers may be formed with two or more layers, and some layers may be repeatedly laminated. As such an example, in recent years, an element configuration called “multi-photon emission” has been proposed in which some layers of the above-mentioned multilayer organic EL element are multilayered for the purpose of improving light extraction efficiency. This is, for example, in an organic EL device composed of a glass substrate / anode / hole transporting layer / electron transporting light emitting layer / electron injection layer / charge generating layer / light emitting unit / cathode, the charge generating layer and the light emitting unit There is a method of laminating a plurality of portions.

  First, materials that can be used for these layers will be specifically exemplified. However, materials that can be used in the present invention are not limited to these.

  As a material that can be used for the hole injection layer, a phthalocyanine compound is effective, and copper phthalocyanine (abbreviation: CuPc), vanadyl phthalocyanine (abbreviation: VOPc), or the like can be used. There is also a material obtained by chemically doping a conductive polymer compound, such as a material obtained by doping polystyrenesulfonic acid (abbreviation: PSS) into polyethylene dioxythiophene (abbreviation: PEDOT) or polyaniline (abbreviation: PANI). You can also. In addition, a thin film of an inorganic semiconductor such as molybdenum oxide (abbreviation: MoOx), vanadium oxide (abbreviation: VOx), nickel oxide (abbreviation: NiOx), or an ultrathin film of an inorganic insulator such as aluminum oxide (abbreviation: Al2O3) is also effective. It is. Also, 4,4 ′, 4 ″ -tris (N, N-diphenyl-amino) -triphenylamine (abbreviation: TDATA), 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenyl-amino] -triphenylamine (abbreviation: MTDATA), N, N'-bis (3-methylphenyl) -N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine (Abbreviation: TPD), 4,4′-bis [N- (1-naphthyl) -N-phenyl-amino] -biphenyl (abbreviation: α-NTPD), 4,4′-bis [N- (4- ( Aromatic amine compounds such as [N, N-di-m-tolyl) amino) phenyl-N-phenylamino] biphenyl (abbreviation: DNTPD) can also be used. Further, a substance exhibiting an acceptor property with respect to the aromatic amine-based compound may be added to the aromatic amine-based compound, and specifically, 2,3,5,6-tetrafluoro-7, which is an acceptor, is added to VOPc. , 7,8,8-tetracyanoquinodimethane (abbreviation: F4-TCNQ) may be added, or α-NPD to which MoOx as an acceptor is added may be used.

  As a material that can be used for the hole transport layer, an aromatic amine compound is preferable, and TDATA, MTDATA, TPD, α-NPD, DNTPD, and the like described in the hole injection material can be used.

  Examples of the electron transporting material that can be used for the electron transporting layer include tris (8-quinolinolato) aluminum (abbreviation: Alq3), tris (4-methyl-8-quinolinolato) aluminum (abbreviation: Almq3), and bis (10-hydroxybenzo). [H] -quinolinato) beryllium (abbreviation: BeBq2), bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum (abbreviation: BAlq), bis [2- (2-hydroxyphenyl) benzoxazola G] (abbreviation: Zn (BOX) 2) and metal complexes such as bis [2- (2-hydroxyphenyl) benzothiazolate] zinc (abbreviation: Zn (BTZ) 2). Further, in addition to the metal complex, 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (abbreviation: PBD), 1,3-bis [5- Oxadiazole derivatives such as (p-tert-butylphenyl) -1,3,4-oxadiazol-2-yl] benzene (abbreviation: OXD-7), 3- (4-tert-butylphenyl) -4 -Phenyl-5- (4-biphenylyl) -1,2,4-triazole (abbreviation: TAZ), 3- (4-tert-butylphenyl) -4- (4-ethylphenyl) -5- (4-biphenylyl) ) -1,2,4-triazole (abbreviation: p-EtTAZ) and other triazole derivatives, 2,2 ′, 2 ″-(1,3,5-benzenetriyl) tris [1-phenyl-1H-benz Imidazole] (abbreviated Imidazole derivatives such as TPBI), bathophenanthroline (abbreviation: can be used phenanthroline derivatives such as BCP): BPhen), bathocuproine (abbreviation.

  Examples of materials that can be used for the electron injection layer include Alq3, Almq3, BeBq2, BAlq, Zn (BOX) 2, Zn (BTZ) 2, PBD, OXD-7, TAZ, p-EtTAZ, TPBI, and the like. An electron transporting material such as BPhen or BCP can be used. In addition, an ultra thin film of an insulator such as an alkali metal halide such as LiF or CsF, an alkaline earth halide such as CaF2, or an alkali metal oxide such as Li2O is often used. Further, an alkali metal complex such as lithium acetylacetonate (abbreviation: Li (acac)) or 8-quinolinolato-lithium (abbreviation: Liq) is also effective. Further, a substance having a donor property with respect to these electron injecting materials may be added to the electron injecting material, and an alkali metal, an alkaline earth metal, a rare earth metal, or the like can be used as a donor. Specifically, a material in which lithium as a donor is added to BCP or a material in which lithium as a donor is added to Alq3 can be used.

  Further, the hole blocking layer is made of a hole blocking material that prevents holes passing through the light emitting layer from reaching the electron injection layer and can form a layer having excellent thin film forming properties. Examples of such a hole blocking material include aluminum complex compounds such as bis (8-hydroxyquinolinato) (4-phenylphenolate) aluminum, and bis (2-methyl-8-hydroxyquinolinato). G) complex compounds such as (g)-(4-phenylphenolate) gallium; and nitrogen-containing condensed aromatic compounds such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (abbreviation: BCP). No.

  The light emitting layer that emits white light is not particularly limited, and for example, the following can be used. That is, the energy level of each layer of the organic EL laminated structure is defined, and light is emitted by using tunnel injection (European Patent No. 0390551). Described (JP-A-3-230584), those having a two-layered light-emitting layer (JP-A-2-220390 and JP-A-2-216790), and a plurality of light-emitting layers. What is divided and composed of materials having different emission wavelengths (Japanese Patent Laid-Open No. 4-51491), a blue light emitter (fluorescent peak 380 to 480 nm) and a green light emitter (480 to 580 nm) are laminated, Further, a structure containing a red phosphor (Japanese Patent Laid-Open No. 6-207170), wherein a blue light-emitting layer contains a blue fluorescent dye and a green light-emitting layer contains a red fluorescent dye It has contained area, such as construction of those (JP-A-7-142169) and the like further containing a green phosphor.

  Further, as the light emitting material used in the present invention, a material known as a conventional light emitting material may be used. The compounds that are preferably used for emitting blue to green or orange to red light are exemplified below. However, the light emitting material is not limited to those specifically exemplified below.

  Blue light emission can be obtained, for example, by using perylene, 2,5,8,11-tetra-t-butylperylene (abbreviation: TBP), 9,10-diphenylanthracene derivative, or the like as a guest material. Further, styryl arylene derivatives such as 4,4'-bis (2,2-diphenylvinyl) biphenyl (abbreviation: DPVBi), 9,10-di-2-naphthylanthracene (abbreviation: DNA), 9,10-bis It can also be obtained from an anthracene derivative such as (2-naphthyl) -2-tert-butylanthracene (abbreviation: t-BuDNA). Further, a polymer such as poly (9,9-dioctylfluorene) may be used.

  Table 20 shows more preferred specific examples.

  Green light emission is due to coumarin-based pigments such as coumarin 30 and coumarin 6, bis [2- (2,4-difluorophenyl) pyridinato] picolinatoiridium (abbreviation: FIrpic), bis (2-phenylpyridinato) acetyl It can be obtained by using acetonatoiridium (abbreviation: Ir (ppy) (acac)) or the like as a guest material. Further, metal complexes such as tris (8-hydroxyquinoline) aluminum (abbreviation: Alq3), BAlq, Zn (BTZ), and bis (2-methyl-8-quinolinolato) chlorogallium (abbreviation: Ga (mq) 2Cl) can also be used. Obtainable. Further, a polymer such as poly (p-phenylenevinylene) may be used.

Table 21 shows more preferred specific examples.

  Emission of orange to red light is due to rubrene, 4- (dicyanomethylene) -2- [p- (dimethylamino) styryl] -6-methyl-4H-pyran (abbreviation: DCM1), 4- (dicyanomethylene) -2-. Methyl-6- (9-julolidyl) ethynyl-4H-pyran (abbreviation: DCM2), 4- (dicyanomethylene) -2,6-bis [p- (dimethylamino) styryl] -4H-pyran (abbreviation: BisDCM) , Bis [2- (2-thienyl) pyridinato] acetylacetonatoiridium (abbreviation: Ir (thp) 2 (acac)), bis (2-phenylquinolinato) acetylacetonatoiridium (abbreviation: Ir (pq) (acac )) Is used as a guest material. It can also be obtained from a metal complex such as bis (8-quinokilinolato) zinc (abbreviation: Znq2) or bis [2-cinnamoyl-8-quinolinolato] zinc (abbreviation: Znsq2). Further, a polymer such as poly (2,5-dialkoxy-1,4-phenylenevinylene) may be used.

  Table 22 shows more preferred specific examples.

  Further, as a material used for the anode of the organic EL element used in the present invention, a material having a large work function (4 eV or more), a metal, an alloy, an electrically conductive compound, or a mixture thereof is preferably used as an electrode material. Specific examples of such an electrode material include metals such as Au, and conductive materials such as CuI, ITO, SNO2, and ZNO. In order to form this anode, a thin film can be formed from these electrode substances by a method such as an evaporation method or a sputtering method. The anode desirably has such a property that, when light emitted from the light emitting layer is extracted from the anode, the transmittance of the anode to the emitted light is greater than 10%. Further, the sheet resistance of the anode is preferably set to several hundreds Ω / cm 2 or less. Further, the thickness of the anode is selected in the range of usually 10 nm to 1 μm, preferably 10 to 200 nm, although it depends on the material.

  As the material used for the cathode of the organic EL device used in the present invention, a metal, an alloy, an electrically conductive compound having a low work function (4 eV or less), and a mixture thereof are used as an electrode material. Specific examples of such an electrode material include sodium, sodium-potassium alloy, magnesium, lithium, magnesium-silver alloy, aluminum / aluminum oxide, aluminum-lithium alloy, indium, and rare earth metals. This cathode can be manufactured by forming a thin film from these electrode substances by a method such as evaporation or sputtering. Here, when the light emitted from the light emitting layer is taken out from the cathode, it is preferable that the transmittance of the cathode with respect to the emitted light be greater than 10%. Further, the sheet resistance as the cathode is preferably several hundreds Ω / cm 2 or less, and the film thickness is usually 10 nm to 1 μm, preferably 50 to 200 nm.

  With respect to the method for producing the organic EL device used in the present invention, an anode, a light emitting layer, a hole injection layer, if necessary, and an electron injection layer, if necessary, are formed by the above-described materials and methods. It may be formed. Further, the organic EL device can be manufactured in the reverse order from the cathode to the anode.

  This organic EL element is manufactured on a light-transmitting substrate. The light-transmitting substrate is a substrate that supports the organic EL element. The light-transmitting substrate preferably has a light transmittance of 50% or more, preferably 90% or more in a visible region of 400 to 700 nm. It is preferable to use a smoother substrate.

  These substrates are not particularly limited as long as they have mechanical and thermal strengths and are transparent. For example, a glass plate, a synthetic resin plate, or the like is suitably used. Examples of the glass plate include a plate formed of soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz, or the like. Examples of the synthetic resin plate include plates made of polycarbonate resin, acrylic resin, polyethylene terephthalate resin, polyether sulfide resin, polysulfone resin, and the like.

  Examples of the method for forming each layer of the organic EL device used in the present invention include dry film forming methods such as vacuum deposition, electron beam irradiation, sputtering, plasma, and ion plating, or spin coating, dipping, flow coating, and ink jet. A wet film forming method such as a method, a method of evaporating a luminous body on a donor film, and a method disclosed in JP-A-2002-534784 or S.A. T. Lee, et al. , Proceedings of SID '02, p. 784 (2002), a laser induced thermal imaging (LITI) method, a printing method (offset printing, flexographic printing, gravure printing, screen printing), an ink jet method, and the like.

  The organic layer is particularly preferably a molecular deposition film. Here, the molecular deposition film refers to a thin film formed by deposition from a material compound in a gaseous state or a film formed by solidification from a material compound in a solution state or a liquid phase state. Can be distinguished from a thin film (molecule accumulation film) formed by the LB method by a difference in an aggregated structure and a higher-order structure and a functional difference caused by the difference. Further, as disclosed in Japanese Patent Application Laid-Open No. 57-51781, after a binder such as a resin and a material compound are dissolved in a solvent to form a solution, the solution is formed into a thin film by a spin coating method or the like. Also, an organic layer can be formed. The thickness of each layer is not particularly limited, but if the thickness is too large, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. Conversely, if the thickness is too small, the pinhole is used. And the like, and it becomes difficult to obtain sufficient light emission luminance even when an electric field is applied. Therefore, the thickness of each layer is suitably in the range of 1 nm to 1 μm, but is more preferably in the range of 10 nm to 0.2 μm.

  In order to improve the stability of the organic EL element against temperature, humidity, atmosphere, and the like, a protective layer may be provided on the surface of the element, or the entire element may be covered or sealed with a resin or the like. In particular, when covering or sealing the entire device, a photocurable resin that is cured by light is preferably used.

  The current applied to the organic EL element used in the present invention is usually DC, but pulse current or AC may be used. The current value and the voltage value are not particularly limited as long as they are within a range in which the element is not destroyed. However, considering the power consumption and the life of the element, it is desirable to emit light efficiently with as little electric energy as possible.

  The driving method of the organic EL element used in the present invention can be driven not only by the passive matrix method but also by the active matrix method. The method of extracting light from the organic EL element of the present invention is applicable not only to the method of bottom emission for extracting light from the anode side, but also to the method of top emission for extracting light from the cathode side. These methods and techniques are described in Junji Kido, "All About Organic EL", published by Nihon Jitsugyo Shuppan (2003).

  The main system of the full color system of the organic EL element used in the present invention is a color filter system. In the color filter method, light of three primary colors is extracted through a color filter using an organic EL element emitting white light. In addition to these three primary colors, white light is partially extracted as it is and used for light emission. Also, the luminous efficiency of the entire device can be increased.

  Further, the organic EL device used in the present invention may employ a microcavity structure. The organic EL device has a structure in which a light emitting layer is sandwiched between an anode and a cathode, and emitted light causes multiple interference between the anode and the cathode. It is a technique to control the emission wavelength extracted from the device by positively utilizing the multiple interference effect by appropriately selecting the optical characteristics such as the ratio and the thickness of the organic layer sandwiched between them. . Thereby, the emission chromaticity can be improved. The mechanism of this multiple interference effect is described in AM-LCD Digest of Technical Papers, OD-2, p. 77-80 (2002).

  As described above, an RGB color filter layer is formed side by side on a glass substrate or the like, and a light emitting layer (backlight) formed using the ITO electrode layer and the organic EL element is mounted on the color filter layer. As a result, color display becomes possible, and a color display device is obtained. At this time, a color display device having a high contrast ratio can be realized by controlling the flow of current at the time of light emission by the TFT.

<Color filters for solid-state imaging devices>
The color filter segment according to the present invention can be formed by a known method without any particular limitation. However, since the filter segment of the image pickup device is as fine as about submicron to about several tens of microns, photolithography is used. Is preferred.
An embodiment of the present invention is a method for manufacturing a color filter, comprising a color filter segment obtained by curing the above-described coloring composition. It includes a color filter segment obtained by curing the coloring composition according to the embodiment of the present invention described above.
The color filter according to the present embodiment includes the above-described green filter segment, red filter segment, and blue filter segment. Other than the colored filter segment according to the present invention, a known colored composition containing a color pigment, containing a color dye, or containing both a color pigment and a color dye may be used. The method for forming the colored filter segment is not particularly limited, but it is common to use a photosensitive colored composition that is a negative resist.
When a color filter segment is formed on a predetermined corresponding photoelectric conversion element, a negative type color resist layer is constituted by a negative type green film formed by a negative type photosensitive green composition, and in this case, the negative type color resist layer is formed. The thickness of the color resist layer is set in the range of 0.1 μm to 3.0 μm.
On the surface of the negative color resist layer formed by the negative colored film, a plurality of portions corresponding to a plurality of photoelectric conversion elements to be formed are subjected to pattern exposure using a photomask.
The photomask has a size 4 to 5 times the size of the pattern to be actually formed, and performs pattern exposure by reducing the size to 1/4 to 1/5 at the time of pattern exposure.
This photomask is a 4 to 5 times reticle, and has a pattern having a size 4 to 5 times the size of the pattern exposed on the surface of the negative type color resist layer. Then, using a stepper exposure device (not shown), the pattern of the photomask is reduced to １ ／ to ５, and the surface of the negative type color resist layer is exposed.
By performing an alkali developing treatment (developing step) subsequent to the exposure step, the uncured portion after the exposure is eluted in the developer, and the photocured portion remains. By this developing step, a patterned film composed of the color filter segments can be formed.
The developing system may be any of a dip system, a shower system, a spray system, a paddle system, and the like, and may be a combination of a swing system, a spin system, and an ultrasonic system.
Before touching the developing solution, the surface to be developed may be moistened with water or the like in advance to prevent uneven development. As the developing solution, an organic alkali developing solution which does not cause damage to the underlying circuit and the like is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds. Examples of the alkaline agent contained in the developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-
Organic alkaline compounds such as [5,4,0] -7-undecene; and inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, and potassium hydrogencarbonate. As the developer, an alkaline aqueous solution obtained by diluting these alkaline agents with pure water so that the concentration thereof becomes 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass is used. . When a developing solution composed of such an alkaline aqueous solution is used, generally, after development, the developing solution is washed (rinsed) with pure water to remove the excess developing solution, followed by drying.
Finally, the filter segment thus formed is subjected to a hardening treatment.
In the manufacturing method of the present invention, after performing the above-described colored layer forming step, exposing step, and developing step, if necessary, a curing step of curing the formed colored pattern by post-heating (post-baking) or post-exposure. May be included. Post-baking is a heat treatment after development to complete the curing, and usually involves a thermal curing treatment at 100 ° C to 270 ° C. In the case of using light, it can be performed by g-line, h-line, i-line, excimer laser such as KrF or ArF, electron beam, X-ray or the like. The irradiation is preferably performed, and the irradiation time is 10 seconds to 180 seconds, preferably 30 seconds to 60 seconds. In the case of using both post-exposure and post-heating, it is preferable to perform post-exposure first.
By repeating the colored layer forming step, the exposing step, and the developing step (and, if necessary, the curing step) by the desired number of hues, a color filter having a desired hue is produced.
<Imaging device>
The solid-state imaging device of the present invention includes the color filter of the present invention. The configuration of the solid-state imaging device of the present invention is a configuration provided with a color filter for the solid-state imaging device of the present invention, and is not particularly limited as long as it functions as a solid-state imaging device. Configuration.
A solid-state image sensor (CCD sensor, CMOS sensor, organic CMOS sensor, etc.) on a substrate
A light-shielding film made of tungsten or the like having only a light-receiving portion of the photodiode formed on the photodiode and the transfer electrode. It has a device protection film made of silicon nitride or the like formed on the film to cover the entire light-shielding film and the photodiode light-receiving portion, and has a configuration in which the solid-state imaging device color filter of the present invention is provided on the device protection film. is there.
Further, a structure having a light collecting means (for example, a microlens or the like; the same applies hereinafter) on the device protective layer and below the color filter (on the side closer to the substrate), a structure having a light collecting means on the color filter, and the like It may be.
The organic CMOS sensor includes a thin panchromatic photosensitive organic photoelectric conversion film as a photoelectric conversion layer and a CMOS signal readout substrate, and an organic material plays a role of capturing light and converting it to an electric signal. It has a two-layered hybrid structure in which an inorganic material plays a role of extracting a signal to the outside, and in principle, the aperture ratio for incident light can be made 100%. Since the organic photoelectric conversion film is a structure-free continuous film and can be laid on the CMOS signal readout substrate, it does not require an expensive fine processing process, and is suitable for filter segment miniaturization.
The arrangement of the color filter segments is not particularly limited, and a known method can be used.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by mass” and “% by mass”, respectively. “PGMAc” means propylene glycol monomethyl ether acetate.

<Weight average molecular weight (Mw) of resin>
The weight average molecular weight (Mw) of the resin was calculated using a TSKgel column (manufactured by Tosoh Corporation), GPC equipped with an RI detector (manufactured by Tosoh Corporation, HLC-8120GPC), and a polystyrene equivalent measured using THF as a developing solvent. It is a weight average molecular weight (Mw).

<Acid value of resin>
To 0.5 to 1.0 parts of the resin solution, 80 ml of acetone and 10 ml of water are added and stirred to dissolve uniformly, and a 0.1 mol / L KOH aqueous solution is used as a titrant, and an automatic titrator (“COM-555”) is used. And the acid value of the resin solution was measured. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

<Number average molecular weight (Mn) of resin>
The number average molecular weight of the present invention was measured by using HLC-8220GPC (manufactured by Tosoh Corporation) as an apparatus, connecting TSK-GEL SUPER HZM-N as a column in duplicate, and using THF as a developing solvent. It is a number average molecular weight (Mn) in conversion.

<Method for identifying azo pigment>
In identifying the azo pigment of the present invention, a MALDI mass spectrometer autoflex III (hereinafter, referred to as TOF-MS) manufactured by Bruker Daltonics, Inc., is used, and the molecular ion peak of the obtained mass spectrum, the mass number obtained by calculation, Further, using a 2400 CHN Element Analyzer manufactured by Perkin-Elmer Co., Ltd., identification was performed by agreement between the ratio of each element obtained and the theoretical value.

<Average primary particle size of azo pigment>
The average primary particle size of the pigment was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission (TEM) electron microscope. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was defined as the particle diameter of the pigment primary particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was determined by approximating the cube of the determined particle size, and the volume average particle size was defined as the average primary particle size.

  First, a method for producing an acrylic resin solution, a resin-type dispersant solution, a colorant, a coloring composition, and a photosensitive coloring composition used in Examples, Production Examples, and Comparative Examples will be described.

<Production method of acrylic resin solution>
(Preparation of acrylic resin solution 1)
196 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirrer in a separable four-necked flask, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. From a tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, and paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 20.7 , A mixture of 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20%. This was added to prepare an acrylic resin solution 1. The weight average molecular weight (Mw) was 26,000.

(Preparation of acrylic resin solution 2)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirrer in a separable four-necked flask, heated to 80 ° C., and purged with nitrogen after the inside of the reaction vessel was replaced with nitrogen. From a tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, nitrogen gas was stopped with respect to the total amount of the obtained copolymer solution, and the mixture was stirred while injecting dry air for 1 hour. After cooling to room temperature, 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK) A mixture of 6.5 parts (MOI), 0.08 part of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours. After the completion of the dropwise addition, the reaction was continued for another hour to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. Cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content became 20%. Thus, an acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18,000.

<Method for producing resin-type dispersant solution>
(Preparation of Resin Dispersant Solution 1)
A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, and 20 parts of benzyl methacrylate, and was replaced with nitrogen gas. The reaction vessel was heated to 80 ° C., and a solution of 0.1 part of 2,2′-azobisisobutyronitrile in 10 parts of 3-mercapto-1,2-propanediol was added. Reacted for hours. The solid content measurement confirmed that 95% had reacted. Add 20 parts of pyromellitic anhydride, 200.0 parts of methoxypropyl acetate, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst, and react at 120 ° C. for 7 hours. Was. The measurement of the acid value confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated to obtain a polyester dispersant having an acid value of 77 mgKOH / g and a number average molecular weight (Mn) of 8,500. Methoxypropyl acetate was added thereto so that the solid content became 40% by solid content measurement, to obtain a resin-type dispersant solution 1 having an aromatic carboxyl group.

(Preparation of Resin Dispersant Solution 2)
A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, and 20 parts of benzyl methacrylate, and was replaced with nitrogen gas. The reaction vessel was heated to 80 ° C., and a solution of 0.1 part of 2,2′-azobisisobutyronitrile in 10 parts of 3-mercapto-1,2-propanediol was added. Reacted for hours. The solid content measurement confirmed that 95% had reacted. 36 parts of trimellitic anhydride, 200.0 parts of methoxypropyl acetate, 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added, and the mixture was reacted at 120 ° C. for 7 hours. Was. Measurement of the acid value confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated to obtain a polyester dispersant having an acid value of 109 mgKOH / g and a number average molecular weight (Mn) of 8,500. Methoxypropyl acetate was added thereto so that the solid content became 40% by solid content measurement, to obtain a resin-type dispersant solution 2 having an aromatic carboxyl group.

(Preparation of Resin Dispersant Solution 3)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 6.5 parts of 3-mercapto-1,2-propanediol, 4.0 parts of pyromellitic anhydride, 0.01 part of dimethylbenzylamine, 41.8 parts of methoxypropyl acetate was charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 ° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70 ° C., and 67 parts of methyl methacrylate, 5.0 parts of methacrylic acid, t-butyl 16.0 parts of acrylate, 10.0 parts of hydroxymethyl methacrylate, and 2.0 parts of ethyl acrylate were charged, and 0.10 part of 2,2'-azobisisobutyronitrile and 60.0 parts of methoxypropyl acetate were added. And reacted for 10 hours. The solid content measurement confirmed that the polymerization had progressed to 95%, and the reaction was terminated to obtain a polyester dispersant having an acid value of 43 mgKOH / g and a number average molecular weight (Mn) of 15,000. To this was added methoxypropyl acetate so that the solid content was 40% by solid content measurement, to obtain a resin-type dispersant solution 3 having an aromatic carboxyl group.

(Preparation of Resin Dispersant Solution 4)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 6.5 parts of 3-mercapto-1,2-propanediol, 4.0 parts of pyromellitic anhydride, 0.01 part of dimethylbenzylamine, 41.8 parts of methoxypropyl acetate was charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 ° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70 ° C., and 67 parts of methyl methacrylate, 5.0 parts of methacrylic acid, t-butyl 16.0 parts of acrylate, 10.0 parts of (3-ethyloxetane-3-yl) methyl methacrylate, and 2.0 parts of ethyl acrylate were charged, and 0.10 part of 2,2′-azobisisobutyronitrile and methoxypropyl 60.0 parts of acetate was added and reacted for 10 hours. The solid content measurement confirmed that the polymerization had progressed to 95%, and the reaction was terminated to obtain a polyester dispersant having an acid value of 47 mgKOH / g and a number average molecular weight (Mn) of 15,000. To this was added methoxypropyl acetate so that the solid content became 40% by solid content measurement, to obtain a resin-type dispersant solution 4 having an aromatic carboxyl group.

<Method for Preparing Resin Having Cationic Group in Side Chain>
75.1 parts of isopropyl alcohol was charged into a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, and heated to the boiling point under a nitrogen stream. Separately, 15.7 parts of methyl methacrylate, 27.3 parts of n-butyl methacrylate, 27.3 parts of 2-ethylhexyl methacrylate, 15.0 parts of hydroxyethyl methacrylate, 2.5 parts of methacrylic acid, dimethylaminoethyl methyl methacrylate chloride salt 12.2 parts and 10.0 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) separately dissolved in 23.4 parts of methyl ethyl ketone were homogenized, then charged in a dropping funnel, and charged in a four-neck separator. The flask was attached to a bull flask and dropped over 2 hours. Two hours after completion of the dropwise addition, it was confirmed from the solid content that the polymerization yield was 98% or more, and the mixture was cooled to 50 ° C. Thereafter, 14.3 parts of methanol was added to obtain a resin having a resin component having a cationic group in a side chain of 40% by mass. The ammonium salt value of the obtained resin was 33 mgKOH / g.

Here, the weight average molecular weight (Mw) of the resin having a cationic group in the side chain was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. The ammonium salt value of the resin (B) having a cationic group in the side chain is determined by titration with a 5% aqueous solution of potassium chromate using a 0.1N aqueous solution of silver nitrate as an indicator. It is a converted value and indicates the ammonium salt value of the solid content.

<Method for producing dye derivative>
The production method and structure of the dye derivative used in the present invention will be described. Note that the present invention is not limited to this.

(Production of dye derivative 1)
The dye derivative 1 represented by the formula 5 was produced with reference to Synthesis Example 3 of Japanese Patent No. 5748665.
Equation 5

(Production of dye derivative 2)
The dye derivative 2 represented by the formula 6 was produced with reference to Production Example 21 of Japanese Patent No. 4396778.
Equation 6

(Production of Dye Derivative 3)
The dye derivative 3 represented by the formula 7 was produced with reference to Production Example 6 of Japanese Patent No. 4983061.
Equation 7

(Production of Dye Derivative 4)
With reference to Example 1 of Japanese Patent No. 5316690, a dye derivative 4 represented by Formula 8 was produced.
Equation 8

(Production of Dye Derivative 5)
16 parts of 5-nitroisophthalic acid and 1.0 part of N, N-dimethylformamide (DMF) were dissolved in 110 parts of toluene. To this, 22.6 parts of thionyl chloride was added dropwise over 25 minutes, and the mixture was refluxed at 110 ° C. for 1 hour to synthesize 5-nitroisophthalic acid dichloride. In 90 parts of toluene, 38.0 parts of 4-amino-N- (3- (diethylamino) propyl) benzamide are dispersed, and the above-mentioned 5-nitroisophthalic acid dichloride is added dropwise at room temperature over 1 hour, and then refluxed for 4 hours. To complete the reaction. After toluene was distilled off while neutralizing with a 10% aqueous sodium carbonate solution, the slurry was reslurried with a 3% aqueous NaOH solution, filtered, and dried to obtain 28.0 parts of a compound represented by the following formula 9.
Equation 9

Next, 25.0 parts of the compound represented by the above formula 9 are dissolved in 100 parts of N-methylpyrrolidone, and 32 parts of sodium hydrosulfide hydrate (containing 65% of sodium hydrosulfide) are added to 55 parts of water. After adding the dissolved aqueous solution, the mixture was refluxed for 6 hours to obtain 20.0 parts of a base compound represented by the following formula 10.
Equation 10

Disperse 20.0 parts of the base compound represented by the above formula 10 in 200 parts of water, adjust the temperature to 5 ° C. by adding ice, add 20.0 parts of a 35% hydrochloric acid aqueous solution, stir for 1 hour, and add sodium nitrite. An aqueous solution prepared by adding 3.60 parts to 11.0 parts of water was added and stirred for 2 hours. Subsequently, an aqueous solution consisting of 59.0 parts of an 80% aqueous acetic acid solution, 65.0 parts of a 25% aqueous sodium hydroxide solution, and 64.0 parts of water was added to obtain a diazonium salt aqueous solution. On the other hand, 18.7 parts of N- [2-methoxy-5-chlorophenyl] -3-hydroxy-2-naphthalenecarbamide and 53.5 parts of a 25% aqueous sodium hydroxide solution were dissolved in 340 parts of methanol to obtain a coupler solution. .

  This coupler solution was injected into the diazonium salt aqueous solution at 5 ° C. for 30 minutes to perform a coupling reaction. The pH at this time was 4.4. After stirring for 1 hour to confirm disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours to obtain 35.8 parts of a dye derivative 5 represented by the formula 11.

Equation 11

(Production of Dye Derivative 6)
The dye derivative 6 represented by the formula 12 was produced with reference to Production Example 3 of Japanese Patent No. 1863188.
Equation 12

<Method for producing colorant>
(Base compound)
The base compounds ([B-1] to [B-18]) used this time are shown in Table 1. Ph in the table represents a phenyl group.

(Production of coupler compound [C-1])

After mixing 167 parts of 3-hydroxy-2-naphthoic acid, 1500 parts of tetrahydrofuran and 1 part of N, N-dimethylformamide, 221 parts of thionyl chloride is added, and the mixture is stirred at room temperature for 1 hour to obtain a carboxylic acid chloride solution. Obtained. Separately, a solution was prepared by mixing 1000 parts of N-methylpyrrolidone and 105 parts of 2,6-diaminoanthraquinone, and a carboxylic acid chloride solution was added dropwise to this solution over 30 minutes. At this time, dropping was performed while maintaining the temperature of the reaction solution at 10 ° C. or lower. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, and the precipitated reaction product was collected by filtration to obtain the desired product. Furthermore, by washing with 1000 parts of methanol and drying under reduced pressure, 249 parts (yield 97.8%) of the coupler compound [C-1] were obtained.

(Production of coupler compound [C-2])
The same as in the production of the coupler compound [C-1] except that 105 parts of 1,5-diaminoanthraquinone was used instead of 105 parts of the 2,6-diaminoanthraquinone used in the production of the coupler compound [C-1]. The operation was performed to obtain 248 parts (yield 97.5%) of the coupler compound [C-2].

(Production of coupler compound [C-3])
Except that 105 parts of 1,4-diaminoanthraquinone was used instead of 105 parts of 2,6-diaminoanthraquinone used in the production of the coupler compound [C-1], the same as in the production of the coupler compound [C-1] was used. The operation was performed to obtain 245 parts (yield 96.2%) of the coupler compound [C-3].

<Manufacture of azo pigments>
[Example 1]
(Production of azo pigment 1)

After adding 185 parts of the base compound [B-1] to 1500 parts of N-methylpyrrolidone,
294 parts of hydrochloric acid was added, and the mixture was cooled to -2 to 0 ° C. After adding 208 parts of a 25% aqueous sodium nitrite solution to this solution, the mixture was stirred for 30 minutes while maintaining the temperature at 0 to 5 ° C. to prepare a diazonium solution. Separately, a coupler solution comprising 216 parts of the coupler compound [C-1], 316 parts of a 25% sodium hydroxide solution, and 1500 parts of methanol was prepared. The prepared diazonium solution and coupler solution were simultaneously dropped into 1000 parts of an acetate buffer solution having a pH of 5.4 over 10 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes and further stirred at 80 ° C., and the precipitated reaction product was collected by filtration, washed with hot water, and dried to obtain 386 parts of azo pigment 1. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 1.

Azo pigment 1

[Example 2]
(Production of azo pigment 2)
An azo pigment was produced in the same manner as in the production of the azo pigment 1, except that 169 parts of the base compound [B-2] was used instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 1. 2 (yield: 97.5%) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 2.

Azo pigment 2

[Example 3]
(Production of azo pigment 3)
The same operation as in the preparation of azo pigment 1 was performed except that 210 parts of base compound [B-3] was used instead of 185 parts of base compound [B-1] used in production of azo pigment 1. 420 parts (yield: 96.5%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 3.

Azo pigment 3

[Example 4]
(Production of azo pigment 4)
The same operation as in the production of azo pigment 1 was carried out except that 181 parts of base compound [B-4] was used instead of 185 parts of base compound [B-1] used in production of azo pigment 1. 395 parts (yield: 97.1%) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 4.

Azo pigment 4

[Example 5]
(Production of azo pigment 5)
The same operation as in the production of azo pigment 1 was carried out except that 185 parts of base compound [B-1] used in production of azo pigment 1 was used, and 222 parts of base compound [B-5] was used. 433 parts (yield: 96.9%) of 5 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 5.

Azo pigment 5

[Example 6]
(Production of azo pigment 6)
An azo pigment was produced in the same manner as in the production of the azo pigment 1, except that 228 parts of the base compound [B-6] was used instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 1. 437 (yield: 96.3%) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 6.

Azo pigment 6

[Example 7]
(Production of azo pigment 7)
An azo pigment was produced in the same manner as in the production of the azo pigment 1, except that 124 parts of the base compound [B-7] was used instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 1. 338 parts (yield: 96.5%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 7.

Azo pigment 7

Example 8
(Production of azo pigment 8)
The same operation as in the production of azo pigment 1 was carried out except that 128 parts of base compound [B-8] was used instead of 185 parts of base compound [B-1] used in production of azo pigment 1. 373 parts (yield: 97.9%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 8.

Azo pigment 8

[Example 9]
(Production of azo pigment 9)
An azo pigment was produced in the same manner as in the production of the azo pigment 1 except that 156 parts of the base compound [B-9] was used instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 1. 403 parts of 9 (yield: 97.7%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 9.

Azo pigment 9

[Example 10]
(Production of azo pigment 10)
An azo pigment was produced in the same manner as in the production of the azo pigment 1, except that 187 parts of the base compound [B-10] was used instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 1. 408 parts (yield: 98.9%) of 10 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 10.

Azo pigment 10

[Example 11]
(Production of azo pigment 11)
The same operation as in the production of azo pigment 1 was carried out except that 190 parts of base compound [B-11] was used instead of 185 parts of base compound [B-1] used in production of azo pigment 1. 402 were obtained (yield: 96.6%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 11.

Azo pigment 11

[Example 12]
(Production of azo pigment 12)
The same operation as in the production of azo pigment 1 was carried out except that 240 parts of base compound [B-12] was used instead of 185 parts of base compound [B-1] used in production of azo pigment 1. 449 parts (yield: 96.4%) of 12 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 12.

Azo pigment 12

Example 13
(Production of azo pigment 13)
An azo pigment was produced in the same manner as in the production of the azo pigment 1, except that 207 parts of the base compound [B-13] was used instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 1. 424 parts (yield: 97.9%) of 13 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 13.

Azo pigment 13

[Example 14]
(Production of azo pigment 14)
The same operation as in the production of azo pigment 1 was performed except that 241 parts of base compound [B-14] was used instead of 185 parts of base compound [B-1] used in production of azo pigment 1. 444 parts (yield: 95.0%) of 14 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 14.

Azo pigment 14

[Example 15]
(Production of azo pigment 15)
An azo pigment was produced in the same manner as in the production of the azo pigment 1 except that 215 parts of the base compound [B-15] was used instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 1. 422 parts (yield: 95.8%) of 15 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 15.

Azo pigment 15

[Example 16]
(Production of azo pigment 16)
An azo pigment was produced in the same manner as in the production of the azo pigment 1 except that 233 parts of the base compound [B-16] was used instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 1. 16 (440 parts, yield: 96.0%) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 16.

[Example 17]
(Production of azo pigment 17)
The same operation as in the production of azo pigment 1 was carried out except that 298 parts of base compound [B-17] was used instead of 185 parts of base compound [B-1] used in production of azo pigment 1. 506 parts (yield: 96.5%) of 17 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 17.

Azo pigment 17

[Example 18]
(Production of azo pigment 18)
An azo pigment was produced in the same manner as in the production of the azo pigment 1, except that 415 parts of the base compound [B-18] was used instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 1. 619 were obtained (yield: 96.5%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 18.

Azo pigment 18

[Example 19]
(Production of azo pigment 19)
An azo pigment was produced in the same manner as in the production of the azo pigment 1, except that 216 parts of the coupler compound [C-2] was used instead of 216 parts of the coupler compound [C-1] used in the production of the azo pigment 1. 395 parts (yield: 96.4%) of 19 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 19.

Azo pigment 19

[Example 20]
(Production of azo pigment 20)
An azo pigment was produced in the same manner as in the production of the azo pigment 19, except that 169 parts of the base compound [B-2] was used instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 19. 390 parts (yield: 98.7%) of 20 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 20.

Azo pigment 20

[Example 21]
(Production of azo pigment 21)
The same operation as in the production of azo pigment 19 was performed except that 210 parts of base compound [B-3] was used instead of 185 parts of base compound [B-1] used in production of azo pigment 19. 430 parts (yield: 98.7%) of 21 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 21.

Azo pigment 21

[Example 22]
(Production of azo pigment 22)
An azo pigment was produced in the same manner as in the production of the azo pigment 19 except that 181 parts of the base compound [B-4] was used instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 19. 396 parts (yield: 97.4%) of 22 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 22.

Azo pigment 22

[Example 23]
(Production of azo pigment 23)
An azo pigment was produced in the same manner as in the production of the azo pigment 19, except that 185 parts of the base compound [B-1] used in the production of the azo pigment 19 was used instead of 222 parts of the base compound [B-5]. 433 parts (yield: 96.7%) of 23 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 23.

Azo pigment 23

[Example 24]
(Production of azo pigment 24)
An azo pigment was produced in the same manner as in the production of the azo pigment 19 except that 228 parts of the base compound [B-6] was used instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 19. 434 parts (yield: 95.8%) of 24 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 24.

Azo pigment 24

[Example 25]
(Production of azo pigment 25)
An azo pigment was produced in the same manner as in the production of the azo pigment 19, except that 124 parts of the base compound [B-7] was used instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 19. 343 parts (yield: 98.0%) of 25 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 25.

Azo pigment 25

[Example 26]
(Production of azo pigment 26)
The same operation as in the production of the azo pigment 19 was carried out except that 128 parts of the base compound [B-8] was used instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 19. 336 parts (yield: 95.2%) of 26 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 26.

Azo pigment 26

[Example 27]
(Production of azo pigment 27)
An azo pigment was produced in the same manner as in the production of the azo pigment 19, except that 207 parts of the base compound [B-13] was used instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 19. 423 parts (yield: 97.8%) of 27 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 27.

Azo pigment 27

[Example 28]
(Production of azo pigment 28)
The same operation as in the production of azo pigment 1 was carried out except that 216 parts of coupler compound [C-3] was used instead of 216 parts of coupler compound [C-1] used in production of azo pigment 1. 352 parts (yield: 97.6%) of 28 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 28.

Azo pigment 28

[Example 29]
(Production of azo pigment 29)
The same operation as in the production of azo pigment 28 was carried out except that 210 parts of base compound [B-3] was used instead of 185 parts of base compound [B-1] used in production of azo pigment 28. 431 parts (yield: 98.9%) of 29 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 29.

Azo pigment 29

[Example 30]
(Production of azo pigment 30)
The same operation as in the production of azo pigment 28 was carried out except that 181 parts of base compound [B-4] was used instead of 185 parts of base compound [B-1] used in production of azo pigment 28. 393 parts (yield: 96.7%) of 30 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 30.

Azo pigment 30

[Example 31]
(Production of azo pigment 31)
An azo pigment was produced in the same manner as in the production of the azo pigment 28 except that 124 parts of the base compound [B-7] was used instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 28. 342 parts (yield: 97.6%) of 31 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 31.

Azo pigment 31

[Example 32]
(Production of Azo Pigment 32) Step of Refining Azo Pigment 4 80 parts of azo pigment 4, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and were heated at 60 ° C. for 6 hours. It was kneaded and subjected to salt milling. The obtained kneaded material was poured into 3 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying at 80 ° C. all day and night. And 78 parts of azo pigment 32 were obtained.

[Example 33]
(Manufacture of Azo Pigment 33) Step of Refining Azo Pigment 22 80 parts of azo pigment 22, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and were heated at 60 ° C. for 6 hours. It was kneaded and subjected to salt milling. The obtained kneaded material was poured into 3 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying at 80 ° C. all day and night. And 78 parts of an azo pigment 33 were obtained.

[Examples 34 to 39]
(Production of azo pigments 34 to 39)
In the production of the azo pigment 32, azo pigments 34 to 39 were obtained in the same manner as the azo pigment 32 except that the azo pigment 4 and the dye derivative were changed to the types and ratios shown in Table 4-2 instead of the azo pigment 4. Was.

[Examples 40 to 41]
(Production of azo pigments 40 to 41)
In the production of the azo pigment 33, azo pigments 40 to 41 were obtained in the same manner as the azo pigment 33 except that the azo pigment 22 and the dye derivative were changed to the types and ratios shown in Table 4-2 instead of the azo pigment 22. Was.

[Production Example 1]
(Production of azo pigment 101)
The following azo pigment 101 was synthesized with reference to JP-A-2014-160160.

Azo pigment 101


[Production Examples 2 to 13]
<Manufacture of other pigments>
(Production of Red Colorant 1 (RCP-1): PR254)
Commercially available C.I. I. Pigment Red 254 (PR254) (“Irgazine Red D3656 HD” manufactured by BASF), 100 parts, 1200 parts of sodium chloride, and 120 parts of diethylene glycol are charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), and are heated at 60 ° C. for 6 hours. It was kneaded and subjected to salt milling. The obtained kneaded material was poured into 3 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, and filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and dried at 80 ° C. for 24 hours. , 98 parts of red colorant 1 (RCP-1). The average primary particle size was 33 nm.

(Production of Red Colorant 2 (RCP-2): PR177)
C. I. Pigment Red 254 (“Irgazine Red D3656 HD” manufactured by BASF), and C.I. I. Pigment Red 177 (PR177) (“Sinilex Red SR3C” manufactured by Sinic) was produced in the same manner as in the production of the red colorant 1 to obtain 97 parts of a red colorant 2 (RCP-2). The average primary particle size was 37 nm.

(Production of Red Colorant 3 (RCP-3): PR242)
C. I. Pigment Red 254 (“Irgazine Red D3656 HD” manufactured by BASF), and C.I. I. Pigment Red 242 (PR242) ("Sandorin Scarlet 4RF" manufactured by Clariant) was carried out in the same manner as in the production of the red colorant 1 to obtain 98 parts of a red colorant 3 (RCP-3). The average primary particle size was 39 nm.

(Production of Red Colorant 4 (RCP-4): PR269)
C. I. Pigment Red 254 (“Irgazine Red D3656 HD” manufactured by BASF), and C.I. I. Pigment Red 269 (PR269) (“Permanent Carmine 3810” manufactured by Sanyo Dyeing Co., Ltd.), and the same procedure as in the production of the red colorant 1 was carried out to obtain 98 parts of a red colorant 4 (RCP-4). The average primary particle size was 35 nm.

(Production of Red Colorant 5 (RCP-5): Brominated Diketopyrrolopyrrole Pigment Formula (4))
Under a nitrogen atmosphere, 200 parts of tert-amyl alcohol dehydrated by molecular sieve and 140 parts of sodium-tert-amyl alkoxide were added to a stainless steel reaction vessel equipped with a reflux tube, and the mixture was heated to 100 ° C. while stirring, and the alcoholate solution was added. Prepared. On the other hand, in a glass flask, 88 parts of diisopropyl succinate, 4-bromobenzonitrile 15
3.6 parts were added and dissolved by heating to 90 ° C. with stirring to prepare a solution of these mixtures. A heated solution of this mixture was slowly dropped into the above-described alcoholate solution heated to 100 ° C. at a constant rate over 2 hours while stirring vigorously. After completion of the dropwise addition, heating and stirring were continued at 90 ° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole-based compound. Further, 600 parts of methanol, 600 parts of water and 304 parts of acetic acid were added to a glass-made reaction vessel equipped with a jacket, and cooled to -10 ° C. The cooled mixture was cooled to 75 ° C. while rotating a shear disk having a diameter of 8 cm at 4,000 rpm using a high-speed stirring disperser, and the alkali metal salt of the diketopyrrolopyrrole compound obtained earlier was cooled to 75 ° C. The solution was added in small portions. At this time, the rate at which the alkali metal salt of the diketopyrrolopyrrole-based compound is added at 75 ° C. while cooling so that the temperature of the mixture of methanol, acetic acid, and water is always kept at −5 ° C. or lower. , Was added in small portions over approximately 120 minutes. After the addition of the alkali metal salt, red crystals precipitated, and a red suspension was formed. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 ° C., and then filtered to obtain a red paste. This paste was redispersed in 3500 parts of methanol cooled to 0 ° C. to form a suspension having a methanol concentration of about 90%, and the mixture was stirred at 5 ° C. for 3 hours to perform particle sizing with crystal transition and washing. Subsequently, the aqueous paste of the diketopyrrolopyrrole-based compound obtained by filtration with an ultrafilter is dried at 80 ° C. for 24 hours and pulverized to obtain a brominated diketo compound represented by the formula (4). 150.8 parts of a pyrrolopyrrole pigment were obtained.

100 parts of the brominated diketopyrrolopyrrole pigment represented by the formula (4) obtained above, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.). The mixture was kneaded for a time and subjected to salt milling. The obtained kneaded material was poured into 3 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, and filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and dried at 80 ° C. for 24 hours. , 98 parts of red colorant 5 (RCP-5). The average primary particle size was 45 nm.
Equation (4)

(Production of Yellow Colorant 1 (YCP-1): PY138)
Quinophthalone yellow pigment C.I. I. Pigment Yellow 138 (“PARIOTOL Yellow L0962-HD” manufactured by BASF), 100 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. . Next, the kneaded material is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry. Filtration and washing are repeated to remove sodium chloride and diethylene glycol, followed by drying at 80 ° C. all day and night. Thus, 90 parts of yellow colorant 1 (YCP-1) was obtained. The average primary particle size was 63 nm.

(Production of Yellow Colorant 2 (YCP-2): PY139)
Isoindoline yellow pigment C.I. I. Pigment Yellow 139 (“Pariotol Yellow L1820” manufactured by BASF), 100 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. Next, the kneaded material is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry. Filtration and washing are repeated to remove sodium chloride and diethylene glycol, followed by drying at 80 ° C. all day and night. Thus, 95 parts of a yellow colorant 2 (YCP-2) was obtained. The average primary particle size was 68 nm.

(Production of yellow colorant 3 (YCP-3): PY150)
Azo yellow pigment C.I. I. Pigment Yellow 150 (“Hosta Palm Yellow HN4G” manufactured by Clariant), 100 parts, sodium chloride 500 parts, and diethylene glycol 250 parts were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. Next, the kneaded material is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry. Filtration and washing are repeated to remove sodium chloride and diethylene glycol, followed by drying at 80 ° C. all day and night. Thus, 90 parts of yellow colorant 3 (YCP-3) was obtained. The average primary particle size was 60 nm.

(Production of Yellow Colorant 4 (YCP-4): PY185)
Isoindoline yellow pigment C.I. I. Pigment Yellow 185 (“PARIOGEN YELLOW D1155” manufactured by BASF), 100 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. The kneaded material was poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, and filtered and washed repeatedly to remove sodium chloride and diethylene glycol, followed by drying at 80 ° C. for 24 hours. 90 parts of yellow colorant 5 (YCP-4) was obtained, and the average primary particle diameter was 66 nm.

(Production of Yellow Colorant 5 (YCP-5): Quinophthalone Compound (b))
To 200 parts of methyl benzoate, 40 parts of 8-aminoquinaldine, 150 parts of 2,3-naphthalenedicarboxylic anhydride, and 154 parts of benzoic acid were added, heated to 180 ° C., and stirred for 4 hours. After cooling to room temperature, the reaction mixture was poured into 5440 parts of acetone, and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 116 parts of a quinophthalone compound (c). As a result of mass spectrometry by TOF-MS, the compound was identified as quinophthalone compound (c).

Quinophthalone compound (c)

  Further, using the quinophthalone compound (c) as a raw material, a compound (c-2) was obtained according to a synthesis method described in JP-A-2008-81566.

Compound (c-2)

To 300 parts of methyl benzoate, 100 parts of compound (c-2), 108 parts of tetrachlorophthalic anhydride, and 143 parts of benzoic acid were added, and the mixture was heated to 180 ° C. and reacted for 4 hours. By TOF-MS, formation of the quinophthalone compound (b) and disappearance of the raw material compound (c-2) were confirmed. Furthermore, after cooling to room temperature, the reaction mixture was poured into 3510 parts of acetone, and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 120 parts of a quinophthalone compound (b). As a result of mass spectrometry using TOF-MS, the compound was identified as quinophthalone compound (b).
Quinophthalone compound (b)

  100 parts of the quinophthalone compound (b) obtained above, 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1 gallon kneader made of stainless steel (manufactured by Inoue Seisakusho), and kneaded at 120 ° C. for 8 hours. Next, the kneaded material is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, and filtration and washing are repeated to remove sodium chloride and diethylene glycol, followed by drying at 80 ° C. all day and night. Thus, 95 parts of yellow colorant 5 (YCP-5) was obtained. The average primary particle size was 62 nm.

(Production of Yellow Colorant 6 (YCP-6): Quinophthalone Compound (t))
To 1200 parts of 98% sulfuric acid, 150 parts of 2,3-naphthalenedicarboxylic anhydride and 230 parts of trichloroisocyanuric acid were added and reacted at 80 ° C. for 4 hours. The reaction solution was poured into 9000 parts of stirred ice water, and the resulting precipitate was filtered, washed with water, washed with a 1% aqueous sodium hydroxide solution, washed with water in this order, and dried to obtain an intermediate (a-1). 220 parts were obtained. To 500 parts of methyl benzoate, 105 parts of the compound (c-2), 150 parts of the intermediate (a-1) and 100 parts of benzoic acid were added, and the mixture was heated to 180 ° C. and stirred for 4 hours. After cooling to room temperature, the reaction mixture was poured into 5000 parts of acetone, and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 183 parts of a quinophthalone compound (t). As a result of mass spectrometry using TOF-MS, the compound was identified as a quinophthalone compound (t).
Quinophthalone compound (t)

  100 parts of the quinophthalone compound (t) obtained above, 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1-gallon kneader made by stainless steel (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. Next, the kneaded material is put into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, and filtration and washing are repeated to remove sodium chloride and diethylene glycol, followed by drying at 80 ° C. overnight. Thus, 95 parts of yellow colorant 6 (YCP-6) was obtained. The average primary particle size was 60 nm.

(Production of Yellow Coloring Agent 7 (YCP-7): Quinophthalone Compound (aa))
In the synthesis of the intermediate (a-1), an intermediate (a-2) was obtained in the same manner except that 230 parts of trichloroisocyanuric acid was changed to 244 parts of N-bromosuccinimide.
To 200 parts of methyl benzoate, 50 parts of 8-aminoquinaldine, 115 parts of the intermediate (a-1) and 140 parts of benzoic acid were added, and the mixture was stirred at 120 ° C for 4 hours. Next, 143 parts of the intermediate (a-2) was further added to the reaction mixture, and the mixture was heated to 180 ° C and stirred for 4 hours while distilling off water. After cooling to room temperature, the reaction mixture was poured into 2,000 parts of acetone, and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 167 parts of a quinophthalone compound (aa). As a result of mass spectrometry by TOF-MS, the compound was identified as a quinophthalone compound (aa).
Quinophthalone compound (aa)

  100 parts of the quinophthalone compound (aa), 500 parts of sodium chloride, and 250 parts of diethylene glycol obtained above were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho), and kneaded at 120 ° C. for 8 hours. Next, the kneaded material is put into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, and filtration and washing are repeated to remove sodium chloride and diethylene glycol, followed by drying at 80 ° C. overnight. Thus, 95 parts of yellow colorant 7 (YCP-7) was obtained. The average primary particle size was 61 nm.

(Production of green colorant 1: PG58)
Phthalocyanine green pigment C.I. I. Pigment Green 58 (manufactured by DIC Corporation, "FASTOGEN GREEN A110") (200 parts), sodium chloride (1400 parts), and diethylene glycol (360 parts) were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C for 6 hours. The kneaded material was put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol. Of the green colorant 1. The average primary particle size was 69 nm.

(Preparation of Blue Colorant 1: PB15: 6)
Phthalocyanine-based blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyo Color Co., Ltd.), 200 parts of sodium chloride, and 360 parts of diethylene glycol are charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. did. Next, the kneaded material was put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying at 85 ° C. for 24 hours. And 190 parts of blue colorant 1. The average primary particle size was 74 nm.

(Preparation of purple colorant 1: PV23)
Dioxazine purple pigment C.I. I. Pigment Violet 23 ("Lionogen Violet RL" manufactured by Toyo Color Co., Ltd.), 200 parts of sodium chloride and 360 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded material was put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying at 85 ° C. for 24 hours. , 190 parts of purple colorant 1 were obtained. The average primary particle size was 69 nm.

(Preparation of Purple Colorant 2: Salt Forming Compound)
C. In the following procedure. I. A purple colorant 2 composed of Acid Red 52 and a resin having a cationic group in a side chain was prepared.
To 2000 parts of water was added 51 parts of a resin having a cationic group in a side chain, and the mixture was sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, 90 parts of water and 10 parts of C.I. I. An aqueous solution in which Acid Red 52 was dissolved was prepared, and added dropwise to the resin solution. After the addition, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react. To confirm the end point of the reaction, the reaction solution was dropped on filter paper, and it was determined that a salt-forming compound was obtained, with the end point at which bleeding disappeared as the end point. After allowing to cool to room temperature with stirring, suction filtration and washing with water were performed to form a counter anion of the resin having a cationic group in the side chain and C.I. I. After removing the salt consisting of the counter cation of Acid Red 52, the salt-forming compound remaining on the filter paper was dried by removing the moisture with a drier, and dried in 32 parts of C.I. I. A purple colorant 2 which is a salt forming compound of Acid Red 52 and a resin having a cationic group in a side chain was obtained. At this time, C.I. I. Acid Red 52 content was 25% by weight.

  The results of mass spectrometry and elemental analysis of the azo pigments produced in Examples 1 to 31 are shown in Tables 3 and 4. Table 4 shows the evaluation results of the average primary particle diameter of the produced pigment.

<Production method of coloring composition>
[Example 101]
(Preparation of coloring composition (RM-1))
The following mixture was stirred and mixed so as to be uniform, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to prepare a coloring composition (RM-1) having a nonvolatile content of 20% by mass.
Red colorant (RP-1): 12.0 parts Acrylic resin solution 1: 19.2 parts Propylene glycol monomethyl ether acetate (PGMAc): 60.8 parts Acidic resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie) (Solid content 52%)): 8.0 parts

[Examples 102 to 141, Comparative Example 1]
(Coloring composition (RM-2 to 41, 101)
Hereinafter, colored compositions (RM-2 to 41, 101) were prepared in the same manner as the colored composition (RM-1) except that the compositions were changed to those shown in Table 5 and Table 5-2.

[Example 142]
(Preparation of coloring composition (RM-42))
The following mixture was stirred and mixed so as to be uniform, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to prepare a coloring composition (RM-42) having a nonvolatile content of 20% by mass.
Red colorant (RP-4): 12.0 parts Acrylic resin solution 1: 19.2 parts Propylene glycol monomethyl ether acetate (PGMAc): 60.5 parts Acidic resin type dispersant solution ("SOLSPERSE-55000" manufactured by Lubrizol Co.) (Solid content: 50%)): 8.3 parts

[Example 143]
(Preparation of coloring composition (RM-43))
The following mixture was stirred and mixed so as to be uniform, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. The solution was filtered through a 0 μm filter to prepare a coloring composition (RM-43) having a nonvolatile component content of 20% by mass.
Red colorant (RP-4): 12.0 parts Acrylic resin solution 1: 19.2 parts Propylene glycol monomethyl ether acetate (PGMAc): 58.4 parts Basic resin type dispersant solution ("Disperbyk-2000" manufactured by BYK-Chemie) (40% solids)): 10.4 parts

[Example 144]
(Preparation of coloring composition (RM-44))
The following mixture was stirred and mixed so as to be uniform, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered with a 0 μm filter to prepare a coloring composition (RM-44) having a nonvolatile content of 20% by mass.
Red colorant (RP-4): 12.0 parts Acrylic resin solution 1: 40.0 parts Propylene glycol monomethyl ether acetate (PGMAc): 48.0 parts

[Example 145]
(Preparation of coloring composition (RM-45))
The following mixture was stirred and mixed so as to be uniform, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to prepare a coloring composition (RM-45) having a nonvolatile component content of 20% by mass.
Red colorant (RP-4): 12.0 parts Acrylic resin solution 1: 19.2 parts Propylene glycol monomethyl ether acetate (PGMAc): 58.4 parts Acid resin type dispersant solution (resin type dispersant solution 1): 10.4 copies

[Examples 146 to 150]
(Coloring composition (RM-46 to 50)
Hereinafter, colored compositions (RM-46 to RM-50) were prepared in the same manner as the colored composition (RM-45) except that the composition was changed to the composition shown in Table 5-3.

[Example 151]
(Preparation of coloring composition (RM-51))
The following mixture was stirred and mixed so as to be uniform, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to prepare a coloring composition (RM-51) having a nonvolatile component content of 20% by mass.
Red colorant (RP-4): 10.8 parts Dye derivative 2: 1.2 parts Acrylic resin solution 1: 19.2 parts Propylene glycol monomethyl ether acetate (PGMAc): 60.8 parts Acidic resin type dispersant solution ( "Disperbyk-110" manufactured by Big Chemie): 8.0 parts

[Examples 152 to 154]
(Coloring composition (RM-52 to 54)
Hereinafter, colored compositions (RM-52 to RM-54) were prepared in the same manner as the colored composition (RM-51) except that the composition was changed to the composition shown in Table 5-3.

[Example 155]
(Preparation of coloring composition (RM-55))
The following mixture was stirred and mixed so as to be uniform, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to prepare a coloring composition (RM-55) having a nonvolatile content of 20% by mass.
Red colorant (RP-4): 10.8 parts Dye derivative 5: 1.2 parts Acrylic resin solution 1: 19.2 parts Propylene glycol monomethyl ether acetate (PGMAc): 58.4 parts Acidic resin type dispersant solution ( Resin-type dispersant solution 1): 10.4 parts

[Example 156]
(Preparation of coloring composition (RM-56))
The following mixture was stirred and mixed so as to be uniform, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to prepare a coloring composition (RM-56) having a nonvolatile content of 20% by mass.
Red colorant (RP-22): 10.8 parts Dye derivative 5: 1.2 parts Acrylic resin solution 1: 19.2 parts Propylene glycol monomethyl ether acetate (PGMAc): 60.8 parts Acidic resin type dispersant solution ( "Disperbyk-110" manufactured by Big Chemie): 8.0 parts

[Comparative Example 2]
(Coloring composition (RCM-2): PR177)
The following mixture was stirred and mixed so as to be uniform, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to prepare a coloring composition (RCM-2) having a nonvolatile component content of 20% by mass.
Red colorant 2 (RCP-2) (PR177): 12.0 parts Acrylic resin solution 1: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acidic resin type dispersant solution (manufactured by BYK Chemie) Disperbyk-110 "): 1.4 parts

[Comparative Example 3]
(Coloring composition (RCM-4): PR269)
The following mixture was stirred and mixed so as to be uniform, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. The solution was filtered through a 0 μm filter to prepare a coloring composition (RCM-4) having a nonvolatile component content of 20% by mass.
Red colorant 4 (RCP-4) (PR269): 12.0 parts Acrylic resin solution 1: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acidic resin type dispersant solution (manufactured by BYK Chemie) Disperbyk-110 "): 1.4 parts

(Coloring composition (RCM-1): PR254)
The following mixture was stirred and mixed so as to be uniform, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to prepare a coloring composition (RCM-1) having a nonvolatile component content of 20% by mass.
Red colorant 1 (RCP-1) (PR254): 12.0 parts Acrylic resin solution 1: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acidic resin type dispersant solution (manufactured by BYK Chemie) Disperbyk-110 "): 1.4 parts

(Coloring composition (RCM-3): PR242)
The following mixture was stirred and mixed so as to be uniform, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to prepare a coloring composition (RCM-3) having a nonvolatile content of 20% by mass.
Red colorant 3 (RCP-3) (PR242): 12.0 parts Acrylic resin solution 1: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acidic resin type dispersant solution (manufactured by BYK Chemie) Disperbyk-110 "): 1.4 parts

(Coloring composition (RCM-5): Formula (4))
The following mixture was stirred and mixed so as to be uniform, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. The solution was filtered through a 0 μm filter to prepare a coloring composition (RCM-5) having a nonvolatile content of 20% by mass.
Red colorant 5 (RCP-5) (Formula (4)): 12.0 parts Acrylic resin solution 1: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acidic resin type dispersant solution (Big Chemie) "Disperbyk-110"): 1.4 parts

(Coloring composition (YCM-1): PY138)
The following mixture was stirred and mixed so as to be uniform, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to prepare a coloring composition (YCM-1) having a nonvolatile component content of 20% by mass.
Yellow colorant 1 (YCP-1) (PY138): 12.0 parts Acrylic resin solution 1: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acidic resin type dispersant solution (by Big Chemie) Disperbyk-110 ": 1.4 parts

(Coloring composition (YCM-2): PY139)
After the following mixture was stirred and mixed so as to be uniform, using zirconia beads having a diameter of 0.5 mm, an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) was used.
, And filtered through a filter having a pore size of 5.0 µm to prepare a colored composition (YCM-2) having a nonvolatile component content of 20% by mass.
Yellow colorant 2 (YCP-2) (PY139): 12.0 parts Acrylic resin solution 1: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acidic resin type dispersant solution (manufactured by BYK Chemie) Disperbyk-110 "): 1.4 parts

(Coloring composition (YCM-3): PY150)
The following mixture was stirred and mixed so as to be uniform, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to prepare a coloring composition (YCM-3) having a nonvolatile component content of 20% by mass.
Yellow colorant 3 (YCP-3) (PY150): 12.0 parts Acrylic resin solution 1: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acidic resin-type dispersant solution (by Big Chemie) Disperbyk-110 ": 1.4 parts

(Coloring composition (YCM-4): PY185)
The following mixture was stirred and mixed so as to be uniform, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to prepare a coloring composition (YCM-4) having a nonvolatile content of 20% by mass.
Yellow colorant 4 (YCP-4) (PY185): 12.0 parts Acrylic resin solution 1: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acidic resin type dispersant solution (manufactured by BYK Chemie) Disperbyk-110 "): 1.4 parts

(Coloring composition (YCM-5): Quinophthalone compound (b))
The following mixture was stirred and mixed so as to be uniform, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to prepare a coloring composition (YCM-5) having a nonvolatile component content of 20% by mass.
Yellow colorant 5 (YCP-5) quinophthalone compound (b)): 12.0 parts Acrylic resin solution 1: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acidic resin type dispersant solution (Big Chemie) "Disperbyk-110": 1.4 parts

(Coloring composition (YCM-6): Quinophthalone compound (t))
The following mixture was stirred and mixed so as to be uniform, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to prepare a coloring composition (YCM-6) having a nonvolatile component content of 20% by mass.
Yellow colorant 6 (YCP-6) quinophthalone compound (t)): 12.0 parts Acrylic resin solution 1: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acidic resin-type dispersant solution (Big Chemie) "Disperbyk-110": 1.4 parts

(Coloring composition (YCM-7): Quinophthalone compound (aa))
The following mixture was stirred and mixed so as to be uniform, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to prepare a coloring composition (YCM-7) having a nonvolatile component content of 20% by mass.
Yellow colorant 7 (YCP-7) quinophthalone compound (aa)): 12.0 parts Acrylic resin solution 1: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acidic resin-type dispersant solution (Big Chemie) "Disperbyk-110": 1.4 parts

(Coloring composition (VCM-1): salt forming compound)
The following mixture was stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 5.0 μm to prepare a coloring composition (VCM-1).
Purple colorant 2 (salt-forming compound): 20.00 parts Propylene glycol monomethyl ether acetate: 80.00 parts

(Evaluation of coloring composition)
The heat resistance, light resistance, foreign matter evaluation, and storage stability of the obtained colored composition and the coating film produced using the same were evaluated by the following methods. Table 5 shows the evaluation results.

(Heat resistance evaluation)
The coloring composition was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater so that the dry film thickness became 2.0 μm, then dried at 70 ° C. for 20 minutes, and then 230 ° C. For 1 hour, and allowed to cool to produce a coated substrate (one embodiment of a color filter). The chromaticity ([L ^* (1), a ^* (1), b ^* (1)]) of the obtained coating film with a C light source was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). It measured using. After that, the sample was heated at 250 ° C. for 1 hour as a heat resistance test, and the chromaticity ([L ^* (2), a ^* (2), b ^* (2)]) was measured using a C light source. And the color difference ΔEab ^* were evaluated and evaluated according to the following four grades.

^{ΔEab * = √ ((L *} (2) - L * (1)) 2 + (a * (2) -a * (1)) 2 + (b * (2) - b * (1)) 2)

A: ΔEab ^* is less than 1.0 (very good)
：: ΔEab ^* is 1.0 or more and less than 2.5 (good)
Δ: ΔEab ^* is 2.5 or more and less than 5.0 (poor)
×: ΔEab ^* is 5.0 or more (extremely poor)

(Light resistance evaluation)
A coated substrate was prepared in the same manner as in the heat resistance evaluation, and the chromaticity ([L ^* (1), a ^* (1), b ^* (1)]) with a C light source was measured using a microspectrophotometer ( The measurement was performed using "OSP-SP100" manufactured by Olympus Optical. Subsequently, an ultraviolet cut filter (“COLORED OPTICAL GLASS L38” manufactured by Hoya Co., Ltd.) was applied onto the substrate, and the substrate was irradiated with ultraviolet light for 100 hours using a 470 W / m ² xenon lamp, and then the chromaticity with a C light source ([[ L ^* (2), a ^* (2), b ^* (2)]) were measured, and the color difference ΔEab ^* was determined by the above formula, and evaluated based on the same criteria as the heat resistance.

(Evaluation of paint foreign matter)
The colored composition is applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater so that the dry film thickness becomes 2.0 μm, and then dried at 70 ° C. for 20 minutes. The coated substrate was produced by heating and cooling at 1 ° C. for 1 hour. Thereafter, the surface of the substrate heated at 250 ° C. for 1 hour was observed. A metallographic microscope “BX60” manufactured by Olympus System was used for the evaluation. The magnification was set to 500 times, and the number of particles observable in five arbitrary visual fields by transmission was counted. The following four grades evaluated.

：: The number of foreign matters is less than 5 (very good)
：: The number of foreign matters is 5 or more and less than 10 (good)
Δ: Number of foreign substances is 10 or more and less than 60 (defective)
×: 60 or more foreign substances (extremely poor)

(Storage stability test method)
The viscosity of the coloring composition at 25 ° C. was measured at 20 rpm using an E-type viscometer (TUE-20L, manufactured by Toki Sangyo Co., Ltd.). From the initial viscosity on the day of the preparation of the coloring composition and the viscosity measured after storage in a constant temperature room at 40 ° C. for 7 days, the viscosity change rate (%) (= (viscosity after storage at 40 ° C. for 7 days−initial viscosity) / initial (Viscosity × 100) was calculated, and the storage stability was evaluated according to the following criteria.

A: Viscosity change rate is less than 10% (very good)
：: The viscosity change rate is 10% or more and less than 20% (good)
Δ: The viscosity change rate is 20% or more and less than 50% (poor)
X: Viscosity change rate of 50% or more (extremely poor)

  As shown in Table 5, the coloring composition using the coloring agent of the present invention had favorable results in heat resistance, light resistance, coating film foreign matter, and storage stability of the coating film. In particular, when compared with the coloring composition using the azo pigment 101 (Comparative Example 1), the dispersion was more stable due to the higher-order steric hindrance of the pigment, so that the quality was improved. In addition, by using a resin-type dispersant having an aromatic carboxylic acid and a dye derivative in combination, excellent results were obtained in heat resistance and light resistance, as well as in coating film foreign matter and storage stability.

<Production method of photosensitive coloring composition for color filter>
[Example 301]
(Photosensitive coloring composition (RR-1))
The following mixture (100 parts in total) was stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 1.0 μm to obtain a photosensitive coloring composition (RR-1).
Coloring composition (RM-1): 23.0 parts Coloring composition (YCM-2): 27.0 parts Acrylic resin solution 2: 7.5 parts Photopolymerizable monomer ("Aronix M-" manufactured by Toagosei Co., Ltd.) 402 "): 2.0 parts Dipentaerythritol hexaacrylate Photopolymerization initiator (" OXE-02 "manufactured by BASF): 1.5 parts Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazol-3-yl]-, 1- (0-acetyloxime)
Cyclohexanone: 39.0 parts

[Examples 302 to 365, Comparative Examples 4 to 13]
(Photosensitive coloring composition (RR-2 to 75))
As shown in Table 6, photosensitive colored compositions (RR-2 to 75) were obtained in the same manner as the photosensitive colored composition (RR-1) except that the types and ratios of the colored compositions were adjusted.
<Evaluation of photosensitive coloring composition for color filter>
The brightness, contrast ratio, and film thickness of the obtained photosensitive coloring composition were measured by the following methods. Table 6 shows the evaluation results. Table 7 shows the evaluation of the transferability.

(Evaluation of brightness)
The obtained photosensitive coloring composition was applied on a glass substrate, dried at 70 ° C. for 20 minutes, and further heated at 230 ° C. for 60 minutes, and the chromaticity of the substrate obtained was x = 0. 683, a coated substrate having y = 0.313 was obtained. The luminance (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

：: 13.5 or more (very good)
：: 13.0 or more and less than 13.5 (good)
△: 12.5 or more, less than 13.0 (practicable)
×: less than 12.5 (bad)

(Contrast ratio evaluation)
Light emitted from the liquid crystal display backlight unit passes through the polarizing plate, is polarized, passes through the coating film of the coloring composition applied on the glass substrate, and reaches the other polarizing plate. At this time, if the polarization planes of the polarization plate and the polarization plate are parallel, light passes through the polarization plate, but if the polarization planes are orthogonal, the light is blocked by the polarization plate. However, when the light polarized by the polarizing plate passes through the coating film of the coloring composition, scattering or the like is caused by the colorant particles, and if a part of the polarization plane is shifted, the light is transmitted when the polarizing plate is parallel. When the polarizing plate is orthogonal, a part of light is transmitted. The transmitted light was measured as the luminance on the polarizing plate, and the ratio between the luminance when the polarizing plate was parallel and the luminance when the polarizing plate was orthogonal was calculated as a contrast ratio.
(Contrast ratio) = (Brightness when parallel) / (Brightness when orthogonal)
Therefore, when scattering occurs due to the coloring agent in the coating film, the luminance at the time of parallelism decreases and the luminance at the time of orthogonality increases, so that the contrast ratio decreases.

Note that a color luminance meter (“BM-5A” manufactured by Topcon Corporation) was used as a luminance meter, and a polarizing plate (“NPF-G1220DUN” manufactured by Nitto Denko Corporation) was used as a polarizing plate. At the time of the measurement, the measurement was performed through a black mask having a hole of 1 cm square in the measurement portion. The same coating film as used for the evaluation of luminance was used.

◎: 8000 or more (very good)
：: 7000 or more to less than 8000 (good)
Δ: 6000 or more to less than 7000 (practicable)
×: less than 6000 (defective)

(Evaluation of film thickness)
The film thickness was measured using the substrate whose luminance was measured. For measuring the film thickness, a surface shape measuring device DEKTAK150 (manufactured by ULVAC-IE) was used.

：: film thickness of less than 2.0 μm ○: film thickness of 2.0 μm or more and less than 2.5 μm Δ: film thickness of 2.5 μm or more and less than 3.0 μm ×: film thickness of 3.0 μm or more

(Evaluation of transferability)
The photosensitive coloring composition for a color filter was applied on a glass substrate using a slit die coater, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 2.4 μm. Next, after the substrate on which the coating film is formed is cooled to room temperature, the coating film is irradiated with radiation containing each wavelength of 365 nm, 405 nm, and 436 nm using a high-pressure mercury lamp through a striped photomask at 1,000 J / m 2. Exposure was performed at an exposure amount of ² . After alkali development, the substrate was washed with ultrapure water, and further post-baked at 230 ° C. for 20 minutes to form red stripe-shaped pixels on the substrate. Subsequently, the transmittance at 520 nm on a glass substrate separated by 8 μm from the red striped pixel was measured (T1). Further, an acrylic resin solution 2 was applied on this substrate using a slit die coater, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 2.5 μm. Further, post-baking was performed at 230 ° C. for 20 minutes. Subsequently, the transmittance at 520 nm on a glass substrate separated by 8 μm from the red striped pixel was measured (T2). The difference between T1 and T2 was evaluated as ΔT (%) using the following four grades. It can be said that the smaller the ΔT value is, the smaller the decrease in luminance due to color transfer to the adjacent other color filter segment is, and the more the transferability is suppressed.

A: ΔT is less than 0.5% (very good)
：: ΔT is 0.5% or more and less than 1.0% (good)
Δ: ΔT is 1.0% or more and less than 3.0% (poor).
×: ΔT is 3.0% or more (extremely poor)

  From the results shown in Table 6, it was clarified that Examples using the coloring agent of the present invention had excellent luminance and were formed into thin films. In particular, C.I. I. Pigment Red 177, C.I. I. Use of Pigment Red 269 or Azo Pigment 101 instead of Pigment Red 269 confirmed a remarkable effect.

  Furthermore, as shown in Table 7, it was confirmed that the coloring composition using the coloring agent of the present invention had good transferability.

<Production method of green and blue photosensitive coloring composition for color filter>
(Green photosensitive coloring composition 1: PG58 / PY138)
The following mixture was stirred and mixed so as to be uniform, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to prepare a green pigment dispersion having a nonvolatile content of 20% by mass.
Green colorant 1 (CI Pigment Green 58): 12.0 parts Acrylic resin solution 1: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acidic resin type dispersant solution (by Big Chemie) "Disperbyk-110"): 1.4 parts

The following mixture was stirred and mixed so as to be uniform, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to prepare a yellow pigment dispersion having a nonvolatile content of 20% by mass.
Yellow colorant 1 (CI Pigment Yellow 138): 12.0 parts Acrylic resin solution 1: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acidic resin type dispersant solution (manufactured by BYK Chemie) "Disperbyk-110": 1.4 parts

Subsequently, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 1 μm to prepare a green photosensitive coloring composition 1.
Green pigment dispersion: 32.0 parts Yellow pigment dispersion: 18.0 parts Acrylic resin solution 2: 7.5 parts Photopolymerizable monomer ("Aronix M-402" manufactured by Toagosei Co., Ltd.): 2.0 parts Dipentaerythritol hexaacrylate Photopolymerization initiator (“OXE-02” manufactured by BASF): 1.5 parts ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (0-acetyloxime)
Cyclohexanone: 39.0 parts

(Blue photosensitive coloring composition 1: PB15: 6 / PV23)
Non-volatile content was 20% by mass in the same manner as the green pigment dispersion except that the green colorant 1 (CI Pigment Green 58) was changed to the blue colorant 1 (CI Pigment Blue 15: 6). Was obtained.

  Except that the green colorant 1 (CI Pigment Green 58) was changed to the purple colorant 1 (CI Pigment Violet 23), the purple color having a nonvolatile content of 20% by mass was the same as the green pigment dispersion. A pigment dispersion was obtained.

  Subsequently, a total of 50.0 parts of the green pigment dispersion 32.0 parts and the yellow pigment dispersion 18.0 parts were replaced with a total of 50.0 parts of the blue dispersion 46.0 parts and the purple dispersion 4.0 parts. Except for the above, a blue photosensitive coloring composition 1 was obtained in the same manner as the green photosensitive coloring composition 1.

<Production and evaluation of color filter>
The red photosensitive coloring composition (RR-4) is applied on a glass substrate on which a black matrix is formed using a slit die coater, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film. Formed. Next, after the substrate on which the coating film is formed is cooled to room temperature, the coating film is irradiated with radiation containing each wavelength of 365 nm, 405 nm, and 436 nm using a high-pressure mercury lamp through a striped photomask at 1,000 J / m 2. Exposure was performed at an exposure amount of ² .
After alkali development, the substrate was washed with ultrapure water, and further post-baked at 230 ° C. for 20 minutes to form red stripe-shaped pixels on the substrate.
Next, a green striped pixel was formed next to the red striped pixel using the green photosensitive coloring composition 1 by the same method. Furthermore, blue striped pixels adjacent to red and green pixels were similarly formed using the blue photosensitive coloring composition 1.
Next, a protective film was formed on the pixels of three colors of red, green, and blue using a photocurable resin composition. In this way, a three-color RGB filter having high luminance and excellent durability was able to be produced.

<Example of manufacturing organic EL element>
Hereinafter, a specific example of manufacturing an organic EL element used as a white light source will be described. In the production examples of organic EL elements, all mixing ratios indicate mass ratios, unless otherwise specified. The vapor deposition (vacuum vapor deposition) was performed in a vacuum of 10 @ -6 Torr (1.33.times.10@-4 Pa) under conditions without temperature control such as substrate heating and cooling. In the evaluation of the light emitting characteristics of the device, the characteristics of an organic EL device having an electrode area of 2 mm × 2 mm were measured.

(Production of Organic EL Element 1 (EL-1))
After treating the washed glass plate with the ITO electrode with oxygen plasma for about 1 minute, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD) is vacuum-deposited, A hole injection layer having a thickness of 150 nm was obtained. On the hole injection layer, the compound (RL-2) and the compound (RL-3) shown in Table 22 were co-deposited at a composition ratio of 100: 2 to form a first light-emitting layer having a thickness of 10 nm. did. Further, the compound (BL-1) and the compound (BL-4) shown in Table 20 were co-evaporated at a composition ratio of 100: 3 to form a second light-emitting layer having a thickness of 20 nm. On this light-emitting layer, a third light-emitting layer was further formed by vapor-depositing α-NPD to a thickness of 5 nm and a compound (GL-3) shown in Table 21 to a thickness of 20 nm. Further, a tris (8-hydroxyquinoline) aluminum complex was vacuum-deposited to form an electron-injection layer having a thickness of 35 nm. Thus, an organic EL device was obtained.

  Further, the organic EL element was hermetically sealed in a dry glow box filled with pure nitrogen to protect the organic EL element from the surrounding environment. This device emitted white light with a light emission luminance of 950 (cd / m2), a maximum light emission luminance of 55000 (cd / m2) and a light emission efficiency of 3.9 (lm / W) at a DC voltage of 5 V. FIG. 2 shows an emission spectrum of the obtained organic EL device (EL-1).

  The peak wavelengths λ1 and λ2 of the organic EL element (EL-1) at which the luminous intensity is maximum in the range of 430 nm to 485 nm and the wavelength of 560 nm to 620 nm, respectively, and the luminous intensity I1 at the wavelength λ1 and the luminous intensity I2 at the wavelength λ2 are shown. Table 8 shows the ratio (I2 / I1).

<Production method of photosensitive coloring composition for color filter>
[Examples 366 to 368, Comparative Example 14]
(Photosensitive coloring composition (RR-76 to 79))
As shown in Table 9, the photosensitive coloring composition (RR-) was prepared in the same manner as the photosensitive coloring composition (RR-1) except that the type and amount of the coloring composition and the amount of the acrylic resin solution 2 were adjusted. 76-79). The amount of the coloring agent in the total solid content of the photosensitive coloring composition (RR-76 to 79) is 35.0% in all cases.

<Production method of green and blue photosensitive coloring composition for color filter>
(Green photosensitive coloring composition 2: PG58 / PY138)
Green photosensitive coloring composition 1 was prepared in the same manner as green photosensitive coloring composition 1 except that the amount of the green pigment dispersion was changed to 34.0 parts and the amount of the yellow pigment dispersion was changed to 16.0 parts. Coloring composition 2 was obtained.

(Blue photosensitive coloring composition 2: PB15: 6 / PV23)
Except that the green pigment dispersion of the green photosensitive coloring composition 1 was changed to 33.0 parts of the blue pigment dispersion and the yellow pigment dispersion was changed to 17.0 parts of the violet pigment dispersion, the same procedure as in the green photosensitive coloring composition 1 was performed. Thus, a blue photosensitive coloring composition 2 was obtained.

<Formation of filter segment>
A black matrix is patterned on a glass substrate, and the photosensitive color composition shown in Table 9 is used on the substrate by a spin coater. In an organic EL device (EL-1) as a light source, x (EL-1) is Each was applied to a film thickness of 0.670 to form a coating film of the coloring composition. The coating was irradiated with 150 mJ / cm2 ultraviolet light through a photomask using an ultra-high pressure mercury lamp. Then, an alkali developing solution comprising 0.15% by mass of sodium carbonate, 0.05% by mass of sodium hydrogen carbonate, 0.1% by mass of an anionic surfactant (“Perylenex NBL” manufactured by Kao Corporation) and 99.7% by mass of water. After removing the unexposed portions by spray development, the substrate was washed with ion-exchanged water and heated at 230 ° C. for 20 minutes to form red filter segments shown in Table 10.

<Evaluation of color characteristics and film thickness>
When the obtained red filter segment is irradiated with light using the organic EL element 1 (EL-1) as a light source, the color characteristics (x, y) of the red filter segment are measured by a microspectrophotometer (“Olympus Optical Co., Ltd.” OSP-SP100 ").
The film thickness was measured using a surface shape measuring device DEKTAK150 (manufactured by ULVAC-IE).
：: Film thickness of less than 2.2 μm ×: Film thickness of 2.2 μm or more

<Preparation of color filter>
[Example 369]
(Color filter (CF-1))
Using the photosensitive coloring composition (RR-76), a red filter segment was formed in the same manner as the above filter segment. Similarly, a green filter segment is formed with a film thickness of y = 0.700 when the organic EL element 1 (EL-1) is used using the green photosensitive coloring composition 2, and then the blue photosensitive coloring composition 2 was used to form a blue filter segment such that y = 0.080 to obtain a color filter (CF-1).

[Examples 370 to 371, Comparative Example 15]
(Color filter (CF-2 to 4))
(Color filter (CF-1)) In the same manner as in Example 369 (color filter (CF-1)), except that the photosensitive coloring composition (RR-76) was replaced with the photosensitive coloring composition described in Table 11, (CF-2 to 4) were obtained.

<Evaluation of color filter>
The color characteristics of the color filters prepared in Examples and Comparative Examples when irradiated with light using the organic EL element 1 (EL-1) were measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). It measured using. The chromaticity point (x, y) in the CIE color system of each color filter segment, the NTSC ratio (the three primary colors of the standard system defined by the US National Television System Committee (NTSC), red (0.67, 0.325), and green) Table 11 shows (0.20, 0.70) and the ratio to the area surrounded by blue (0.14, 0.08).

  From the results of Tables 10 and 11, it was clarified that Examples using the coloring agent of the present invention can be made into a thin film while maintaining a wide color reproducibility of 99% of NTSC ratio.

Reference Signs List 10 liquid crystal display device 11 transparent substrate 12 TFT array 13 transparent electrode layer 14 alignment layer 15 polarizing plate 21 transparent substrate 22 color filter 23 transparent electrode layer 24 alignment layer 25 polarizing plate 30 backlight unit 31 white LED light source LC liquid crystal

Claims (13)

An azo pigment comprising a compound represented by the following general formula (1).

General formula (1)


[In the general formula (1), R ₁ represents a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent. . R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent. ] The azo pigment according to claim 1, comprising a compound represented by the following general formula (2).

General formula (2)


[In the general formula (2), R ₄ represents a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent. . R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent. ]   A colorant for a color filter comprising the azo pigment according to claim 1.   A coloring composition for a color filter comprising at least a coloring agent and a binder resin, wherein the coloring agent contains the coloring agent for a color filter according to claim 3.   The coloring composition for a color filter according to claim 4, further comprising a resin-type dispersant having an acidic substituent.   The colored composition for a color filter according to claim 5, wherein the resin-type dispersant having an acidic substituent is a resin-type dispersant having an aromatic carboxyl group.   The coloring composition for a color filter according to any one of claims 4 to 6, further comprising a dye derivative, wherein the dye derivative contains a dye derivative having a basic substituent. The colorant further comprises C.I. I. Pigment Red 254, C.I. I. Pigment Red 242, C.I. I. Pigment yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 150, and at least one selected from the group consisting of a yellow pigment represented by the following general formula (3) and a brominated diketopyrrolopyrrole pigment. Coloring composition for color filters.

General formula (3)


[In the general formula (3), Z _{1 to} Z ₁₃ each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and a substituent. It may have an aryl group, -SO ₃ H, -COOH, and monovalent to trivalent metal salt thereof acidic groups, alkylammonium salt, an optionally substituted phthalimidomethyl group, or a substituent The following shows a sulfamoyl group which may be possessed.
Adjacent groups of Z _{1 to} Z ₄ and / or Z _{10 to} Z ₁₃ may combine to form an aromatic ring which may have a substituent. ]
  The colored composition for a color filter according to any one of claims 4 to 8, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.   A color filter comprising, on a substrate, a filter segment formed from the coloring composition for a color filter according to any one of claims 4 to 9.   A liquid crystal display device comprising the color filter according to claim 10.   A solid-state imaging device comprising the color filter according to claim 10.   An organic EL display device comprising the color filter according to claim 10.