JP2019194298A - Azo pigment, color filter colorant, coloring composition, and color filter - Google Patents

Abstract

To provide a color filter coloring composition which is excellent in fastness such as heat resistance and light resistance, causes few particles in a coating and has good storage stability, and in addition has a high luminance and a high contrast ratio and can reduce the film thickness in expressing the same color.SOLUTION: An azo pigment comprises compounds represented by the general formulas (1) and (2) in the figure.SELECTED DRAWING: Figure 1

Description

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

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. Other typical liquid crystal display devices include an in-plane switching (IPS) method in which a pair of electrodes is provided on one substrate and electrolysis is applied in a direction parallel to the substrate, negative dielectric anisotropy Vertical alignment (VA) method for vertically aligning nematic liquid crystal with optical properties, and Optical Convencence Bend (OCB) method in which the optical axes of uniaxial retardation films are orthogonal to each other to perform optical compensation Etc., and each has been put to practical use.

  A liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and has recently been used in televisions, personal computer monitors, and the like. There is an increasing demand for brightness.

  A color filter is a surface of a transparent substrate such as glass, in which two or more kinds of fine band (striped) filter segments of different hues are arranged in parallel or crossing each other, or fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

  Generally, in a color liquid crystal display device, a transparent electrode for driving a 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. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof must generally be performed at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.

  Quality items required for the color filter include brightness and contrast ratio. When a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disturbed, and when light must be blocked (OFF state), light must leak or be transmitted (ON) In other words, the transmitted light is attenuated in the state), resulting in a blurred screen. Therefore, in order to realize a high-quality liquid crystal display device, high contrast is indispensable.

  If a color filter with low luminance is used, the light transmittance is low, resulting in a dark screen. In order to obtain a bright screen, it is necessary to increase the number of backlights that are light sources. For this reason, from the viewpoint of suppressing an increase in power consumption, increasing the brightness of color filters has become a trend. Furthermore, as described above, since the color liquid crystal device has been used for televisions, personal computer monitors, and the like, the demand for high reliability and high brightness is increasing for the color filter.

  The red filter segment, which is one of the three primary colors (red, green, blue; RGB) of the color filter substrate, has excellent light resistance and heat resistance, such as diketopyrrolopyrrole pigment, anthraquinone pigment or perylene pigment as a colorant. Are generally used alone or in combination.

  Among the pigment types, C.I. which is a diketopyrrolopyrrole pigment from the viewpoint of luminance. 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 these, C.I. I. Pigment Red 177 has a spectral transmittance of C.I. I. Since it is lower than CI Pigment Red 254 and the spectral shape is poor, C.I. I. As Pigment Red 177 was added, there was a defect that caused a decrease in luminance. Therefore, C.C. I. Development of an alternative material for Pigment Red 177 is desired.

  In recent years, in order to achieve high brightness and high coloring power, C.I. I. Although it has been proposed to use an azo pigment represented by Pigment Red 269 or a disazo pigment described in Patent Document 3 as a main pigment, the affinity of the pigment to the solvent, the acidity of the pigment surface, and the like have been proposed. I. Pigment red 254 and C.I. I. Since it is different from CI Pigment Red 177 and the like, it has inferior dispersibility, fluidity and storage stability, and further has inferior heat resistance and light resistance, and a practical color filter has not been obtained. In addition, C.I. I. In the case of an azo pigment such as CI 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 dye transfer properties.

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

JP 2008-304521 A Special table 2007-533802 gazette JP 2014-160160 A

  The object of the present invention is not only excellent in fastness such as heat resistance and light resistance, few coating film foreign matter, good storage stability and transferability, but also high brightness and contrast ratio, and expresses the same color It is to provide a colored composition for a color filter that sometimes has a thin film thickness.

  As a result of intensive studies, the present inventors have found that the above problem 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 characterized by comprising compounds represented by the following general formulas (1) and (2).

General formula (1)

[In General Formula (1), R ₁ represents a halogen atom, an alkyl group which may have a substituent, or an alkoxyl group which may have a substituent. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group that may have a substituent, or a phenyl group that may have a substituent.
X _{1 to} X ₈ each independently represents a hydrogen atom, an alkyl group that may have a substituent, an alkoxyl group that may have a substituent, or a halogen atom. ]

General formula (2)
[In General Formula (2), R ₁ represents a halogen atom, an alkyl group which may have a substituent, or an alkoxyl group which may have a substituent. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group that may have a substituent, or a phenyl group that may have a substituent.
X _{1 to} X ₈ each independently represents a hydrogen atom, an alkyl group that may have a substituent, an alkoxyl group that may have a substituent, or a halogen atom. ]

  In addition, in the embodiment of the present invention, the content of the compound represented by the general formula (2) with respect to the total amount of the compounds represented by the general formulas (1) and (2) is 0.1 to 20.0. It is related with the said azo pigment which is the mass%.

  An embodiment of the present invention also relates to a color filter colorant comprising the azo pigment.

  An embodiment of the present invention is a color filter coloring composition comprising at least a colorant and a binder resin, wherein the colorant is the color filter colorant. Related to things.

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

  An embodiment of the present invention also 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.

  The embodiment of the present invention further 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 an embodiment of the present invention, the colorant further contains 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 150, the yellow pigment represented by the following general formula (3), and at least one selected from the group consisting of brominated diketopyrrolopyrrole pigments are included.

General formula (3)
[In General Formula (3), Z _{1 to} Z ₁₃ each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. An aryl group which may have, —SO ₃ H, —COOH, and monovalent to trivalent metal salts, alkylammonium salts, phthalimidomethyl groups which may have a substituent, or substituents of these acidic groups; The sulfamoyl group which may have is shown.
The adjacent groups of Z _{1 to} Z ₄ and / or Z _{10 to} Z ₁₃ may be united to form an aromatic ring which may have a substituent. ]

  In addition, the embodiment of the present invention further relates to the color filter coloring composition, further comprising a photopolymerizable monomer.

  An embodiment of the present invention also relates to a color filter comprising a filter segment formed on the substrate from the color filter coloring composition.

An embodiment of the present invention also relates to a liquid crystal display device including the color filter.

Moreover, the embodiment of this invention is related with a solid-state image sensor provided with the said color filter.

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

  According to the present invention, excellent in fastness such as heat resistance and light resistance, few coating film foreign matters, good storage stability, high brightness and contrast ratio, film thickness when expressing the same color There exists the outstanding effect that the coloring composition for color filters and color filter which become thin can be provided.

FIG. 1 is a schematic cross-sectional view of a liquid crystal display device.

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

<Azo pigment>
First, the azo pigments represented by the general formulas (1) and (2) of the present invention will be described. In the present specification, “azo pigment represented by the general formulas (1) and (2)” is abbreviated as “pigment”, and “colorant for color filter” is abbreviated as “colorant”. There is.

  In the azo pigment of the present invention, the compounds represented by the general formulas (1) and (2) are essential components, and the general formula (1) It is preferable that content of the compound represented by 2) is 0.1-20.0 mass%, and it is especially preferable that it is 0.1-10.0 mass%.

General formula (1)

In general formula (1), R ₁ represents a halogen atom, an alkyl group which may have a substituent, or an alkoxyl group which may have a substituent. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group that may have a substituent, or a phenyl group that may have a substituent.
X _{1 to} X ₈ each independently represents a hydrogen atom, an alkyl group that may have a substituent, an alkoxyl group that may have a substituent, or a halogen atom.

General formula (2)

In General Formula (2), R ₁ represents a halogen atom, an alkyl group that may have a substituent, or an alkoxyl group that may have a substituent. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group that may have a substituent, or a phenyl group that may have a substituent.
X _{1 to} X ₈ each independently represents a hydrogen atom, an alkyl group that may have a substituent, an alkoxyl group that may have a substituent, or a halogen atom.

In the general formulas (1) and (2), examples of the “halogen atom” in R ₁ include fluorine, bromine, chlorine, and iodine. Among these, chlorine is preferable.

In the general formulas (1) and (2), as the “alkyl group optionally having substituent (s)” for R ₁ , methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert- Butyl group, isobutyl group, tert-amyl group, 2-ethylhexyl group, stearyl group, chloromethyl group, trichloromethyl group, trifluoromethyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-nitroethyl group, cyclopentyl group , A cyclohexyl group, a dimethylcyclohexyl group, and the like. Among these, a methyl group and a trifluoromethyl group are preferable.

In general formulas (1) and (2), R _{1 represents} an “alkoxyl group which may have a substituent”.
As methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, n-octyloxy group, 2-ethylhexyloxy group, trifluoromethoxy group, cyclohexyloxy group, stearyloxy group, 2- (Diethylamino) ethoxy group and the like can be mentioned. Among these, a methoxy group and a trifluoromethoxy group are preferable, and a methoxy group is particularly preferable.

In R ₂ and R ₃ in the general formulas (1) and (2), the “alkyl group which may have a substituent” includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. Group, tert-butyl group, isobutyl group, tert-amyl group, 2-ethylhexyl group, stearyl group, chloromethyl group, trichloromethyl group, trifluoromethyl group, 2-methoxyethyl group, 2-hydroxyethyl group, 2- Examples include chloroethyl group, 2-nitroethyl group, cyclopentyl group, cyclohexyl group, dimethylcyclohexyl group, and the like, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, isobutyl group. A 2-hydroxyethyl group is preferred.

In general formulas (1) and (2), in R ₂ and R ₃ , the substituent of the “optionally substituted phenyl group” may have a halogen atom or a substituent in R ₁ . Examples thereof include an alkyl group and an alkoxyl group which may have a substituent. Besides these, a hydroxyl group, an amino group, —NR ₄ R ₅ , a sulfo group, —SO ₂ NR ₆ R ₇ , —COOR ₈ , -CONR ₉ R _10, a nitro group, a cyano group.

R _{4 to} R ₁₀ each independently represent a hydrogen atom or an alkyl group which may have a substituent,
As the “alkyl group which may have a substituent”, an alkyl group substituted with an amino group, a monoalkylamino group or a dialkylamino group is preferable.

In general formulas (1) and (2), in X _{1 to} X ₈ , the “optionally substituted alkyl group” has the same meaning as in R ₁ , and is a methyl group, an ethyl group, trifluoro A methyl group is preferred.

In general formulas (1) and (2), in X _{1 to} X ₈ , the “optionally substituted alkoxyl group” has the same meaning as in R ₁ , and a methoxy group and a trifluoromethoxy group are preferable.

  Furthermore, the azo pigment of the present invention may contain compounds represented by the following general formulas (4) to (8).

General formula (4)

In General Formula (4), R ₁ represents a halogen atom, an alkyl group that may have a substituent, or an alkoxyl group that may have a substituent. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group that may have a substituent, or a phenyl group that may have a substituent.
X _{1 to} X ₈ each independently represents a hydrogen atom, an alkyl group that may have a substituent, an alkoxyl group that may have a substituent, or a halogen atom.

General formula (5)

In General Formula (5), R ₁ represents a halogen atom, an alkyl group that may have a substituent, or an alkoxyl group that may have a substituent. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group that may have a substituent, or a phenyl group that may have a substituent.

General formula (6)

In General Formula (6), R ₁ represents a halogen atom, an alkyl group that may have a substituent, or an alkoxyl group that may have a substituent. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group that may have a substituent, or a phenyl group that may have a substituent.
X _{1 to} X ₈ each independently represents a hydrogen atom, an alkyl group that may have a substituent, an alkoxyl group that may have a substituent, or a halogen atom.

General formula (7)

In General Formula (7), R ₁ represents a halogen atom, an alkyl group that may have a substituent, or an alkoxyl group that may have a substituent. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group that may have a substituent, or a phenyl group that may have a substituent.
X _{1 to} X ₈ each independently represents a hydrogen atom, an alkyl group that may have a substituent, an alkoxyl group that may have a substituent, or a halogen atom.

General formula (8)

In General Formula (8), R ₁ represents a halogen atom, an alkyl group that may have a substituent, or an alkoxyl group that may have a substituent. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group that may have a substituent, or a phenyl group that may have a substituent.
X _{1 to} X ₈ each independently represents a hydrogen atom, an alkyl group that may have a substituent, an alkoxyl group that may have a substituent, or a halogen atom.

In the general formula (4) ~ (8), R 1 ~R 3, and X ₁ to X ₈ are the same meanings as R ₁ to R _3, and X ₁ to X ₈ in the general formula (1).

<Colorant for color filter>
The colorant for a color filter of the present invention is characterized by containing an azo pigment made of a compound represented by the general formulas (1) and (2). The colorant for color filter of the present invention includes a pigment other than the pigment containing the compounds represented by the above general formulas (1) and (2) within a range that does not impair the effects of the present invention in order to adjust chromaticity. Alternatively, other colorants such as dyes may be used in combination. These pigments / dyes can be used alone or in admixture of two or more at any ratio as required.

  Examples of other colorants include 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 red dyes include xanthene dyes, azo (pyridone series, barbituric acid series, etc.) dyes, disazo dyes, anthraquinone dyes, and methine dyes. In addition, lake pigments obtained by forming these dyes, forms of inorganic salts of acidic dyes having acidic groups such as sulfonic acid and carboxylic acid, salt-forming compounds of acidic dyes and nitrogen-containing compounds, and sulfonic acid amide compounds of acidic dyes It may be.

In addition, C.I. I. 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 series, azo series (pyridone series, barbituric acid series, metal complex series, etc.), disazo series, and methine series.

Preferred colorants to be used in combination are azo, naphtholazo, diketopyrrolopyrrole, anthraquinone, quinophthalone, and perylene dyes from the viewpoint of fastness such as heat resistance and light resistance and chromaticity region. Is mentioned. Specifically, C.I. I. Pigment red 269, 177, 254, 242 and C.I. I. Pigment yellow 138, 139, 150, 185, yellow pigments represented by the following general formula (3), and brominated diketopyrrolopyrrole pigments.
In particular, from the viewpoint of luminance and coloring power, C.I. I. Pigment red 254, 242, C.I. I. Pigment Yellow 138, 139, 150, a yellow pigment represented by the following general formula (3), and a brominated diketopyrrolopyrrole pigment are more preferable.

General formula (3)

[In General Formula (3), Z _{1 to} Z ₁₃ each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. An aryl group which may have, —SO ₃ H, —COOH, and monovalent to trivalent metal salts, alkylammonium salts, phthalimidomethyl groups which may have a substituent, or substituents of these acidic groups; The sulfamoyl group which may have is shown.
The adjacent groups of Z _{1 to} Z ₄ and / or Z _{10 to} Z ₁₃ may be united 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 thereof include alkyl groups 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 methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutyloxy group, tert-butyloxy group, neopentyloxy group, 2, 3 -In addition to 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 group And an alkoxyl group having a substituent such as a benzyloxy group.

  In addition, examples of the aryl group which may have a substituent include an aryl group such as a phenyl group, a naphthyl group, an anthranyl group, a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p- 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, 2-aminoanthraquinonyl group and other aryl groups having a substituent.

Examples of acidic groups include —SO ₃ H and —COOH, and monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, and aluminum salts. Etc. In addition, as the alkyl ammonium salt of acidic group, quaternary alkyl such as ammonium salt of long chain monoalkylamine such as octylamine, laurylamine, stearylamine, palmityltrimethylammonium, dilauryldimethylammonium, distearyldimethylammonium salt, etc. An ammonium salt is mentioned.

The “substituent” in the phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N—CH ₂ —) which may have a substituent and the sulfamoyl group (H ₂ NSO ₂ —) which may have a substituent "Includes the above halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, and the like.

The adjacent groups of 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. The aromatic ring herein includes a hydrocarbon aromatic ring and a heteroaromatic ring. The hydrocarbon aromatic ring includes a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring and the like, and the heteroaromatic ring includes pyridine. And a ring, a pyrazine ring, a pyrrole ring, a quinoline ring, a quinoxaline ring, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyrazole ring, an indole ring, and a carbazole ring.

  Specific examples of the yellow pigment represented by the general formula (3) used in the colorant for color filter of the present invention include the following quinophthalone compounds (a) to (ad), and the present invention includes them. It is not limited. Moreover, although the quinophthalone compound used by this invention can be manufactured by the method of patent gazette 2930774, for example, this invention is not limited to these.

The dyes that can be used in combination are red and purple, and preferably have any form of oil-soluble dyes, acid dyes, direct dyes, and basic dyes.
Among these, use of a xanthene oil-soluble dye, a xanthene basic dye, and a xanthene acid dye is preferable because of excellent hue. In addition, lake pigments obtained by forming these dyes, forms of inorganic salts of acidic dyes having acidic groups such as sulfonic acid and carboxylic acid, salt-forming compounds of acidic dyes and nitrogen-containing compounds, and sulfonic acid amide compounds of acidic dyes It may be.

Examples of xanthene 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., which is a rhodamine-based oil-soluble dye having high color developability. 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 preferable.
Examples of xanthene basic dyes include C.I. I. Basic Red 1 (Rhodamine 6 GCP), 8 (Rhodamine G), C.I. I. Examples thereof include basic violet 10 (rhodamine B). Among these, C.I. I. Basic Red 1, C.I. I. It is preferable to use basic violet 10.
Examples of xanthene acid dyes include C.I. I. Acid Red 51 (erythrosin (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 Phloxin 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. It is preferable to use Acid Violet 9.
Among these, 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 rhodamine acid dye 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 acid dye, is particularly excellent in terms of color developability, heat resistance and light resistance. I. Most preferably, Acid Red 52 is used.

  When used in combination with the above red pigment, yellow pigment, orange pigment, and dye, the content of the pigment containing the compounds represented by the general formulas (1) and (2) is 10 in 100% by mass of the total colorant. It is -90 mass%, Preferably it is 20-80 mass%. When the content of the pigment containing the compounds represented by the general formulas (1) and (2) is less than 10% by mass, the effect of excellent brightness 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 dispersed for 1 minute with an ultrasonic cleaner to prepare a measurement sample. This sample was photographed with a transmission electron microscope (“JEM-1200EX” manufactured by JEOL Ltd.), and three photographs (for three fields of view) in which primary particles of 100 or more pigments can be confirmed were taken. The size of primary particles was measured. Specifically, the short axis diameter and major axis diameter of the primary particles of each pigment are measured in nm units, the average is the primary particle diameter of the pigment, and a total of 300 distributions are created in 5 nm increments. The number average particle size was calculated by approximating the median value of the increments (for example, 8 nm in the case of 6 nm or more and 10 nm or less) as the particle size of those particles and calculating based on the particle size and the number thereof.

<Miniaturization of colorant>
The pigment used in the present invention can be used after being refined. The pigment containing the compounds represented by the general formulas (1) and (2) is also preferably used after being refined, but the refinement method is not particularly limited. For example, wet grinding, dry grinding Any of the dissolution precipitation methods can be used, and as exemplified in the present invention, a salt milling treatment by a kneader method which is one kind of wet grinding can be performed.

  The primary particle size of the refined pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. A particularly preferable range is a range of 25 to 85 nm.

  Salt milling is a process of heating a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent using a kneader such as a kneader, trimix, two-roll mill, three-roll mill, ball mill, attritor or sand mill. Then, after mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  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 from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by mass, and most preferably 300 to 1000 parts by mass with respect to 100 parts by mass of the colorant, from the viewpoint of both processing efficiency and 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) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. 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 weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the colorant.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. It is preferable that the usage-amount of resin is the range of 5-200 mass parts with respect to 100 mass parts of coloring agents.

  Further, when the pigment is subjected to a 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 an optionally substituted phthalimidomethyl group is introduced into an organic pigment, anthraquinone, acridone, or triazine. It is done. These can be used alone or in admixture of two or more.

  The amount of these pigment derivatives used is preferably 2 to 30 parts by mass, and most preferably 5 to 20 parts by mass with respect to 100 parts by mass of the colorant.

<Coloring composition for color filter>
The color composition for a color filter of the present invention is composed of a binder resin in addition to the colorant described above.

<Binder resin>
The binder resin disperses, dyes, or penetrates the colorant, and examples thereof include a thermoplastic resin. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the 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 also be used.

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

  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, 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 colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the colorant carrier and 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 the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  Since the binder resin has good film formability and various resistances, it is preferably used in an amount of 20 parts by mass or more with respect to 100 parts by mass of the total mass of the colorant, the colorant concentration is high, and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 1000 parts by mass or less.

  Examples of the thermoplastic resin used for the binder resin include 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 copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group.
Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (i) and (ii).

[Method (i)]
As 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. Then, the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to convert the unsaturated ethylenic double bond and the carboxyl group to There is a way to introduce.

  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 epoxy cyclohexyl (meth) acrylates, and these may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Further, 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 increased.

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

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

  Examples of unsaturated ethylenic monomers 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 or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing coating film foreign matter, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

<Organic solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent is included to facilitate the formation. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and 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-dimethylacetami 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 Lenglycol 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 in admixture of two or more at any ratio as required.

  The solvent can be used in an amount of 100 to 10000 parts by mass, preferably 500 to 5000 parts by mass with respect to 100 parts by mass of the colorant in the coloring composition.

<Photopolymerizable monomer>
Photopolymerizable monomers that may be added to the colored composition of the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 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 diglycy Luether 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, methylolated melamine (meth) acrylic acid ester, epoxy (meth) acrylate, urethane acrylate and other acrylic acid esters and methacrylic acid esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, ru (meth) acrylamide, N-vinylformamide, acrylonitrile and the like. These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

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

<Photopolymerization initiator>
In the colored composition of the present invention, a photopolymerization initiator is added to form a filter segment by photolithography by curing the composition by ultraviolet irradiation, and a solvent development type or alkali development type photosensitive coloring composition is added. It can be prepared in the form of

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl 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 compound such as benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 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 Thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-meth) Cyphenyl) -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, 2 -(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 oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6- Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole A imidazole compound; a titanocene compound, or the like. These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The photopolymerization initiator content is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 5 to 400 parts by mass from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer.
Sensitizers include unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, Michler's ketone derivatives and the like. These sensitizers can be used singly or in combination of two or more at any ratio as required.

Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special Examples include, but are not limited to, sensitizers described in “Functional Materials” (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.
Among the sensitizers, particularly preferred sensitizers include thioxanthone derivatives, Michler 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 colored composition, and 5 to 50 parts by mass from the viewpoint of photocurability and developability. It is more preferable that

<Multifunctional 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 polyfunctional thiol together with the above-mentioned photopolymerization initiator, in the radical polymerization process after light irradiation, it acts as a chain transfer agent and generates a thiyl radical that is less susceptible to polymerization inhibition by oxygen. The composition becomes highly sensitive. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable.

  Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropioate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3- Mercaptopropionate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropionate) ), Dipentaerythritol hexakis (3-mercaptopropionate), trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s- Examples include triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine. These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

0.05-100 mass parts is preferable with respect to 100 mass parts of coloring agents, and, as for content of a polyfunctional thiol, 1.0-50.0 mass parts is more preferable.
By using 0.05 part by mass or more of polyfunctional thiol, better development resistance can be obtained. When a monofunctional thiol having one thiol (SH) group is used, such an improvement in development resistance cannot be obtained.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. 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 Toray Dow Corning, 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. In general, the leveling agent content is preferably 0.003 to 1.0 parts by mass with respect to 100 parts by mass of the total mass of the colored composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

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

  An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used. Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And polyethylene glycol monolaurate. Other examples include amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Ultraviolet absorber, polymerization inhibitor>
The coloring composition for a color filter of the present invention can 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 absorber 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, etc. 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, 2,4-di Benzophenone series such as droxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, salicylate series such as phenyl salicylate, 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 ] Hindered amines such as [(2,2,6,6-tetramethyl-4-piperidinyl) imino]. These ultraviolet absorbers can be used singly or in combination of two or more at any ratio as required.

  Examples of the polymerization inhibitor include hydroquinone such as methyl hydroquinone, t-butyl hydroquinone, 2,5-di-t-butyl hydroquinone, 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 dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate, etc. And manganese salt compounds, 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxylamine, etc. Toroso compounds and their ammonium salts or aluminum salts and the like. These polymerization inhibitors can be used singly or as a mixture of two or more at any ratio as required.

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 with respect to 100 parts by mass of the colorant in the coloring composition.
By using 0.01 part by mass or more of the ultraviolet absorber or the polymerization inhibitor, better resolution can be obtained.

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

  Preferable examples of the antioxidant include hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfide-based antioxidants. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants. These antioxidants can be used singly or as a mixture of two or more at any ratio as required.

  As the hindered phenol-based antioxidant, 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- And di-t-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

  In the hindered amine antioxidant, 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 -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.

  As the phosphorus-based antioxidant, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine- 6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2- Yl) oxy] ethyl] amine, ethylbisphosphite (2,4-ditert-butyl-6-methylphenyl).

  As sulfide-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 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 in a total of 100 parts by mass of the solid content of the color filter coloring composition. When the amount of the antioxidant is less than 0.1 parts by mass, the effect of increasing the transmittance is small, and when the amount is more than 5 parts by mass, the hardness is greatly reduced, and the sensitivity of the color filter coloring composition is greatly decreased.

<Other ingredients>
The coloring composition for a color filter of the present invention contains an adhesion improver such as a silane coupling agent or an amine compound that has a function of reducing dissolved oxygen in order to improve adhesion to a transparent substrate. Can be made.

  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, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxy (Cyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, epoxysilanes such as γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (Aminoethyl) γ-amino 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 with respect to 100 parts by mass of the colorant in the coloring composition.

  Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 -2-ethylhexyl dimethylaminobenzoate, N, N-dimethyl paratoluidine, etc. are mentioned.

<Method for producing colored composition for color filter>
The coloring composition for a color filter of the present invention includes a kneader, a two-roll mill, a three-roll mill, a ball mill, a coloring agent in a colorant carrier such as a resin and / or a solvent, together with a dispersion aid as necessary. It can be produced by finely dispersing 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 even if it is added later to the prepared colorant dispersion. When the solubility of the colorant such as a dye is high, specifically, it is highly soluble in the solvent to be used, and if it is dissolved and no foreign matter is confirmed by stirring, it is finely dispersed as described above. There is no need.

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition comprises the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other pigment dispersants, and additives. Etc. can be prepared by mixing them. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

<Dispersing aid>
When dispersing the colorant in the colorant carrier, it is preferable to contain not only the resin-type dispersant but also a dispersion aid such as a pigment derivative and a surfactant as appropriate. Since the dispersion aid has a great effect of preventing reaggregation of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has luminance and storage stability. Become good.

<Resin type dispersant>
The colored composition for a color filter of the present invention preferably further contains a resin type dispersant having an acidic substituent.
The resin-type dispersant has a colorant-affinity part having the property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant to the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is 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, and 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 -SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 160 manufactured by Nippon Lubrizol Corporation, such as P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc. 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.

In addition, 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 preferable because the effect of preventing reaggregation of the colorant after dispersion is particularly large. . As the resin-type dispersant having an aromatic carboxyl group, those containing the following (S1) or (S2) are preferable.
(S1) A resin-type dispersant that 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. A resinous dispersant that is a coalescence.

[Resin type dispersant (S1)]
The resin-type dispersant (S1) can be produced by a known method such as WO2008 / 007776, JP2008-029901A, or JP2009-155406A. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at the terminal. For example, the ethylenically unsaturated monomer (r) is polymerized in the presence of the compound (q) having a hydroxyl group. 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 it is preferable that there are a plurality of terminal hydroxyl groups, a compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

  That is, a polymer having two hydroxyl groups at one end, which is a more preferable example, includes the monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. It can obtain as a polymer (p1) which polymerized the ethylenically unsaturated monomer (r) containing. The hydroxyl group of the polymer (p) having a hydroxyl group reacts with the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride to form an ester bond, while the anhydride ring is opened, and the carboxylic acid Produce.

[Resin type dispersant (S2)]
The resin-type dispersant (S2) can be produced by a known method such as JP2009-155406A, JP2010-185934A, JP2011-157416A, 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 the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride. can get. In particular, in the presence of a reaction product of the hydroxyl group of the compound (q1) having two hydroxyl groups and one thiol group in the molecule and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride. And a polymer obtained by polymerizing the ethylenically unsaturated monomer (r) containing the monomer (r1).

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

  The resin-type dispersant is preferably used in an amount of about 5 to 200 parts by mass with respect to the total amount of the colorant, and more preferably about 5 to 100 parts by mass from the viewpoint of film formability.

<Dye derivative>
It is preferable that the coloring composition for a color filter of the present invention further contains a pigment derivative. The pigment derivative may be contained in the azo pigment.
As the dye derivative used in the present invention, a known dye derivative having an organic group, an acidic group, a basic group, a neutral group or the like can be used. For example, compounds having acidic functional groups such as sulfo group, carboxy group, and phosphoric acid group and amine salts thereof, compounds having basic functional groups such as sulfonamide group and tertiary amino group at the terminal, phenyl group and phthalimide Examples thereof include compounds having a neutral functional group such as an alkyl group. Examples of organic dyes include diketopyrrolopyrrole pigments, copper phthalocyanine, zinc phthalocyanine, aluminum phthalocyanine, halogenated copper phthalocyanine, halogenated zinc phthalocyanine, halogenated aluminum phthalocyanine, metal-free phthalocyanine and other phthalocyanine pigments, aminoanthraquinone, diamino Anthraquinone pigments such as dianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thiazine indigo pigment, triazine pigment, Benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, kinoff Ron pigments, naphthol pigments, threne pigments, metal complex pigments, azo, disazo, azo pigments such as polyazo, and the like.
More specifically, Japanese Patent Application Laid-Open Nos. 61-246261, 63-264673, 09-272812, 10-245501, 10-265697, and 11-199796, JP 2001-172520, JP 2001-220520, JP 2002-201377, JP 2003-165922, JP 2003-168208, JP 2003-2003. JP 171594, JP 2004-217842, JP 2005-213404, JP 2006-291194, JP 2007-079094, JP 2007-226161, JP 2007-314681. Gazette, JP2007-314785A, JP2008-3 281, JP2009-57478, WO2009 / 025325, WO2009 / 081930, JP2011-162662, WO2011-052617, JP2012-172092 and JP2012-2. Nos. 208329, 2012-226110, WO2012 / 102399, JP2014-5439, WO2016 / 16351, JP2017-156397, JP5753266, etc. These may 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. However, an acidic group, a basic group, a neutral group, or the like may be added to the organic dye residue. The compound having the functional group is synonymous with the pigment 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 of pigments is remarkable. Further, organic pigment residues derived from diketopyrrolopyrrole pigments, anthraquinone pigments, quinophthalone pigments and azo pigments are preferred from the viewpoint of hue and contrast ratio.

<Surfactant>
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, 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 alkylbetaines such as betaine acetate and alkylimidazolines, and these may be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When adding a surfactant, it is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass with respect to 100 parts by mass of the colorant. When the content of the surfactant is less than 0.1 parts by mass, it is difficult to obtain the added effect. 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 a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. 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. The at least one filter segment is formed from the colored composition of the present invention.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method. The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film 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 alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate 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 above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, 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 method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

  A black matrix can be formed in advance before forming each color filter segment on a base material such as a transparent substrate or a reflective substrate. Examples of the black matrix include, but are not limited to, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, and a resin film in which a light shielding agent is dispersed. Further, 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. Further, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

  The dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 μm, more preferably 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 bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

  As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. In addition, 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 in order to drive the liquid crystal after forming the panel.

<Liquid crystal display device>
A liquid crystal display device provided with the color filter of the present invention will be described.
The 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. In the present invention, it is preferable to use a white LED in that the red reproduction region is widened. FIG. 1 is a schematic cross-sectional view of a liquid crystal display device 10 provided with a color filter of the present invention. The apparatus 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 that are arranged 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). A TFT (thin film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. 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 so as to cover the color filter 22 and further, a transparent electrode layer 23 made of, for example, ITO is formed thereon, and the alignment layer 24 covers the transparent electrode layer 23. Is provided.

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

  White LED light sources include those in which a fluorescent filter is formed on the surface of a blue LED, and those in which a phosphor is contained in a resin package of a blue LED. The wavelength (maximum emission intensity within a range of 430 nm to 485 nm ( λ3), a wavelength (λ4) at which the emission intensity is maximum within a range of 530 nm to 580 nm, a wavelength (λ5) at which the emission intensity is maximum within a range of 600 nm to 650 nm, and a wavelength The ratio (I4 / I3) of the emission intensity I3 at λ3 to the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 (I5 / I3 ) Is a white LED light source (LED1) having a spectral characteristic of 0.1 or more and 1.3 or less, or has a wavelength (λ1) with a maximum emission intensity in the range of 430 nm to 485 nm. The second emission intensity peak wavelength (λ2) is 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 or more and 0. A white LED light source (LED2) having a spectral characteristic of 0.7 or less is preferred.

  Specific examples of LED1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation), NSSW304D-HG-V1 (manufactured by Nichia Corporation), and the like.

  Specific examples of the LED 2 include NSSW 440 (manufactured by Nichia Corporation), NSSW304D (manufactured by Nichia Corporation), and the like.

<Color filters for solid-state image sensors>
The color filter segment according to the present invention can be formed using a known method without any particular limitation. However, since the filter segment of the image pickup element is as fine as submicron to several tens of microns, optical lithography is used. Is preferred.
An embodiment of the present invention is a method for producing a color filter, comprising a color filter segment obtained by curing the above-described colored composition. It includes a color filter segment obtained by curing the colored 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 color filter segment according to the present invention, a known color composition containing a color pigment, a color dye, or both a color pigment and a color dye may be used. The method for forming the colored filter segment is not particularly limited, but a photosensitive coloring composition that is a negative resist is generally used.
When the 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 from a negative type photosensitive green composition, and in this case, a negative type The thickness of the color resist layer is set in the range of 0.1 μm to 3.0 μm.
A plurality of portions corresponding to the plurality of photoelectric conversion elements to be formed are subjected to pattern exposure on the surface of the negative color resist layer formed of the negative coloring film using a photomask.
The photomask has a size that is 4 to 5 times the size of the pattern that is actually formed, and the pattern exposure is performed by reducing the size to 1/4 to 1/5 during pattern exposure.
This photomask is a 4 to 5 times reticle, and has a pattern with a size 4 to 5 times larger than the size of the pattern exposed on the surface of the negative color resist layer. Then, using a stepper exposure apparatus (not shown), the pattern of the photomask is reduced to ¼ to し て to expose the surface of the negative color resist layer.
Subsequent to the exposure step, an alkali development treatment (development step) is performed to elute the uncured portion after the exposure into the developer and leave the photocured portion. By this development step, a patterned film composed of color filter segments can be formed.
The development method may be any of a dip method, a shower method, a spray method, a paddle method, etc., and a swing method, a spin method, an ultrasonic method, or the like may be combined with these.
Before the developer is touched, the surface to be developed can be previously moistened with water or the like to prevent uneven development. As the developer, an organic alkali developer that does not damage the underlying circuit or 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 ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, Organic alkali compounds such as 0] -7-undecene, and inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like.
As the developer, an alkaline aqueous solution obtained by diluting these alkaline agents with pure water so that the concentration is 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass is preferably used. . When a developer composed of such an alkaline aqueous solution is used, generally, after development, the developer is washed (rinsed) with pure water to remove the excess developer and then dried.
Finally, the filter segment thus formed is hardened.
In the production method of the present invention, after performing the above-described colored layer forming step, exposure step, and development step, if necessary, a curing step in which the formed colored pattern is cured by post-heating (post-baking) or post-exposure. May be included. The post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 100 ° C. to 270 ° C. is performed. 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, etc., but with an existing high-pressure mercury lamp at a low temperature of about 20-50 ° C. Preferably, the irradiation time is 10 seconds to 180 seconds, preferably 30 seconds to 60 seconds. In the case of combined use of post-exposure and post-heating, post-exposure is preferably performed first.
By repeating the colored layer forming step, the exposure step, and the developing step (and, if necessary, the curing step) described above for the desired number of hues, a color filter having a desired hue is produced.

<Image sensor>
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 is a configuration that functions as a solid-state imaging device. Can be mentioned.
A transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD sensor, CMOS sensor, organic CMOS sensor, etc.) is provided on the substrate, and the photodiode and the transfer electrode are disposed on the photodiode and the transfer electrode. A light-shielding film made of tungsten or the like that is open only in the light-receiving part of the photodiode, and a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part, It is the structure which has the color filter for solid-state image sensors of this invention on a device protective film.
Further, a configuration having a light collecting means (for example, a microlens, etc., the same shall apply hereinafter) on the device protection layer and under the color filter (on the side close to the substrate), a structure having the light collecting means on the color filter, etc. 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 the organic material plays a role of capturing light and converting it into an electric signal. This is a two-layer hybrid structure in which an inorganic material plays a role of taking out a signal to the outside. In principle, the aperture ratio can be 100% with respect to incident light. The organic photoelectric conversion film is a structure-free continuous film that can be laid on a CMOS signal reading substrate, so that 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.
<Organic EL display device>
The organic EL display device in the present invention is a display device having a color filter formed of the red coloring composition for an organic EL display device of the present invention and a white light emitting organic EL element (hereinafter referred to as an organic EL element) as a light source. Preferably there is.

(Organic EL element (white light-emitting organic EL element))

  An organic EL element is comprised from the element which formed the organic layer of one layer or a multilayer between the anode and the cathode. Here, the single-layer organic EL element refers to an element composed of only a light emitting layer between an anode and a cathode, while the multilayer organic EL element refers to a hole or a hole in the light emitting layer in addition to the light emitting layer. Hole injection layer, hole transport layer, hole blocking layer, electron injection for the purpose of facilitating electron injection and smooth recombination of holes and electrons in the light emitting layer It refers to a laminate of layers. Therefore, typical element configurations of the multilayer organic EL element 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 Hole injection layer / light emitting layer / hole blocking layer / electron injection layer / cathode, (6) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron injection layer / cathode, (7) Examples include an anode / light emitting layer / hole blocking layer / electron injection layer / cathode, and (8) an element configuration laminated in a multilayer structure such as anode / light emitting layer / electron injection layer / cathode. However, the organic EL element used in the present invention is not limited to these.

  Moreover, each organic layer mentioned above may be formed by the layer structure of 2 or more layers, respectively, and several layers may be laminated | stacked repeatedly. As such an example, an element configuration called “multi-photon emission” in which a part of the multilayer organic EL element is multilayered has been proposed in recent years for the purpose of improving light extraction efficiency. For example, in an organic EL device composed of a glass substrate / anode / hole transport layer / electron transporting light emitting layer / electron injection layer / charge generating layer / light emitting unit / cathode, the charge generating layer and light emitting unit There is a method of laminating a plurality of portions.

  First, materials that can be used for each of these layers are 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-based compound is effective, and copper phthalocyanine (abbreviation: CuPc), vanadyl phthalocyanine (abbreviation: VOPc), or the like can be used. There are also materials obtained by chemically doping conductive polymer compounds, such as polyethylenedioxythiophene (abbreviation: PEDOT) doped with polystyrene sulfonic acid (abbreviation: PSS), polyaniline (abbreviation: PANI), or the like. You can also Further, thin films of inorganic semiconductors such as molybdenum oxide (abbreviation: MoO _x ), vanadium oxide (abbreviation: VO _x ), nickel oxide (abbreviation: NiO _x ), and inorganic insulation such as aluminum oxide (abbreviation: Al ₂ O ₃ ) An ultra-thin body film is also effective. In addition, 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- (N, Aromatic amine compounds such as (N-di-m-tolyl) amino) phenyl-N-phenylamino] biphenyl (abbreviation: DNTPD) can also be used. Further, a substance showing acceptability with respect to these aromatic amine compounds may be added to the aromatic amine compound, specifically, 2,3,5,6-tetrafluoro-7 which is an acceptor for VOPc. , 7,8,8-tetracyanoquinodimethane (abbreviation: F4-TCNQ), or α-NPD to which acceptor MoO _x 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 for the hole injection material can be used.

  Examples of the electron transport material that can be used for the electron transport layer include tris (8-quinolinolato) aluminum (abbreviation: Alq3), tris (4-methyl-8-quinolinolato) aluminum (abbreviation: Almq3), bis (10-hydroxybenzo). [H] -quinolinato) beryllium (abbreviation: BeBq2), bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum (abbreviation: BAlq), bis [2- (2-hydroxyphenyl) benzoxazola And metal complexes such as zinc (substantially: Zn (BOX) 2) and bis [2- (2-hydroxyphenyl) benzothiazolate] zinc (substantially: Zn (BTZ) 2). In addition to metal complexes, 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-EtTA Z) 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.

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, described above. Electron transport materials such as BPhen and 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 CaF ₂ , or an alkali metal oxide such as Li ₂ O is often used. In addition, alkali metal complexes such as lithium acetylacetonate (abbreviation: Li (acac)) and 8-quinolinolato-lithium (abbreviation: Liq) are also effective. Further, a substance exhibiting a donor property with respect to these electron injection materials may be added to the electron injection material, and alkali metals, alkaline earth metals, rare earth metals, and the like can be used as donors. Specifically, a material obtained by adding lithium as a donor to BCP or a material obtained by adding lithium as a donor to Alq ₃ can be used.

  Furthermore, a hole blocking material that can prevent holes from passing through the light emitting layer from reaching the electron injection layer and form a layer having excellent thin film formability is used for the hole blocking layer. Examples of such hole blocking materials include aluminum complex compounds such as bis (8-hydroxyquinolinato) (4-phenylphenolato) aluminum, and bis (2-methyl-8-hydroxyquinolina). -To) (4-phenylphenolato) gallium complex compounds such as gallium, nitrogen-containing condensed aromatic compounds such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (abbreviation: BCP) Can be mentioned.

  Although there is no restriction | limiting in particular as a light emitting layer which obtains white light emission, 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 using tunnel injection (European Patent No. 0390551). Similarly, a white light-emitting element is an example of an element using tunnel injection. What is described (JP-A-3-230584), a light-emitting layer having a two-layer structure (JP-A-2-220390 and JP-A-2-216790), and a plurality of light-emitting layers A layered material 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), Further, a red phosphor is included (Japanese Patent Laid-Open No. 6-207170), the blue light emitting layer contains a blue fluorescent dye, and the green light emitting layer is 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. Examples of compounds suitably used for blue, green, orange to red light emission are shown below. However, the light emitting material is not limited to those specifically exemplified below.

  Blue light emission can be obtained by using perylene, 2,5,8,11-tetra-t-butylperylene (abbreviation: TBP), 9,10-diphenylanthracene derivative, or the like as a guest material, for example. Further, styrylarylene 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). A polymer such as poly (9,9-dioctylfluorene) may also be used.

  Further preferred specific examples are shown in Table 11.

Green light is emitted from coumarin dyes 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. In addition, metal complexes such as tris (8-hydroxyquinoline) aluminum (abbreviation: Alq ₃ ), BAlq, Zn (BTZ), bis (2-methyl-8-quinolinolato) chlorogallium (abbreviation: Ga (mq) ₂ Cl) Can also be obtained from A polymer such as poly (p-phenylene vinylene) may also be used.

Further preferred specific examples are shown in Table 12.

  Light emission from orange to red is caused by 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) )) Etc. as a guest material. It can also be obtained from a metal complex such as bis (8-quinolinolato) zinc (abbreviation: Znq2) or bis [2-cinnamoyl-8-quinolinolato] zinc (abbreviation: Znsq2). A polymer such as poly (2,5-dialkoxy-1,4-phenylenevinylene) may be used.

  Further preferred specific examples are shown in Table 13.

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

The material used for the cathode of the organic EL device used in the present invention is a material having a work function (4 eV or less) metal, alloy, electrically conductive compound and a mixture thereof as an electrode substance. Specific examples of such electrode materials 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 produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. Here, when light emitted from the light-emitting layer is extracted from the cathode, the transmittance of the cathode for light emission is preferably greater than 10%. Further, the sheet resistance as the cathode is preferably several hundred Ω / cm ² or less, and the film thickness is usually 10 nm to 1 μm, preferably 50 to 200 Nm.

  Regarding the method for producing the organic EL device used in the present invention, an anode, a light emitting layer, a hole injection layer as necessary, and an electron injection layer as necessary are formed by the above materials and methods, and finally a cathode is formed. What is necessary is just to form. Moreover, an organic EL element can also be produced from the cathode to the anode in the reverse order.

  This organic EL element is manufactured on a translucent substrate. This translucent substrate is a substrate that supports the organic EL element, and for the translucency, it is desirable that the transmittance of light in the visible region of 400 to 700 nm is 50% or more, preferably 90% or more, Further, it is preferable to use a smooth substrate.

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

  As a method for forming each layer of the organic EL element used in the present invention, a dry film forming method such as vacuum deposition, electron beam beam irradiation, sputtering, plasma, ion plating, or spin coating, dipping, flow coating, inkjet A wet film-forming method such as a method, a method of vapor-depositing a light emitter on a donor film, JP-A-2002-534882, and S. T.A. Lee, et al. , Proceedings of SID'02, p. LITI (Laser Induced Thermal Imaging) method described in 784 (2002), printing (offset printing, flexographic printing, gravure printing, screen printing), inkjet, and the like can also be applied.

  The organic layer is particularly preferably a molecular deposited film. Here, the molecular deposited film is a thin film formed by deposition from a material compound in a gas phase state or a film formed by solidifying from a material compound in a solution state or a liquid phase state. Can be classified from a thin film (accumulated film) formed by the LB method according to a difference in an agglomerated structure and a higher-order structure and a functional difference resulting therefrom. Also, as disclosed in JP-A-57-51781, a binder such as a resin and a material compound are dissolved in a solvent to form a solution, and then this is thinned by a spin coat method or the like. Also, an organic layer can be formed. The film thickness of each layer is not particularly limited, but if the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. Conversely, if the film thickness is too thin, the pinhole is used. Or the like, and even when an electric field is applied, it is difficult to obtain sufficient light emission luminance. Accordingly, the thickness of each layer is suitably in the range of 1 nm to 1 μm, but more preferably in the range of 10 nm to 0.2 μm.

  Further, in order to improve the stability of the organic EL element with respect to 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 the entire element is covered or sealed, 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 a direct current, but a pulse current or an alternating current may be used. The current value and the voltage value are not particularly limited as long as they are within the range that does not destroy the element. However, considering the power consumption and life of the element, it is desirable to efficiently emit light with as little electrical 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. Further, the method for extracting light from the organic EL device 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 Shinji Kido, “All about organic EL”, published by Nihon Jitsugyo Shuppansha (published in 2003).

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

  Furthermore, the organic EL element used in the present invention may adopt a microcavity structure. This is because the organic EL device has a structure in which the light emitting layer is sandwiched between the anode and the cathode, and the emitted light causes multiple interference between the anode and the cathode, but the reflectance and transmission of the anode and the cathode This is a technology that actively uses the multiple interference effect and controls the emission wavelength extracted from the device by appropriately selecting the optical characteristics such as the rate and the film thickness of the organic layer sandwiched between them. . Thereby, it is also possible to improve the emission chromaticity. For the mechanism of this multiple interference effect, see J.A. Yamada et al., AM-LCD Digest of Technical Papers, OD-2, p. 77-80 (2002).

  As described above, an RGB color filter layer is produced in parallel with a glass substrate, and a light emitting layer (backlight) produced using the ITO electrode layer and the organic EL element is placed on the color filter layer. As a result, color display is 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 current flow during light emission by the TFT.

  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 “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 measured using a TSKgel column (manufactured by Tosoh Corporation) and GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector using THF (tetrahydrofuran) as a developing solvent. It is a weight average molecular weight (Mw) in terms of polystyrene.

<Resin acid value>
The acid value of the resin was determined by potentiometric titration using a 0.1N potassium hydroxide / ethanol solution. The acid value of the resin indicates the acid value of the solid content.

<Azo pigment identification method>
LC-MS spectrum was used for identification of the azo pigment used in the present invention. The LC-MS spectrum was measured under the following conditions.

Apparatus: Nippon Waters Co., Ltd. UPLC H-Class / XevoTQD
Column: Symmetry C18 5micron (Nippon Waters Corporation)
Eluent:
(A) H ₂ O
(B) DMF (N, N-dimethylformamide)
Eluent conditions: (A) :( B) = 10: 90 (volume ratio)
Flow rate: 0.400 ml / min Injection volume: 1 μl
Column temperature: 40 ° C
Measurement wavelength: 300 nm

The obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.
Further, in the chromatogram obtained at the measurement wavelength under the above conditions, the peak area of the compound represented by the general formula (1) and the total peak area of the compound represented by the general formula (2) are as follows: From the ratio of the peak area of the compound represented by the general formula (2), the content of the compound represented by the general formula (2) with respect to the total amount of the compounds represented by the general formulas (1) and (2) Was calculated.

<Contrast ratio of coating film>
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the dried coating film of the colored composition applied on the glass substrate, and reaches the polarizing plate. If the polarizing planes of the polarizing plate and the polarizing plate are parallel, light passes through the polarizing plate, but if the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the dried coating film of the colored composition, scattering by the pigment particles occurs, resulting in deviation in a part of the polarization plane. When the amount of light transmitted through the plate is reduced and the polarizing plates are orthogonal, part of the light is transmitted through the polarizing plate. This transmitted light was measured as the luminance on the polarizing plate, and the ratio (contrast ratio) between the luminance when the polarizing plate was parallel and the luminance when it was orthogonal was calculated.
(Contrast ratio) = (Luminance when parallel) / (Luminance when orthogonal)
A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, a black mask with a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.

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

<Method for producing acrylic resin solution>
(Preparation of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 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 an acrylic resin solution. After cooling to room temperature, sample about 2 parts of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add methoxypropyl acetate to the previously synthesized resin solution so that the nonvolatile content is 20%. Acrylic resin solution 1 was prepared by addition. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, and the temperature was raised to 80 ° C. From the 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 completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain an acrylic resin solution. After cooling to room temperature, sample about 2 parts of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20%. Thus, an acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18000.

<Method for Producing Resin Type Dispersant Solution>
(Preparation of resin-type dispersant solution 1)
A reaction vessel equipped with a gas introduction 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 replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution prepared by dissolving 0.1 part of 2,2′-azobisisobutyronitrile in 10 parts of 3-mercapto-1,2-propanediol was added. Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. 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 were added and reacted at 120 ° C. for 7 hours. It was. The acid value was measured to confirm that 98% or more of the acid anhydride had been half-esterified, and the reaction was completed to obtain a polyester dispersant having an acid value of 77 mgKOH / g and a weight average molecular weight of 8500. The methoxypropyl acetate was added here so that it might become 40% of solid content by solid content measurement, and the resin type dispersing agent solution 1 which has an aromatic carboxyl group was obtained.

(Preparation of Resin Type Dispersant Solution 2)
A reaction vessel equipped with a gas introduction 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 replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution prepared by dissolving 0.1 part of 2,2′-azobisisobutyronitrile in 10 parts of 3-mercapto-1,2-propanediol was added. Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. 36 parts of trimellitic anhydride, 200.0 parts of methoxypropyl acetate, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 7 hours. It was. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride had been half-esterified, and the reaction was completed to obtain a polyester dispersant having an acid value of 109 mgKOH / g and a weight average molecular weight of 8500. Methoxypropyl acetate was added thereto so that the solid content was 40% as measured by solid content to obtain a resin-type dispersant solution 2 having an aromatic carboxyl group.

(Preparation of resin-type dispersant solution 3)
In a reaction vessel equipped with a gas introduction 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 Charge 16.0 parts of acrylate, 10.0 parts of hydroxymethyl methacrylate, 2.0 parts of ethyl acrylate, add 0.10 parts of 2,2′-azobisisobutyronitrile and 60.0 parts of methoxypropyl acetate. Reacted for 10 hours. The solid content measurement confirmed that the polymerization had progressed 95%, the reaction was terminated, and a polyester dispersant having an acid value of 43 mgKOH / g and a weight average molecular weight of 15000 was obtained. Methoxypropyl acetate was added thereto so as to obtain a solid content of 40% by solid content measurement, thereby obtaining a resin-type dispersant solution 3 having an aromatic carboxyl group.

(Preparation of Resin Type Dispersant Solution 4)
In a reaction vessel equipped with a gas introduction 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, 2.0 parts of ethyl acrylate, 0.10 parts 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 95%, the reaction was terminated, and a polyester dispersant having an acid value of 47 mgKOH / g and a weight average molecular weight of 15000 was obtained. Methoxypropyl acetate was added thereto so that the solid content was 40% as measured by solid content to obtain a resin-type dispersant solution 4 having an aromatic carboxyl group.

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

(Production of pigment derivative 1)
With reference to Synthesis Example 3 of Japanese Patent No. 5748665, a pigment derivative 1 represented by Formula 5 was produced.
Formula 5

(Production of pigment derivative 2)
With reference to Production Example 21 of Japanese Patent No. 4396778, Dye Derivative 2 represented by Formula 6 was produced.
Equation 6

(Production of pigment derivative 3)
With reference to Production Example 6 of Japanese Patent No. 4983061, a dye derivative 3 represented by Formula 7 was produced.
Equation 7

(Production of pigment 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 pigment 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 refluxed at 110 ° C. for 1 hour to synthesize 5-nitroisophthalic acid dichloride. 4-Amino-N- (3- (diethylamino) propyl) benzamide (38.0 parts) was dispersed in 90 parts of toluene, and 5-nitroisophthalic acid dichloride was added dropwise thereto at room temperature over 1 hour, followed by refluxing for 4 hours. To complete the reaction. Toluene was distilled off while neutralizing with a 10% aqueous sodium carbonate solution, followed by reslurry, filtration and drying with a 3% aqueous NaOH solution to obtain 28.0 parts of a compound represented by the following formula 9.
Equation 9

Subsequently, 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% sodium hydrosulfide) is dissolved in 55 parts of water. After the dissolved aqueous solution was added, the mixture was refluxed for 6 hours to obtain 20.0 parts of a base compound represented by the following formula 10.
Equation 10

  20.0 parts of the base compound represented by the above formula 10 is dispersed in 200 parts of water, ice is added to adjust the temperature to 5 ° C., 20.0 parts of 35% hydrochloric acid aqueous solution is added and stirred for 1 hour, and then 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 form a diazonium salt aqueous solution. On the other hand, 18.7 parts of N- [2-methoxy-5-chlorophenyl] -3-hydroxy-2-naphthalenecarboxamide and 53.5 parts of 25% aqueous sodium hydroxide solution were dissolved in 340 parts of methanol to obtain a coupler solution. .

  This coupler solution was poured into the diazonium salt aqueous solution at 5 ° C. for 30 minutes to carry out a coupling reaction. The pH at this time was 4.4. After stirring for 1 hour and confirming the 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 the dye derivative 5 represented by Formula 11.

Equation 11

(Production of pigment derivative 6)
With reference to Production Example 3 of Japanese Patent No. 1863188, a pigment derivative 6 represented by Formula 12 was produced.
Formula 12

<Method for producing colorant>
(Base compound)
The base compounds ([B-1] to [B-4]) used this time are listed in Table 1.

(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 was added, and the mixture was stirred at room temperature for 1 hour to prepare a carboxylic acid chloride solution. Obtained. Separately, a solution in which 1000 parts of N-methylpyrrolidone and 110 parts of bis (3-aminophenyl) sulfone were mixed was prepared, and a carboxylic acid chloride solution was dropped into this solution over 30 minutes. At this time, dropping was carried out 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 then the precipitated reaction product was collected by filtration to obtain the desired product. Furthermore, it wash | cleaned with 1000 parts of methanol, and 252 parts (yield 96.3%) of coupler compounds [C-1] were obtained by drying under reduced pressure.

(Production of coupler compounds [C-2] to [C-4])
Instead of 110 parts of bis (3-aminophenyl) sulfone used in the production of the coupler compound [C-1], the diamines described in Table 2 and the parts by mass of the coupler compound [C-1] were changed. The same operations as in the production were performed to produce coupler compounds [C-2] to [C-4].

<Manufacture of azo pigments>
Hereinafter, the compound represented by the general formula (1) is abbreviated as A1, and the compound represented by the general formula (2) is abbreviated as A2.
[Example 1]
(Production of Azo Pigment 1)

After adding 169 parts of base compound [B-1] to 1500 parts of N-methylpyrrolidone, 35
294 parts of% hydrochloric acid was added and cooled to −2 to 0 ° C. After adding 208 parts of 25% aqueous sodium nitrite solution to this solution, the mixture was stirred for 30 minutes while maintaining at 0 to 5 ° C. to prepare a diazonium solution. Separately, a coupler solution consisting of 225 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 added dropwise to 1000 parts of a pH 5.4 acetate buffer solution over 10 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes, and further stirred while maintaining at 80 ° C. The precipitated reaction product was collected by filtration, washed with hot water, dried, and dried to azo pigment 1 (A1-1 and A2- 388 parts of 1). As a result of LC-MS spectrum measurement, the content of A2-1 was 4.3% by mass.

Azo pigment 1

[Example 2]
(Production of Azo Pigment 2)
Except for changing the mass part of the coupler compound [C-1] used in the production of the azo pigment 1 to 239 parts, the same operation as in the production of the azo pigment 1 was carried out to obtain the azo pigment 2 (A1-1 and A2-1). Of 392 parts). As a result of LC-MS spectrum measurement, the content of A2-1 was 11.8% by mass.

[Example 3]
(Production of Azo Pigment 3)
Instead of 169 parts of the base compound [B-1] used in the production of the azo pigment 1, 181 parts of the base compound [B-2] was used, and the mass part of the coupler compound [C-1] was changed to 220 parts. Except for the above, the same operation as in the production of azo pigment 1 was carried out to obtain 397 parts of azo pigment 3 (mixture of A1-2 and A2-2). As a result of LC-MS spectrum measurement, the content of A2-2 was 0.2% by mass.

Azo pigment 3

[Example 4]
(Production of Azo Pigment 4)
Except for changing the mass part of the coupler compound [C-1] used in the production of the azo pigment 3 to 226 parts, the same operation as in the production of the azo pigment 3 was carried out to obtain the azo pigment 4 (A1-2 and A2-2). 399 parts). As a result of LC-MS spectrum measurement, the content of A2-2 was 5.5% by mass.

[Example 5]
(Production of Azo Pigment 5)
Except having changed the mass part of the coupler compound [C-1] used by manufacture of the azo pigment 3 into 238 parts, operation similar to manufacture of the azo pigment 3 was performed, and azo pigment 5 (A1-2 and A2-2) To obtain 401 parts). As a result of LC-MS spectrum measurement, the content of A2-2 was 9.5% by mass.

[Example 6]
(Production of Azo Pigment 6)
Except for changing the mass part of the coupler compound [C-1] used in the production of the azo pigment 3 to 247 parts, the same operation as in the production of the azo pigment 3 was performed, and the azo pigment 6 (A1-2 and A2-2) was obtained. 400 parts). As a result of LC-MS spectrum measurement, the content of A2-2 was 14.1% by mass.

[Example 7]
(Production of azo pigment 7)
Except having changed the mass part of the coupler compound [C-1] used by manufacture of the azo pigment 3 into 255 parts, operation similar to manufacture of the azo pigment 3 was performed, and azo pigment 7 (A1-2 and A2-2) Of 405 parts). As a result of LC-MS spectrum measurement, the content of A2-2 was 18.9% by mass.

[Example 8]
(Production of azo pigment 8)
Except that the mass part of the coupler compound [C-1] used in the production of the azo pigment 3 was changed to 265 parts, the same operation as in the production of the azo pigment 3 was performed, and the azo pigment 8 (A1-2 and A2-2) was obtained. 403 parts). As a result of LC-MS spectrum measurement, the content of A2-2 was 23.6% by mass.

[Example 9]
(Production of azo pigment 9)
The same procedure as in the production of azo pigment 1 was performed except that 128 parts of base compound [B-3] was used instead of 169 parts of base compound [B-1] used in the production of azo pigment 1. 318 parts of 9 (mixture of A1-3 and A2-3) was obtained. As a result of LC-MS spectrum measurement, the content of A2-3 was 4.5% by mass.

Azo pigment 9

[Example 10]
(Production of Azo Pigment 10)
Except that the mass part of the coupler compound [C-1] used in the production of the azo pigment 9 was changed to 235 parts, the same operation as in the production of the azo pigment 9 was carried out to obtain the azo pigment 10 (A1-3 and A2-3). 322 parts). As a result of LC-MS spectrum measurement, the content of A2-3 was 13.7% by mass.

[Example 11]
(Production of Azo Pigment 11)
An azo pigment was prepared in the same manner as in the production of azo pigment 1 except that 190 parts of base compound [B-4] was used instead of 169 parts of base compound [B-1] used in the production of azo pigment 1. 395 parts of 11 (mixture of A1-4 and A2-4) was obtained. As a result of LC-MS spectrum measurement, the content of A2-4 was 4.1% by mass.

Azo pigment 11

[Example 12]
(Production of azo pigment 12)
Except that the mass part of the coupler compound [C-1] used in the production of the azo pigment 11 was changed to 233 parts, the same operation as in the production of the azo pigment 11 was carried out to obtain the azo pigment 12 (A1-4 and A2-4). 393 parts). As a result of LC-MS spectrum measurement, the content of A2-4 was 11.5% by mass.

[Example 13]
(Production of azo pigment 13)
The same procedure as in the production of azo pigment 3 was performed, except that 231 parts of coupler compound [C-2] was used instead of 220 parts of coupler compound [C-1] used in the production of azo pigment 3. 395 parts of 13 (mixture of A1-5 and A2-5) was obtained. As a result of measuring the LC-MS spectrum, the content of A2-5 was 1.3% by mass.

Azo pigment 13

[Example 14]
(Production of azo pigment 14)
Except that the mass part of the coupler compound [C-2] used in the production of the azo pigment 13 was changed to 235 parts, the same operation as in the production of the azo pigment 13 was performed, and the azo pigment 14 (A1-5 and A2-5) was obtained. 399 parts). As a result of LC-MS spectrum measurement, the content of A2-5 was 5.1% by mass.

[Example 15]
(Production of azo pigment 15)
Except for changing the mass part of the coupler compound [C-2] used in the production of the azo pigment 13 to 242 parts, the same operation as in the production of the azo pigment 13 was performed to obtain the azo pigment 15 (A1-5 and A2-5). 400 parts). As a result of LC-MS spectrum measurement, the content of A2-5 was 9.4% by mass.

[Example 16]
(Production of azo pigment 16)
Except that the mass part of the coupler compound [C-2] used in the production of the azo pigment 13 was changed to 248 parts, the same operation as in the production of the azo pigment 13 was carried out to obtain the azo pigment 16 (A1-5 and A2-5). 399 parts). As a result of LC-MS spectrum measurement, the content of A2-5 was 15.8% by mass.

[Example 17]
(Production of azo pigment 17)
Except for changing the mass part of the coupler compound [C-2] used in the production of the azo pigment 13 to 255 parts, the same operation as in the production of the azo pigment 13 was performed, and the azo pigment 17 (A1-5 and A2-5) was obtained. Of 402) was obtained. As a result of LC-MS spectrum measurement, the content of A2-5 was 18.7% by mass.

[Example 18]
(Production of azo pigment 18)
Except for changing the mass part of the coupler compound [C-2] used in the production of the azo pigment 13 to 265 parts, the same operation as in the production of the azo pigment 13 was performed, and the azo pigment 18 (A1-5 and A2-5) was produced. Of 405 parts). As a result of LC-MS spectrum measurement, the content of A2-5 was 24.7% by mass.

[Example 19]
(Production of Azo Pigment 19)
The same procedure as in the production of azo pigment 3 was carried out except that 250 parts of coupler compound [C-3] was used instead of 220 parts of coupler compound [C-1] used in the production of azo pigment 3. 415 parts of 19 (mixture of A1-6 and A2-6) was obtained. As a result of measuring the LC-MS spectrum, the content of A2-6 was 4.8% by mass.

Azo pigment 19

[Example 20]
(Production of azo pigment 20)
Except that the mass part of the coupler compound [C-3] used in the production of the azo pigment 19 was changed to 256 parts, the same operation as in the production of the azo pigment 19 was performed to obtain the azo pigment 20 (A1-6 and A2-6). 420 parts) was obtained. As a result of LC-MS spectrum measurement, the content of A2-6 was 12.3% by mass.

[Example 21]
(Production of Azo Pigment 21)
The same procedure as in the production of azo pigment 3 was carried out except that 246 parts of coupler compound [C-4] was used instead of 220 parts of coupler compound [C-1] used in the production of azo pigment 3. 415 parts of 21 (a mixture of A1-7 and A2-7) were obtained. As a result of LC-MS spectrum measurement, the content of A2-7 was 5.5% by mass.

Azo pigment 21

[Example 22]
(Production of azo pigment 22)
Except that the mass part of the coupler compound [C-4] used in the production of the azo pigment 21 was changed to 256 parts, the same operation as in the production of the azo pigment 21 was performed to obtain the azo pigment 22 (A1-7 and A2-7). 417 parts). As a result of LC-MS spectrum measurement, the content of A2-7 was 11.5% by mass.

[Example 23]
(Manufacture of azo pigment 23) Refinement process of azo pigment 4 80 parts of azo pigment 4, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and heated at 60 ° C for 6 hours Kneaded and salt milled. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of azo pigment 23 were obtained.

[Example 24]
(Production of Azo Pigment 24) Refinement Step of Azo Pigment 14 80 parts of azo pigment 14, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) at 60 ° C. for 6 hours. Kneaded and salt milled. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of azo pigment 24 were obtained.

[Examples 25 to 30]
(Production of Azo Pigment 25-30)
In the production of the azo pigment 23, azo pigments 25 to 30 were obtained in the same manner as the azo pigment 23 except that the azo pigment 4 and the dye derivative were changed to the types and ratios shown in Table 3 instead of the azo pigment 4.

[Examples 31 to 36]
(Production of azo pigments 31 to 36)
In the production of the azo pigment 24, azo pigments 31 to 36 were obtained in the same manner as the azo pigment 24 except that the azo pigment 14 and the dye derivative were changed to the types and ratios shown in Table 3 instead of the azo pigment 14.

[Production Example 1]
(Production of azo pigment 37)
The following azo pigment 37 was synthesized with reference to JP 2014-160160 A.

Azo pigment 37

[Production Examples 2 to 13]
<Manufacture of other pigments>
(Production of red colorant 1 (RCP-1): PR254)
Commercially available C.I. I. 100 parts of Pigment Red 254 (PR254) ("Irgazine Red D3656 HD" manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) for 6 hours at 60 ° C. Kneaded and salt milled. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of red colorant 1 (RCP-1) were obtained. 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) was added to C.I. I. Except for changing to CI Pigment Red 177 (PR177) (“Sinilex Red SR3C” manufactured by Sonic), 97 parts of Red Colorant 2 (RCP-2) were obtained in the same manner as in the production of Red Colorant 1. 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) was added to C.I. I. Pigment Red 242 (PR242) (“Sandorin Scallet 4RF” manufactured by Clariant) was used in the same manner as in the production of Red Colorant 1 to obtain 98 parts of 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) was added to C.I. I. Except for changing to Pigment Red 269 (PR269) (“Permanent Carmine 3810” manufactured by Sanyo Dyeing Co., Ltd.), 98 parts of Red Colorant 4 (RCP-4) were obtained in the same manner as in Production of Red Colorant 1. The average primary particle size was 35 nm.

(Production of Red Colorant 5 (RCP-5): Brominated Diketopyrrolopyrrole Pigment Formula (4))
To a stainless steel reaction vessel equipped with a reflux tube, 200 parts of tert-amyl alcohol dehydrated with molecular sieves and 140 parts of sodium-tert-amyl alkoxide are added in a nitrogen atmosphere, and heated to 100 ° C. with stirring to obtain an alcoholate solution. Prepared. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and dissolved by heating to 90 ° C. with stirring to prepare a solution of these mixtures. The heated solution of the mixture was slowly dropped into the alcoholate solution heated to 100 ° C. at a constant rate over 2 hours with vigorous stirring. After completion of the dropwise addition, heating and stirring were continued for 2 hours at 90 ° C. to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Furthermore, 600 parts of methanol, 600 parts of water and 304 parts of acetic acid were added to a reaction vessel with a glass jacket, and cooled to -10 ° C. While cooling this mixture with a high-speed stirring disperser and rotating a shear disk having a diameter of 8 cm at 4000 rpm, the alkali metal salt of the diketopyrrolopyrrole compound obtained above was cooled to 75 ° C. The solution was added in small portions. At this time, the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C. while cooling so that the temperature of the mixture consisting of methanol, acetic acid and water is always kept at −5 ° C. or lower. Was added in small portions over approximately 120 minutes. After addition of the alkali metal salt, red crystals were precipitated to form a red suspension. 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 re-dispersed in 3500 parts of methanol cooled to 0 ° C. to make a suspension with a methanol concentration of about 90%, and stirred at 5 ° C. for 3 hours to perform particle sizing and washing with crystal transition. Subsequently, the resulting diketopyrrolopyrrole compound aqueous paste was filtered off with an ultrafiltration machine, dried at 80 ° C. for 24 hours, and pulverized, whereby brominated diketo represented by the formula (4) 150.8 parts of 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 product is poured into 3 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of red colorant 5 (RCP-5) were obtained. The average primary particle size was 45 nm.
Formula (4)

(Production of Yellow Colorant 1 (YCP-1): PY138)
Quinophthalone yellow pigment C.I. I. 500 parts of Pigment Yellow 138 (BASF “Pariotor Yellow L0962-HD”), 500 parts of sodium chloride and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. . Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. And 490 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. 500 parts of Pigment Yellow 139 (“Pariotol Yellow L1820” manufactured by BASF), 500 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 product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. And 510 parts of yellow colorant 2 (YCP-2) were obtained. The average primary particle size was 68 nm.

(Production of yellow colorant 3 (YCP-3): PY150)
Azo-based yellow pigments C.I. I. 500 parts of Pigment Yellow 150 (“Hosta Palm Yellow HN4G” manufactured by Clariant), 500 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 product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 500 parts of yellow colorant 3 (YCP-3) were obtained. The average primary particle size was 60 nm.

(Production of Yellow Colorant 4 (YCP-4): 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. Further, after cooling to room temperature, the reaction mixture was added to 5440 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol and dried to obtain 116 parts of quinophthalone compound (c). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (c).

Quinophthalone compound (c)

  Furthermore, using quinophthalone compound (c) as a raw material, compound (c-2) was obtained according to the 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, heated to 180 ° C., and reacted for 4 hours. The formation of the quinophthalone compound (b) and the disappearance of the starting compound (c-2) were confirmed by TOF-MS. Furthermore, after cooling to room temperature, the reaction mixture was added to 3510 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol, and dried to obtain 120 parts of quinophthalone compound (b). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (b).
Quinophthalone compound (b)

  500 parts of the quinophthalone compound (b) obtained above, 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. And 480 parts of yellow colorant 4 (YCP-4) was obtained. The average primary particle size was 62 nm.

(Production of Yellow Colorant 5 (YCP-5): 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 treated in the order of filtration, water washing, 1% sodium hydroxide aqueous solution washing and water washing, followed by drying to obtain 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, heated to 180 ° C., and stirred for 4 hours. Furthermore, after cooling to room temperature, the reaction mixture was added to 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 by TOF-MS, it 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 stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 95 parts of yellow colorant 5 (YCP-5) were obtained. The average primary particle size was 60 nm.

(Production of Yellow Colorant 6 (YCP-6): Quinophthalone Compound (aa))
In the synthesis of the intermediate (a-1), synthesis was performed in the same manner except that 230 parts of trichloroisocyanuric acid was changed to 244 parts of N-bromosuccinimide, to obtain an intermediate (a-2).
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 stirred at 120 ° C. for 4 hours. Subsequently, 143 parts of intermediate (a-2) was further added to the reaction mixture, heated to 180 ° C., and stirred for 4 hours while distilling off water. After cooling to room temperature, the reaction mixture was added to 2000 parts of acetone and stirred for 1 hour at room temperature. The product was separated by filtration, washed with methanol and dried to obtain 167 parts of quinophthalone compound (aa). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone compound (aa).
Quinophthalone compound (aa)

  100 parts of the quinophthalone compound (aa) obtained above, 500 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 product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, 95 parts of yellow colorant 6 (YCP-6) was obtained. The average primary particle size was 61 nm.

(Production of green colorant 1: PG58)
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. The kneaded product was put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight, 190 ° C. Part of the green colorant 1 was obtained, and the average primary particle size was 69 nm.

(Preparation of blue colorant 1: PB15: 6)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyocolor Co., Ltd.) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged in a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. did. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of blue colorant 1 were obtained. The average primary particle size was 74 nm.

(Preparation of purple colorant 1: PV23)
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLEET RL” manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of purple colorant 1 were obtained. The average primary particle size was 69 nm.

  The results of LC-MS in the azo pigments produced in Examples 1 to 36 and the evaluation results of the average primary particle diameter of all the produced pigments are shown in Table 3.

<Method for producing colored composition>
[Example 37]
(Preparation of colored composition (RM-1))
The following mixture was stirred and mixed so as to be uniform, and then 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. It filtered with a 0 micrometer filter and produced the coloring composition (RM-1) whose non-volatile component is 20 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 Big Chemie) (Solid content 52%): 8.0 parts

[Examples 38 to 72, Comparative Example 1]
(Coloring composition (RM-2 to 37)
Hereinafter, colored compositions (RM-2 to 37) were prepared in the same manner as the colored composition (RM-1) except that the composition was changed to the composition shown in Table 4-1.

[Example 73]
(Preparation of colored composition (RM-38))
The following mixture was stirred and mixed so as to be uniform, and then 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. It filtered with a 0 micrometer filter and produced the coloring composition (RM-38) whose non-volatile component is 20 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 ("LULPERSE-55000" manufactured by Lubrizol) (Solid content 50%)): 8.3 parts

[Example 74]
(Preparation of colored composition (RM-39))
The following mixture was stirred and mixed so as to be uniform, and then 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. It filtered with a 0 micrometer filter and produced the coloring composition (RM-39) whose non-volatile component is 20 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) (Solid content 40%)): 10.4 parts

[Example 75]
(Preparation of colored composition (RM-40))
The following mixture was stirred and mixed so as to be uniform, and then 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. It filtered with a 0 micrometer filter and produced the coloring composition (RM-40) whose non-volatile component is 20 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 76]
(Preparation of colored composition (RM-41))
The following mixture was stirred and mixed so as to be uniform, and then 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. It filtered with a 0 micrometer filter and produced the coloring composition (RM-41) whose non-volatile component is 20 mass%.
Red colorant (RP-4): 12.0 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

[Examples 77 to 79]
(Coloring composition (RM-42 to 44)
Hereinafter, a colored composition (RM-42 to 44) was prepared in the same manner as the colored composition (RM-41) except that the composition was changed to the composition shown in Table 4-2.

[Example 80]
(Coloring composition (RM-45)
A colored composition (RM-45) was prepared in the same manner as the colored composition (RM-38) except that the red colorant (RP-4) was changed to the red colorant (RP-14).

[Example 81]
(Coloring composition (RM-46)
A colored composition (RM-46) was prepared in the same manner as the colored composition (RM-39) except that the red colorant (RP-4) was changed to the red colorant (RP-14).

[Example 82]
(Coloring composition (RM-47)
A colored composition (RM-47) was prepared in the same manner as the colored composition (RM-40) except that the red colorant (RP-4) was changed to the red colorant (RP-14).

[Example 83]
(Coloring composition (RM-48)
A colored composition (RM-48) was prepared in the same manner as the colored composition (RM-41) except that the red colorant (RP-4) was changed to the red colorant (RP-14).

[Examples 84 to 86]
(Coloring composition (RM-49-51)
Hereinafter, colored compositions (RM-49 to 51) were prepared in the same manner as the colored composition (RM-48) except that the composition was changed to the composition shown in Table 4-2.

[Example 87]
(Preparation of colored composition (RM-52))
The following mixture was stirred and mixed so as to be uniform, and then 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. It filtered with a 0 micrometer filter and produced the coloring composition (RM-52) whose non-volatile component is 20 mass%.
Red colorant (RP-4): 10.8 parts Dye derivative 1: 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 Co., Ltd.): 8.0 parts

[Examples 88 to 92, 95 to 100]
(Coloring composition (RM-53-57, 60-65)
Hereinafter, colored compositions (RM-53 to 57, 60 to 65) were prepared in the same manner as the colored composition (RM-52) except that the composition was changed to the composition shown in Table 4-3.

[Example 93]
(Preparation of colored composition (RM-58))
The following mixture was stirred and mixed so as to be uniform, and then 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. It filtered with a 0 micrometer filter and produced the coloring composition (RM-58) whose non-volatile component is 20 mass%.

Red colorant (RP-4): 10.8 parts Dye derivative 4: 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

[Examples 94, 101, 102]
(Coloring composition (RM-59, 66, 67)
Hereinafter, a colored composition (RM-59, 66, 67) was prepared in the same manner as the colored composition (RM-58) except that the composition was changed to the composition shown in Table 4-3.

[Comparative Example 2]
(Coloring composition (RCM-2): PR177)
The following mixture was stirred and mixed so as to be uniform, and then 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. It filtered with a 0 micrometer filter and produced the coloring composition (RCM-2) whose non-volatile component is 20 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 Big 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 then 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. It filtered with a 0 micrometer filter and produced the coloring composition (RCM-4) whose non-volatile component is 20 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 Big Chemie “ Disperbyk-110 "): 1.4 parts

(Coloring composition (RCM-1): PR254)
The following mixture was stirred and mixed so as to be uniform, and then 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. It filtered with a 0 micrometer filter and produced the coloring composition (RCM-1) whose non-volatile component is 20 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 Big Chemie “ Disperbyk-110 "): 1.4 parts

(Coloring composition (RCM-3): PR242)
The following mixture was stirred and mixed so as to be uniform, and then 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. It filtered with a 0 micrometer filter and produced the coloring composition (RCM-3) whose non-volatile component is 20 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 then 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 colored composition (RCM-5) having a non-volatile component 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 (Bic Chemie) "Disperbyk-110" manufactured by the company): 1.4 parts

(Coloring composition (YCM-1): PY138)
The following mixture was stirred and mixed so as to be uniform, and then 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. It filtered with a 0 micrometer filter and produced the coloring composition (YCM-1) whose non-volatile component is 20 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 (manufactured by Big Chemie “ Disperbyk-110 ": 1.4 parts

(Coloring composition (YCM-2): PY139)
The following mixture was stirred and mixed so as to be uniform, and then 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. It filtered with a 0 micrometer filter and produced the coloring composition (YCM-2) whose non-volatile component is 20 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 Big Chemie “ Disperbyk-110 "): 1.4 parts

(Coloring composition (YCM-3): PY150)
The following mixture was stirred and mixed so as to be uniform, and then 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. It filtered with a 0 micrometer filter and produced the coloring composition (YCM-3) whose non-volatile component is 20 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): Quinophthalone compound (b))
The following mixture was stirred and mixed so as to be uniform, and then 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. It filtered with a 0 micrometer filter and produced the coloring composition (YCM-4) whose non-volatile component is 20 mass%.
Yellow colorant 4 (YCP-4) 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 (Bic Chemie) "Disperbyk-110" manufactured by KK: 1.4 parts

(Coloring composition (YCM-5): Quinophthalone compound (t))
The following mixture was stirred and mixed so as to be uniform, and then 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. It filtered with a 0 micrometer filter and produced the coloring composition (YCM-5) whose non-volatile component is 20 mass%.
Yellow colorant 5 (YCP-5) 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 (Bic Chemie) "Disperbyk-110" manufactured by KK: 1.4 parts

(Coloring composition (YCM-6): Quinophthalone compound (aa))
The following mixture was stirred and mixed so as to be uniform, and then 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. It filtered with a 0 micrometer filter and produced the coloring composition (YCM-6) whose non-volatile component is 20 mass%.
Yellow colorant 6 (YCP-6) 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 (Bic Chemie) "Disperbyk-110" manufactured by KK: 1.4 parts

(Evaluation of coloring composition)
The obtained colored composition and the coating film produced using the same were subjected to heat resistance, light resistance, foreign matter evaluation and storage stability by the following methods. The evaluation results are shown in Tables 4-1 to 4-3.

(Heat resistance evaluation)
The coloring composition was applied on a glass substrate having a size of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater so as to have a dry film thickness of 2.0 μm, then dried at 70 ° C. for 20 minutes, and then 230 ° C. The coating film substrate (one aspect of the color filter) was produced by heating and cooling for 60 minutes. The chromaticity ([L ^* (1), a ^* (1), b ^* (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. After that, as a heat resistance test, the sample was heated at 250 ° C. for 1 hour, and the chromaticity ([L ^* (2), a ^* (2), b ^* (2)]) with a C light source was measured. The color difference ΔEab ^* was determined and evaluated in the following four stages.

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

(Light resistance evaluation)
A coated substrate is 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 is measured with a microspectrophotometer ( Measurement was performed using “OSP-SP100” manufactured by Olympus Optical Co., Ltd. Subsequently, an ultraviolet cut filter (“COLORED OPTICAL GLASS L38” manufactured by Hoya Co., Ltd.) is attached on the substrate, and irradiated with ultraviolet rays using a 470 W / m ² xenon lamp for 100 hours, and then the chromaticity ([ L ^* (2), a ^* (2), b ^* (2)]) were measured, and the color difference ΔEab ^* was determined by the above formula and evaluated according to the same criteria as heat resistance.

(Coating foreign material evaluation)
The coloring composition is applied on a glass substrate having a size of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater so as to have a dry film thickness of 2.0 μm, then dried at 70 ° C. for 20 minutes, and then 230 A coating film substrate was prepared by heating and cooling at 60 ° C. for 60 minutes. The evaluation was performed by observing the surface using a metal microscope “BX60” manufactured by Olympus System. The magnification was 500 times, and the number of particles that were observable in arbitrary 5 fields of view through transmission was counted. Evaluation was made in the following four stages.

A: Less than 5 foreign objects (very good)
○: The number of foreign matters is 5 or more and less than 10 (good)
Δ: The number of foreign matters is 10 or more and less than 60 (defects)
×: The number of foreign matters is 60 or more (very bad)

(Storage stability test method)
The viscosity at 25 ° C. of the colored composition was measured at a rotation speed of 20 rpm using an E-type viscometer (TUE-20L type manufactured by Toki Sangyo Co., Ltd.). The viscosity change rate (%) (= ((viscosity after storage for 7 days at 40 ° C.−initial viscosity) / The 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)
○: Viscosity change rate is 10% or more and less than 20% (good)
Δ: Viscosity change rate is 20% or more and less than 50% (defect)
X: Viscosity change rate is 50% or more (very poor)

As shown in Tables 4-1 to 4-3, the coloring composition using the colorant of the present invention had good results in the heat resistance, light resistance, coating foreign matter, and storage stability of the coating film. .
In particular, the coloring of the present invention in which the content of the compound represented by the general formula (2) is 0.1 to 20.0% by mass with respect to the total amount of the compounds represented by the general formulas (1) and (2). The colorant having a favorable result was a particularly good result.
In addition, when compared with a colored composition using the azo pigment 37 (Comparative Example 1), the dispersion was more stable due to the high-order steric hindrance of the pigment, so that the quality was improved. In particular, by using a resin-type dispersant having an aromatic carboxylic acid and a pigment derivative in combination, the result was excellent in heat resistance and light resistance, and excellent in coating film foreign matter and storage stability.

<Method for producing photosensitive coloring composition for color filter>
[Example 103]
(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).
Colored composition (RM-1): 23.0 parts Colored composition (RCM-1): 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 104 to 177, Comparative Examples 4 to 15]
(Photosensitive coloring composition (RR-2 to 87))
As shown in Table 5, photosensitive colored compositions (RR-2 to 87) were obtained in the same manner as the photosensitive colored composition (RR-1) except that the type and ratio of the colored composition were adjusted.

<Evaluation of photosensitive coloring composition for color filter>
The brightness | luminance of the obtained photosensitive coloring composition, contrast ratio, and the film thickness were performed with the following method. Table 5 shows the evaluation results. In addition, Table 6 shows the evaluation of the transferability.

(Evaluation of brightness)
The obtained photosensitive coloring composition is applied onto a glass substrate, dried at 70 ° C. for 20 minutes, and further heated at 230 ° C. for 60 minutes, so that the chromaticity of the substrate is x = 0. A coated substrate such that 683, 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.).

(Evaluation of contrast ratio (CR))
The contrast ratio was measured using the substrate whose luminance was measured.

(Evaluation of film thickness)
The film thickness was measured using the substrate whose luminance was measured. A surface shape measuring device DEKTAK150 (manufactured by ULVAC-ES) was used for measuring the film thickness.

(Evaluation of transferability)
The photosensitive coloring composition for color filters was applied on a glass substrate using a slit die coater and then pre-baked for 2 minutes on a hot plate at 90 ° C. 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, radiation containing each wavelength of 365 nm, 405 nm, and 436 nm is applied to the coating film through a striped photomask using a high-pressure mercury lamp at 1,000 J / m. The exposure amount was 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 pixels on the substrate. Subsequently, the transmittance at 520 nm on the glass substrate separated from the red stripe pixel by 8 μm was measured (T1). Further, the acrylic resin solution 2 was applied onto the substrate using a slit die coater, and then pre-baked for 2 minutes on a 90 ° C. hot plate 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 the glass substrate separated from the red stripe pixel by 8 μm was measured (T2). The difference between T1 and T2 was set as ΔT (%) and evaluated in the following four stages. It can be said that the smaller the ΔT value, the less the luminance is reduced due to the color transfer to the adjacent other color filter segment, and the dye transfer property 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% (defect)
X: ΔT is 3.0% or more (very poor)

  From the results shown in Table 5, it was revealed that the examples using the colorant of the present invention have excellent luminance and become a thin film. In particular, C.I. conventionally used as a bluish pigment. I. Pigment red 177, C.I. I. By using it instead of CI Pigment Red 269 or Azo Pigment 37, a remarkable effect was confirmed.

  Furthermore, as shown in Table 6, it was confirmed that the color composition using the colorant of the present invention has good dye transfer properties.

<Method for producing 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 then 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. Filtration through a 0 μm filter produced 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 then 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. Filtration through a 0 μm filter produced 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 (by Big Chemie) "Disperbyk-110": 1.4 parts

Subsequently, the 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 Etanone, 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)
The non-volatile content is 20% by mass in the same manner as the green pigment dispersion, except that the green colorant 1 (CI Pigment Green 58) is changed to the blue colorant 1 (CI Pigment Blue 15: 6). Of blue pigment dispersion was obtained.

  Purple color with a non-volatile content of 20% by mass in the same manner as the green pigment dispersion, except that green colorant 1 (CI Pigment Green 58) was changed to purple colorant 1 (CI Pigment Violet 23) A pigment dispersion was obtained.

  Subsequently, 30.0 parts of the green pigment dispersion and 18.0 parts of the yellow pigment dispersion were replaced with a total of 50.0 parts of 46.0 parts of the blue dispersion and 4.0 parts of the purple dispersion. A blue photosensitive coloring composition 1 was obtained in the same manner as in the green photosensitive coloring composition 1 except for the above.

<Production and evaluation of color filter>
The red photosensitive coloring composition (RR-1) was applied on a glass substrate on which a black matrix was formed using a slit die coater, and then pre-baked for 2 minutes on a hot plate at 90 ° C. to form a coating film. Formed. Next, after the substrate on which the coating film is formed is cooled to room temperature, radiation containing each wavelength of 365 nm, 405 nm, and 436 nm is applied to the coating film through a striped photomask using a high-pressure mercury lamp at 1,000 J / m. The exposure amount was 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 pixels on the substrate.
Next, green stripe pixels were formed next to the red stripe pixels by using the green photosensitive coloring composition 1 by the same method. Further, blue stripe-like 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 pixel composed of three colors of red, green, and blue using a photocurable resin composition. In this manner, an RGB three-color filter having high luminance and excellent durability was able to be created.

DESCRIPTION OF SYMBOLS 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 the compounds represented by the following general formulas (1) and (2).

General formula (1)


[In General Formula (1), R ₁ represents a halogen atom, an alkyl group which may have a substituent, or an alkoxyl group which may have a substituent. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group that may have a substituent, or a phenyl group that may have a substituent.
X _{1 to} X ₈ each independently represents a hydrogen atom, an alkyl group that may have a substituent, an alkoxyl group that may have a substituent, or a halogen atom. ]

General formula (2)


[In General Formula (2), R ₁ represents a halogen atom, an alkyl group which may have a substituent, or an alkoxyl group which may have a substituent. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group that may have a substituent, or a phenyl group that may have a substituent.
X _{1 to} X ₈ each independently represents a hydrogen atom, an alkyl group that may have a substituent, an alkoxyl group that may have a substituent, or a halogen atom. ]   The azo compound according to claim 1, wherein the content of the compound represented by the general formula (2) with respect to the total amount of the compounds represented by the general formulas (1) and (2) is 0.1 to 20% by mass. Pigments.   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 is the coloring agent for a color filter according to claim 3.   Furthermore, the coloring composition for color filters of Claim 4 containing the resin-type dispersing agent which has 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. It contains at least 1 sort (s) chosen from the group which consists of the pigment yellow 150, the yellow pigment represented by following General formula (3), and a brominated diketopyrrolopyrrole pigment, It is any one of Claims 4-7 characterized by the above-mentioned. Coloring compositions for color filters.

General formula (3)

[In General Formula (3), Z _{1 to} Z ₁₃ each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. An aryl group which may have, —SO ₃ H, —COOH, and monovalent to trivalent metal salts, alkylammonium salts, phthalimidomethyl groups which may have a substituent, or substituents of these acidic groups; The sulfamoyl group which may have is shown.
The adjacent groups of Z _{1 to} Z ₄ and / or Z _{10 to} Z ₁₃ may be united to form an aromatic ring which may have a substituent. ]   Furthermore, the photopolymerizable monomer is included, The coloring composition for color filters as described in any one of Claims 4-8 characterized by the above-mentioned.   A color filter comprising a filter segment formed on the substrate from the colored composition for 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.