JP6089877B2 - Quinophthalone compound and coloring composition containing the same - Google Patents

Description

  The present invention relates to a novel quinophthalone compound and a coloring composition containing the compound, and particularly used for the production of a color filter suitably used for a color liquid crystal display device, a color imaging device, an organic EL display device and the like. The present invention relates to a coloring composition.

  The color liquid crystal display device controls the amount of light passing through the second polarizing plate by controlling the degree of polarization of the light that has passed through the first polarizing plate by the liquid crystal layer sandwiched between the two polarizing plates. This is a display device that performs display by using a twisted nematic (TN) type liquid crystal. The liquid crystal display device can perform color display by providing a color filter between two polarizing plates. Therefore, liquid crystal display devices are being developed for use in televisions and personal computer monitors.

  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.

  In general, a color filter is formed in a fine strip (stripe) shape formed of a red filter layer (R), a green filter layer (G), and a blue filter layer (B) formed on the surface of a transparent substrate such as glass. The filter segments (pixels) are arranged in parallel or intersecting with each other, or the fine filter segments are arranged in a constant vertical and horizontal arrangement. 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. Recently, in addition to a red filter layer (R), a green filter layer (G), and a blue filter layer (B), a filter segment including a yellow filter layer (Y) has been used.

  A transparent electrode for driving a liquid crystal is generally formed on the color filter used in the color liquid crystal display device by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Is formed. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to perform the formation process at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. or higher, and the color filter is required to have heat resistance.

  Contrast and brightness are important quality items required for color filters. When a color filter with low contrast 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 state) ), The transmitted light attenuates, resulting in a blurred screen. Therefore, in order to realize a high-quality liquid crystal display device, it is essential to increase the contrast.

  If a color filter with low brightness 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 as light sources. However, from the viewpoint of suppressing power consumption, the color filter has become highly bright.

  Furthermore, as described above, since color liquid crystal devices have been used for televisions, personal computer monitors, etc., there is a demand for a wide color reproduction region and high reliability as well as higher contrast and higher brightness for color filters. It is high.

In addition, a color image sensor represented by a C-MOS (Complementary Metal Oxide Semiconductor: Complementary Metal Oxide Semiconductor), CCD (Charge Coupled Device), etc. has a red filter layer (R) on the light receiving element, In general, the color filters having filter segments of the primary colors of the additive color mixture of the green filter layer (G) and the blue filter layer (B) are arranged and separated. Further, since high sensitivity can be obtained compared to the primary color filter, a color filter having filter segments of cyan, magenta, and yellow (CMY) corresponding to the complementary colors of red, green, and blue is often used. Complementary color filters are often used in video cameras and the like that are difficult to use an auxiliary light source such as a flash.
In recent years, there has been an increasing demand for high transmittance, that is, lightness and high reliability even for color filters used in color imaging devices.

  The color filter production method includes a dyeing method using a dye or a salt-forming dye as a colorant, a dye dispersion method, a pigment dispersion method using a pigment as a colorant, a printing method, and an electrodeposition method. Among these, the dyeing method or the dye dispersion method has a drawback that the heat resistance and light resistance are slightly inferior because the colorant is a dye. Therefore, a pigment having excellent heat resistance and light resistance is used as a colorant for the color filter, and a pigment dispersion method is often used as a manufacturing method because of the accuracy and stability of the forming method.

  In the pigment dispersion method, a color resist is formed by mixing and blending a photosensitive agent or an additive into a resin in which pigment particles as a colorant are dispersed in a resin, and this color resist is applied onto a substrate by a coating device such as a spin coater. In this method, a color filter is produced by forming a coating film by the above, performing selective exposure through a mask with an aligner or a stepper, patterning by alkali development and thermosetting, and repeating this operation.

  In general, the pigment particles are subjected to a micronization treatment and a pigment dispersion in which the micronized pigment is brought close to the primary particles as much as possible is used to suppress light scattering by the pigment and achieve high contrast. In addition, since the transparency of the dispersion is improved, the spectral spectrum of the dispersion has high transmittance, and high brightness is realized. By using this dispersion as a color resist, a color filter having high contrast and high brightness can be obtained.

  As described above, in order to increase the contrast and brightness of the color filter, it is required to disperse the finely processed pigment in a finer state (good dispersibility). However, since the finer pigment has a large surface area, the cohesive force between the pigment particles becomes strong, and when the dispersibility of the pigment is insufficient, the dispersion becomes highly viscous and the contrast of the color filter is increased. There is a problem that it is significantly deteriorated. It is often difficult to achieve both a high level of dispersibility and contrast.

  In order to solve such problems, various dye derivatives have been developed. For example, Patent Documents 1 to 5 propose coloring compositions using a quinophthalone compound as a pigment derivative. In the quinophthalone compounds proposed in these patent documents, it is impossible to obtain a coloring composition satisfying all of brightness, contrast, dispersibility, and heat resistance when dispersing a finely-treated pigment. Development of quinophthalone compounds has been desired. Patent Documents 6 to 7 describe quinophthalone compounds having a phthalimide group substituted by sulfonic acid as intermediates of Examples, but the specification for utility in color filter applications is not described. .

JP 2003-167112 A JP 2002-179799 A JP 2002-121456 A JP 2004-307854 A JP 2007-156395 A JP 2008-050420 A JP 2008-081566 A

This invention makes it a subject to achieve the following objectives.
That is, an object of the present invention is to provide a coloring composition for a color filter excellent in brightness, contrast, dispersibility, and heat resistance.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a novel quinophthalone compound, and a coloring composition for a color filter containing this and a coloring agent has solved the above problems. As a result, the present invention has been found.

  That is, an embodiment of the present invention is a colored composition comprising a colorant [A], a pigment derivative, a binder resin, and an organic solvent, and the pigment derivative is represented by the following general formula (1). It is related with the coloring composition characterized by being a quinophthalone compound [B].

[In General Formula (1), R _{1 to} R ₅ and R _{6 to} R ₁₁ each independently have a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group that may have a substituent, or a substituent. which may alkoxyl group, an optionally substituted aryl group, an ester group, a sulfo group; a carboxyl group; and monovalent to trivalent metal salt thereof acidic group; an alkyl ammonium salt, Z ₁ is - Represents SO ₂ — or —CO—, and Z ₂ represents a halogen atom, a hydroxyl group, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryl which may have a substituent. An aromatic ring residue which may have a substituent selected from the group consisting of a group, a sulfo group; a carboxyl group; and a monovalent to trivalent metal salt of these acidic groups; an alkylammonium salt. However, at least one of R _{1 to} R ₅ , R _{6 to} R ₁₁ , and Z ₂ is a sulfo group, a carboxyl group, a metal salt of a sulfo group, a metal salt of a carboxyl group, an alkyl ammonium salt of a sulfo group, and a carboxyl A group selected from the group consisting of alkylammonium salts of groups. ]

Further, in an embodiment of the present invention, at least one of R _{1 to} R ₅ , R _{6 to} R ₁₁ , and Z ₂ is a sulfo group, a metal salt of a sulfo group, a metal salt of a carboxyl group, and an alkyl of a sulfo group It is related with the said coloring composition which is group containing the group chosen from the group which consists of ammonium salt.

An embodiment of the present invention also relates to the above colored composition, wherein Z ₁ is —CO—.

  In another embodiment of the present invention, the colorant [A] is a group consisting of a quinophthalone pigment, a metal phthalocyanine pigment, an isoindoline pigment, an azo metal complex pigment, a diketopyrrolopyrrole pigment, and an anthraquinone pigment. It is related with the said coloring composition which is any 1 or more types chosen from more.

  Moreover, the embodiment of this invention is related with the said coloring composition which contains a photopolymerizable monomer and / or a photoinitiator further.

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

  Moreover, the embodiment of this invention is related with the quinophthalone compound represented by General formula (1).

  According to the present invention, by using the quinophthalone compound represented by the general formula (1) in combination with a colorant, a color composition for a color filter having good brightness, contrast, heat resistance and low viscosity is provided. be able to.

1 is an infrared absorption spectrum of the quinophthalone compound (B-1) produced in Example 1. FIG. FIG. 2 is an infrared absorption spectrum of the quinophthalone compound (B-2) produced in Example 2. FIG. 3 is an infrared absorption spectrum of the quinophthalone compound (B-3) produced in Example 3. 4 is an infrared absorption spectrum of the quinophthalone compound (B-4) produced in Example 4. FIG.

  Hereinafter, the present invention will be described in detail. In this specification, “CI” means a color index.

The present invention is a color composition and a color filter color composition containing a colorant [A], a dye derivative, a binder resin, and an organic solvent, and the dye derivative is represented by the general formula (1). It contains a quinophthalone compound [B].
Hereinafter, each component which comprises the coloring composition of this invention is explained in full detail.

<Colorant [A]>
The colorant that can be used in the coloring composition of the present invention can be arbitrarily selected from conventionally known various pigments and dyes. The following are typical pigments that can be used in the present invention.

  Examples of red pigments that can be used in the present invention include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208,209,210,216,220,221,224,226,242,246,254,255,264,270,272,273,274,276,277,278,279,280,281,2 2,283,284,285,286,287 or diketopyrrolopyrrole pigment described in JP-T 2011-523433 discloses the like, but not particularly limited thereto. Also, red dyes such as xanthene, azo, disazo, and anthraquinone can be used. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338.

  Examples of the orange pigment that can be used in the present invention include C.I. I. Pigment Orange 38, 43, 71, 73, etc. are mentioned, but it is not particularly limited to these.

  Examples of yellow pigments that can be used in the present invention include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 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, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176 177,179,180,181,182,185,187,188,193,194,198,199,213,214,218,219,220 or 221, and the like, but not particularly limited thereto. Also, yellow dyes such as quinoline, azo, disazo, and methine can be used.

  Examples of the green pigment that can be used in the present invention include C.I. I. Examples thereof include zinc phthalocyanine pigments described in CI Pigment Green 7, 10, 36, 37, 58, JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, and the like. It is not limited to.

  Examples of blue pigments that can be used in the present invention include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, JP 2004-333817, Examples include aluminum phthalocyanine pigments described in Japanese Patent No. 4893859, but are not limited thereto.

  Among the colorants, quinophthalone pigments, metal phthalocyanine pigments, isoindoline pigments, azo metal complex pigments, diketopyrrolopyrrole pigments, and anthraquinones because of the color characteristics of the quinophthalone compound [B] described later Any one pigment selected from the group consisting of pigments is preferably used alone or in combination of two or more. Further, among these, quinophthalone pigments and metal phthalocyanine pigments are particularly preferable.

Examples of the quinophthalone pigment include C.I. I. Pigment Yellow 138 or a quinophthalone compound represented by General Formula (3) is preferable.

[In General Formula (3), R _{101 to} R ₁₁₃ 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. The aryl group which may have is shown. The adjacent groups of R _{101 to} R ₁₀₄ and / or R _{105 to} R ₁₀₈ may be combined to form an aromatic ring which may have a substituent. ]

The alkyl group that may have a substituent, the alkoxyl group that may have a substituent, and the aryl group that may have a substituent in R _{101 to} R ₁₁₃ have the same meanings as those in the general formula (1) described later. It is.

In addition, adjacent groups of R _{101 to} R ₁₀₄ and / or R _{105 to} R ₁₀₈ together form an aromatic ring that 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.

  The metal phthalocyanine pigment is preferably a halogenated copper phthalocyanine pigment, a halogenated zinc phthalocyanine pigment, or an aluminum phthalocyanine pigment. More preferably, C.I. I. Pigment Green 7, 36, 58, or an aluminum phthalocyanine compound represented by the general formula (4).

[In the general formula (4), X _{1 to} X ₄ may each independently have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. A cycloalkyl group, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, Alternatively, it represents an arylthio group which may have a substituent. Y _{1 to} Y ₄ each independently represent a halogen atom, a nitro group, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent.
M represents Al-Z.
Z represents a hydroxyl group, a chlorine atom, or —OP (═O) R ₂₀₁ R ₂₀₂ , wherein R _{201 to} R ₂₀₂ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, Represents an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent, and R _{201 to} R ₂₀₂ are bonded to each other to form a ring; May be formed.
m ₁ , m ₂ , m ₃ , m ₄ , n ₁ , n ₂ , n ₃ , and n ₄ each independently represent an integer of 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + N ₃ and m ₄ + n ₄ are each 0 to 4, and may be the same or different. ]

The alkyl group that may have a substituent in X _{1 to} X ₄ or R _{201 to} R _202, the alkoxyl group that may have a substituent, and the aryl group that may have a substituent will be described later. It is synonymous with that of general formula (1).

  Examples of the cycloalkyl group which may have a substituent include a cyclopentyl group, a cyclohexyl group, an adamantyl group, a 2,5-dimethylcyclopentyl group, and a 4-tert-butylcyclohexyl group.

  Examples of the heterocyclic group which may have a substituent include pyridyl group, pyrazyl group, piperidino group, pyranyl group, morpholino group, acridinyl group, 3-methylpyridyl group, N-methylpiperidyl group, N-methylpyrrolyl group and the like. Can be mentioned.

  The aryloxy group which may have a substituent includes a phenoxy group, a naphthoxy group, an anthryloxy group, a p-methylphenoxy group, a p-nitrophenoxy group, a p-methoxyphenoxy group, and a 2,4-dichlorophenoxy group. , Pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group and the like.

  Examples of the alkylthio group which may have a substituent include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group, methoxyethylthio group, amino group Examples include an ethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, and a phenylcarbonylaminoethylthio group.

  Examples of the arylthio group which may have a substituent include phenylthio group, 1-naphthylthio group, 2-naphthylthio group, 9-anthrylthio group, chlorophenylthio group, trifluoromethylphenylthio group, cyanophenylthio group, nitrophenylthio group. Group, 2-aminophenylthio group, 2-hydroxyphenylthio group and the like.

As substituents of 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, , X _{1 to} X ₄ are the same as the substituents.

In the general formula (4), Z is more preferably —OP (═O) R ₂₀₁ R ₂₀₂ from the viewpoint of dispersibility and brightness.

  Examples of the isoindoline pigment include C.I. I. Pigment Yellow 139, 185, and the azo metal complex pigment include C.I. I. Pigment Yellow 150 and the diketopyrrolopyrrole pigment include C.I. I. Pigment Red 254, brominated diketopyrrolopyrrole pigments described in JP-T-2011-523433, and the anthraquinone pigments include C.I. I. Pigment Red 177 is preferable.

<Miniaturization of pigment>
When the colorant used in the coloring composition of the present invention is a pigment, it is preferably used after being refined. There are no particular limitations on the method of miniaturization. For example, any of wet grinding, dry grinding, and dissolution precipitation can be used. As exemplified in the present invention, salt milling treatment by a kneader method, which is one type of wet grinding. Etc. can be made finer. It is preferable that the average primary particle diameter calculated | required by TEM (transmission electron microscope) of a pigment is the range of 5-90 nm. When the thickness is smaller than 5 nm, dispersion in an organic solvent becomes difficult, and when the thickness is larger than 90 nm, a sufficient contrast ratio may not be obtained. For these reasons, a more preferable average primary particle size is in the range of 10 to 70 nm.

  Salt milling is a batch or continuous type of mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent, such as a kneader, 2-roll mill, 3-roll mill, ball mill, attritor, sand mill, planetary mixer, etc. In this process, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water after mechanically kneading while heating using a kneader. 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. In view of processing efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight, based on 100 parts by weight of the pigment.

  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 pigment.

  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. The amount of the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

<Dye derivative>
(Quinophthalone compound [B])
Next, the quinophthalone compound [B] represented by the general formula (1) will be described.
The quinophthalone compound of the present invention not only exhibits excellent color characteristics (lightness) as a pigment, but can also have dispersibility. In addition, the quinophthalone compound of the present invention can be used as a dye or a pigment derivative for dispersing pigments in paints, printing inks, color filter coloring compositions, inkjet ink applications, and the like.

First, Z ₁ and Z ₂ in the general formula (1) will be described.
Z ₁ represents —SO ₂ — or —CO—, and more preferably —CO—.
Z ₂ represents an aromatic ring residue which may have a substituent described later.

  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.

It continues and demonstrates the substituent in R < ₁ > -R < ₅ >, R < ₆ > -R < ₁₁ > and Z < ₂ > in General formula (1).
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, diethylaminoethyl group, benzyl group, 4-methylbenzyl group, 4-tert-butyl Examples thereof include alkyl groups having a substituent such as a benzyl group, a 4-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 group, 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-nitro Examples include an alkoxyl group having a substituent such as a propoxy group and 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.

  In addition, as used herein, an ester group means a monovalent residue in which a hydrogen atom on a carbonyl group of a formate ester is released. Specifically, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylalkoxycarbonyl group More specifically, a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, a phenoxycarbonyl group, a benzyloxycarbonyl group, and the like can be given.

  Further, in this specification, “sulfo group; carboxyl group; and monovalent to trivalent metal salts of these acidic groups; alkylammonium salts” means sulfo group, carboxyl group, metal salt of sulfo group, metal of carboxyl group Salt, alkylammonium salt of sulfo group and alkylammonium salt of carboxyl group are meant.

  Examples of the monovalent to trivalent metal salt of a sulfo group or a carboxyl group include sodium salt, potassium salt, magnesium salt, calcium salt, iron salt, aluminum salt and the like. Examples of the alkyl ammonium salts include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine and stearylamine, quaternary alkylammonium salts such as palmityltrimethylammonium, dilauryldimethylammonium and distearyldimethylammonium salts. Is mentioned.

In the quinophthalone compound [B] of the general formula (1) used in the colored composition of the present invention, R _{1 to} R ₅ , R _{6 to} R ₁₁ or Z ₂ may be an alkyl group which may have a substituent, In the case of any of an alkoxyl group that may have a substituent, an aryl group that may have a substituent, and an ester group, at least one of the substituents is a sulfo group, a carboxyl group, or a sulfo group Alternatively, it is a metal salt of a carboxyl group, or an alkyl ammonium salt of a sulfo group or a carboxyl group.

As a preferable embodiment, among R _{1 to} R ₅ , R _{6 to} R ₁₁ and Z ₂ , a halogen atom, an alkyl group which may have a substituent, and an alkoxyl group which may have a substituent are preferable. An aryl group which may have a substituent, an ester group, a sulfo group and a carboxyl group are mentioned, more preferably a halogen atom, a sulfo group and a carboxyl group, and still more preferably a sulfo group.

As another preferred embodiment, R _{1 to} R ₅ , R _{6 to} R ₁₁ , and Z ₂ may have an aromatic ring residue or substituent having an alkyl group which may have a substituent. In the case of either an aromatic ring residue having a good alkoxyl group or an aromatic ring residue having an aryl group which may have a substituent, among these substituents, preferred substituents include a halogen atom, a substituent And an alkyl group, an alkoxyl group, an aryl group, an ester group, a sulfo group, and a carboxyl group, and more preferable substituents include a halogen atom, a sulfo group, and a carboxyl group, and further preferable substituents. As such, a sulfo group may be mentioned. In particular, when used as a coloring composition for a color filter, it is preferable from the viewpoint of color characteristics (lightness) and dispersibility.

When used as a coloring composition for a color filter, R _{1 to} R ₅ , R _{6 to} R ₁₁ , and Z ₂ other than a sulfo group or a carboxyl group have an alkyl group or a substituent that may have a substituent. Or an aryl group that may have a substituent, or an ester group, the substituents are each independently a hydrogen atom, an alkyl group that may have a substituent, or An alkoxyl group which may have a substituent is preferable from the viewpoint of color characteristics (lightness). R _{6 to} R ₁₁ are preferably hydrogen atoms from the viewpoint of color characteristics (lightness) and dispersibility.

Each of the substituents Z ₂ is independently a hydrogen atom, a sulfo group or a carboxyl group, a metal salt of a sulfo group or a carboxyl group, or an alkyl ammonium salt of a sulfo group or a carboxyl group, and at least one of them , A sulfo group, a metal salt of a sulfo group, or an alkyl ammonium salt of a sulfo group is preferable from the viewpoint of color characteristics (lightness) and dispersibility.

  Specific examples of the quinophthalone compound [B] used in the colored composition of the present invention include those shown below, but the present invention is not limited thereto. Moreover, among the following exemplary compounds, a sulfo group or a carboxyl group can be derived into its metal salt or alkylammonium salt by an ion exchange reaction.

  The weight ratio of the colorant [A] and the quinophthalone compound [B] represented by the general formula (1) is preferably in the range of [A]: [B] = 60: 40 to 99: 1, [A]: [B] is more preferably in the range of 80:20 to 97: 3. More preferably, the range is [A]: [B] = 85: 15 to 95: 5.

<Method for producing quinophthalone compound>
The quinophthalone compound of the present invention can be produced, for example, by the following method. Hereinafter, typical production methods of the quinophthalone compound represented by the general formula (1) will be described. First, about 2 to 3 equivalents of naphthalenedicarboxylic anhydrides represented by the following general formula (6) are added in benzoic acid to 1 equivalent of the 8-aminoquinaldines represented by the following general formula (5). The compound represented by the following general formula (7) can be obtained by performing a condensation reaction by heating at about 160 to 200 ° C. in a nitrogen atmosphere.

Wherein, R ₂₃ to R ₂₇ have the same meanings as R ₁ to R ₅ in the general formula (1). ]

[In formula, R < ₂₈ > -R < ₃₃ > is synonymous with R < ₆ > -R < ₁₁ > in General formula (1). ]

[Wherein, R _{34 to} R ₃₈ and R _{39 to} R ₅₀ have the same meanings as R _{1 to} R ₅ and R _{6 to} R ₁₁ in the general formula (1). ]

  Then, the compound represented by the following general formula (8) is obtained by heating the compound represented by the above general formula (7) in an alkaline aqueous solution such as potassium hydroxide at about 60 ° C. to 100 ° C. be able to.

Wherein, R ₅₁ to R ₅₅ and R ₅₆ to R ₆₁ have the same meanings as R ₁ to R ₅ and R ₆ to R ₁₁ in the general formula (1). ]

  Subsequently, about 1 equivalent of the compound represented by the general formula (8), the phthalic acid represented by the following general formula (9) or the phthalic anhydride represented by the following general formula (10) A compound represented by the following general formula (11) can be obtained by heating 2 equivalents in benzoic acid in a nitrogen atmosphere at about 160 to 200 ° C. to cause a condensation reaction.

[Wherein, Z ₅ has the same meaning as Z ₂ in formula (1). ]

[Wherein, Z ₆ has the same meaning as Z ₂ in the general formula (1). ]

[Wherein, R _{62 to} R ₆₆ , R _{67 to} R ₇₂ and Z ₇ have the same meanings as R _{1 to} R _5, R _{6 to} R ₁₁ and Z ₂ in the general formula (1). ]

  Subsequently, the quinophthalone compound represented by the general formula (1) is obtained by heating the compound represented by the general formula (11) in an alkaline aqueous solution such as sodium hydroxide at about 10 ° C. to 50 ° C. Can do.

  The quinophthalone compound represented by the general formula (1) can also be produced by the following method.

  About 1 equivalent of the compound represented by the general formula (8), aromatic carboxylic acids represented by the following general formula (12) or aromatic sulfonic acids represented by the following general formula (13) A compound represented by the general formula (1) can be obtained by subjecting 2 equivalents to an acid chloride using thionyl chloride or the like in an organic solvent such as N, N-dimethylformamide and the like, followed by a condensation reaction. However, the manufacturing method of a quinophthalone compound is not limited to these methods.

[Wherein, R _{84 to} R ₈₈ are synonymous with the substituent that Z ₂ in the general formula (1) may have. ]

Wherein, R ₈₉ to R ₉₃ is, Z ₂ is as defined substituents that have the general formula (1). ]

  The quinophthalone compound of the present invention may be used in combination of two or more quinophthalone compounds according to the intended use. At this time, quinophthalone compounds produced separately may be mixed together, or may be produced by synthesizing two or more quinophthalone compounds and used at the same time.

(Other pigment derivatives)
Examples of the dye derivative other than the quinophthalone compound [B] include compounds obtained by introducing a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group into an organic pigment, anthraquinone, acridone, or triazine. For example, JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717. JP, 128-128669, JP 2003-167112, JP 2004-091497, JP 2004-307854, JP 2007-156395, JP 2008-094873. , JP2008-094986, JP2008-095007 Distribution, JP 2008-195916, JP-use those described in Patent No. 4,585,781 discloses such, may be used in combination one or more of these quinophthalone compounds [B] and.

<Binder resin>
The binder resin used in the coloring composition of the present invention is one that disperses, dyes, or penetrates a colorant, and includes 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 5,000 to 100,000, more preferably in the range of 7,000 to 80,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 2,000 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 developer is poor, and it may be difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern may not remain.

  The binder resin is preferably used in an amount of 20 parts by weight or more based on 100 parts by weight of the total weight of the colorant because the film formability and various resistances are good, and 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 weight 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 obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfo 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 into 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. Moreover, when an etrahydrophthalic 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 foreign matter on the coating film, 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.

(Thermosetting compound)
In the present invention, a thermosetting compound may be further contained in combination with the thermoplastic resin which is a binder resin.

  Examples of the thermosetting compound include epoxy compounds and / or resins, benzoguanamine compounds and / or resins, rosin-modified maleic acid compounds and / or resins, rosin-modified fumaric acid compounds and / or resins, melamine compounds and / or resins, Examples include urea compounds and / or resins, phenol compounds and / or resins, but the present invention is not limited thereto.

<Organic solvent>
In the coloring composition of the present invention, the coloring agent is sufficiently dispersed and permeated in the coloring agent carrier, and is applied onto 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 ethyl lactate, benzyl alcohol, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl- 1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 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, N, N-dimethyl Acetamide, N, N-dimethylformamide, n-butyl alcohol, n-butyl Benzene, n-propyl acetate, o-xylene, o-diethylbenzene, 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 acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl Ether, ethylene glycol Dimonomethyl 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, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl Chill 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 propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, Acetic acid Propyl, and dibasic acid esters.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  Among them, the dispersibility of the coloring agent, the penetrability, and the coating property of the coloring composition are good, so that ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  In addition, the organic solvent can be used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the colorant because the colored composition can be adjusted to an appropriate viscosity to form a desired colored film having a uniform thickness. Is preferred.

<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) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate 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, til (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 blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight based on the total weight of the colorant (100 parts by weight), and 10 to 300 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<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, or Benzoin compounds such as dimethyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) Nyl) -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 an oxime ester compound such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; An imidazole compound; or a titanocene compound or the like is used.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the photopolymerization initiator is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as 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, or Michler's ketone derivatives, biimidazole derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, Camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, or 4,4′-tetra (t-butylperoxyca Rubonyl) benzophenone, 4,4′-diethylaminobenzophenone and the like.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

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

<Multifunctional thiol>
The coloring composition of the present invention can contain a polyfunctional thiol that functions as a chain transfer agent.
The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene,
2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine and the like. These polyfunctional thiols can be used singly or in combination of two or more in any ratio as necessary.

  The content of the polyfunctional thiol is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight based on the weight (100% by weight) of the total solid content of the color filter coloring composition. . When the polyfunctional thiol content is less than 0.1% by weight, the effect of adding the polyfunctional thiol is insufficient, and when it exceeds 30% by weight, the sensitivity is too high and the resolution may be lowered.

<Antioxidant>
The coloring composition of the present invention can contain an antioxidant. The antioxidant increases the transmittance of the coating film in order to prevent the photopolymerization initiator and thermosetting compound contained in the colored composition from being oxidized and yellowing due to a thermal process during thermal curing or ITO annealing. be able to. 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.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

  These antioxidants can be used singly or in combination of two or more at any ratio as required.

  When the content of the antioxidant is 0.5 to 5.0% by weight based on the solid content weight of the color filter coloring composition (100% by weight), brightness and sensitivity are more preferable.

<Amine compound>
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

  Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<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 0.5% by weight based on the total weight of the coloring composition (100% by weight).

  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 amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Til-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.

<Other additive components>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition.

<Method for producing colored composition>
The coloring composition of the present invention comprises a colorant [A] in a colorant carrier such as a binder resin and / or a solvent, preferably together with a dispersion aid, a kneader, a two-roll mill, a three-roll mill, a ball mill, 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. Also, the quinophthalone compound [B] may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. 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 includes the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other pigment dispersants, and additives. Etc. can be mixed and adjusted. 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, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a large effect of preventing reaggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has lightness and viscosity stability. Become good. The dye derivative is as described above.

<Resin type dispersant>
The resin-type dispersant has a colorant-affinity part that has the property of adsorbing to the additive colorant and a part that is compatible with the colorant carrier, and is adsorbed to the additive colorant and dispersed in 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 may be used alone or in combination, it is not necessarily limited thereto.

Among the above-mentioned dispersants, a polymer dispersant having a basic functional group is preferable because the viscosity of the dispersion is lowered and a high contrast is exhibited with a small addition amount, and a nitrogen atom-containing graft copolymer or side chain is preferable. Nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having functional groups including tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles and the like are preferred.
The resin-type dispersant is preferably used in an amount of about 5 to 200% by weight based on the total amount of the colorant, and more preferably about 10 to 100% by weight from the viewpoint of film formability.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167 manufactured by Big Chemie Japan. 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164, 6919 , 21116, 21324 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, or LACTIMON, LACTIMON-WS or BYKUMEN, etc., SOLSPERS manufactured by Lubrizol Japan -3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500 EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, manufactured by BASF Japan, etc., 41000, 41090, 53095, 55000, 56000, 76500, etc. 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Etc.

<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 can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When the surfactant is added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the blending amount of the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the content is more than 55 parts by weight, the dispersion may be affected by an excessive dispersant. .

<Removal of coarse particles>
The colored composition of the present invention is prepared by means of centrifugal separation, filtration with a sintered filter or a membrane filter, and the like. Coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more It is preferable to remove the mixed dust. 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, a color filter using the colored composition of the present invention will be described.
The color filter comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment. Further, in addition to the three color filter segments, a yellow filter segment may be provided.
Preferably, at least one green filter segment is formed using the coloring composition for a color filter of the present invention. Also, at least one yellow filter segment is formed using the colored composition of the present invention.

  A red filter segment, a green filter segment, and a yellow filter segment can be formed using the coloring composition containing the coloring agent and coloring agent carrier which were described in the said coloring agent [A].

  The blue filter segment can be formed using a normal blue coloring composition including a blue colorant and a colorant carrier. Examples of the blue colorant include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, JP 2004-333817, Blue pigments such as aluminum phthalocyanine pigments described in Japanese Patent No. 4893859 are used. Moreover, a purple coloring agent can be used together with a blue coloring composition. Examples of purple colorants that can be used in combination include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 27, 29, 30, 31, 32, Mention may be made of purple pigments such as 37, 39, 40, 42, 44, 47, 49 and 50. In addition, a basic dye or a salt-forming compound of an acid dye exhibiting blue or purple can be used. When using a dye, a triarylmethane dye, an anthraquinone dye, a cyanine dye, or a xanthene dye is preferable in terms of lightness.

<Color filter manufacturing method>
The color filter can be manufactured 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, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also 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 transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. 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. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

  The color filter of the present invention is bonded to a counter substrate using a sealant, and after injecting liquid crystal from an injection port provided in a seal portion, the injection port is sealed, and a polarizing film or a retardation film is formed on the substrate as necessary. A color liquid crystal display device is manufactured by pasting to the outside. This color liquid crystal display device includes Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertical Alignment (VA), Optically Convencend Bend (OCB). ) Etc., and can be used in a liquid crystal display mode in which colorization is performed.

  Moreover, the color filter of this invention can also be used for manufacture of a color image pick-up element and an organic electroluminescence display.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, unless otherwise specified, “part” and “%” mean “part by weight” and “% by weight”, respectively.

  The average primary particle diameter of the pigment and the weight average molecular weight (Mw) of the resin are as follows.

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

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

  Then, the binder resin solution used by the Example and the comparative example and the manufacturing method of a coloring agent are demonstrated.

<Method for producing binder 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, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The methoxypropyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight. Was added to prepare an acrylic resin solution 1. 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 obtained copolymer solution, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz, 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 wt% Thus, an acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18000.

<Method for Producing Colorant [A]>
(Production of colorant (A-1))
C. I. 100 parts of Pigment Green 7 (“Lionol Green YS-07” manufactured by Toyocolor Co., Ltd.), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. did. This kneaded product is poured into 3000 parts 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. for 24 hours to color. Agent (A-1) was obtained. The average primary particle size was 28.2 nm.

(Production of colorant (A-2))
C.I. used in the colorant (A-1) I. Pigment Green 7 is C.I. I. A colorant (A-2) was obtained in the same manner as the colorant (A-1) except that it was changed to CI Pigment Green 58 (“FASTGEN GREEN A110” manufactured by DIC). The average primary particle size was 32.5 nm.

(Production of colorant (A-3))
A colorant (A-3) which is an aluminum phthalocyanine pigment was obtained by the same production method as the blue colorant (PB-1) described in the examples of Japanese Patent No. 4893859. The average primary particle size was 31.2 nm.

(Production of colorant (A-4))
C.I. used in the colorant (A-1) I. Pigment Green 7 is C.I. I. A colorant (A-4) was obtained in the same manner as the colorant (A-1) except that it was changed to CI Pigment Yellow 138 (trade name Paliotor Yellow K0961HD manufactured by BASF). The average primary particle size was 27.5 nm.

(Production of colorant (A-5))
To 100 parts of methyl benzoate, 40 parts of 8-aminoquinaldine, 110 parts of 2,3-naphthalenedicarboxylic anhydride and 154 parts of benzoic acid are added, heated to 180 ° C., and stirred for 6 hours while distilling off water. went. After cooling to room temperature, the reaction mixture was added to 1200 parts of methanol and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure. Subsequently, 900 parts of water and 150 parts of potassium hydroxide were added to the product, heated to 90 ° C., and stirred for 16 hours. After cooling to room temperature, 200 parts of 36% hydrochloric acid was added dropwise. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure. Subsequently, the above product was added to 300 parts of methyl benzoate, 73 parts of tetrachlorophthalic anhydride and 123 parts of benzoic acid were further added, heated to 180 ° C., and stirred for 5 hours while distilling off water. After cooling to room temperature, the reaction mixture was added to 1200 parts of methanol and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure. As a result of mass spectrometry by TOF-MS, the following formula (3-1) was identified.
C.I. used in the colorant (A-1) I. A coloring agent (A-5) was obtained in the same manner as the coloring agent (A-1) except that CI Pigment Green 7 was changed to a quinophthalone pigment of the following formula (3-1). The average primary particle size was 28.7 nm.

(Production of colorant (A-6))
C.I. used in the colorant (A-1) I. Pigment Green 7 is C.I. I. A colorant (A-6) was obtained in the same manner as the colorant (A-1) except that it was changed to CI Pigment Yellow 150 (trade name E4GN manufactured by LANXESS). The average primary particle size was 25.5 nm.

(Production of colorant (A-7))
C.I. used in the colorant (A-1) I. Pigment Green 7 is C.I. I. A colorant (A-7) was obtained in the same manner as the colorant (A-1) except that it was changed to CI Pigment Yellow 185 ("Paliogen Yellow D1155" manufactured by BASF). The average primary particle size was 29.8 nm.

(Production of colorant (A-8))
C.I. used in the colorant (A-1) I. Pigment Green 7 is C.I. I. A colorant (A-8) was obtained in the same manner as the colorant (A-1) except that it was changed to CI Pigment Red 254 ("Irgafore Red B-CF" manufactured by BASF). The average primary particle size was 24.9 nm.

(Production of colorant (A-9))
C.I. used in the colorant (A-1) I. Pigment Green 7 is C.I. I. A colorant (A-9) was obtained in the same manner as the colorant (A-1) except that it was changed to CI Pigment Red 177 ("chromophthaled red A2B" manufactured by BASF Japan). The average primary particle size was 23.5 nm.

<Method for producing quinophthalone compound [B]>
Prior to the production of the quinophthalone compound, a method for identifying the quinophthalone compound used in the present invention will be described.

(Identification method of quinophthalone compound)
The quinophthalone compound of the present invention was identified by elemental analysis, infrared absorption spectrum, and MALDI TOF-MS spectrum. Elemental analysis was performed using a Perkin Elmer 2400 CHN Elegant Analyzer. The infrared absorption spectrum was measured by a KBr tablet method using a Fourier transform infrared spectrophotometer FT / IR-410 manufactured by JASCO Corporation with a resolution of 2 cm −1. The MALDI TOF-MS spectrum uses the MALDI mass spectrometer “autoflex III” manufactured by Bruker Daltonics, Inc. to identify the obtained compound with the coincidence between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. It was.

[Example 1]
(Production of quinophthalone compound (B-1))
To 100 parts of methyl benzoate, add 40 parts of 8-aminoquinaldine, 115 parts of 2,3-naphthalenedicarboxylic anhydride and 154 parts of benzoic acid, heat to 180 ° C., and stir for 6 hours while distilling off water. went. After cooling to room temperature, the reaction mixture was added to 1200 parts of methanol and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure. Subsequently, 900 parts of water and 150 parts of potassium hydroxide were added to the product, heated to 90 ° C., and stirred for 16 hours. After cooling to room temperature, 200 parts of 36% hydrochloric acid was added dropwise. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure. Subsequently, the product was added to 300 parts of methyl benzoate, 87 parts of tetrachlorophthalic anhydride and 123 parts of benzoic acid were further added, heated to 180 ° C., and stirred for 5 hours while distilling off water. After cooling to room temperature, the reaction mixture was added to 1200 parts of methanol and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration and further washed with methanol. Subsequently, 3000 parts of water and 75 parts of sodium hydroxide were added to the product, heated to 40 ° C., and stirred for 3 hours. After cooling to room temperature, 200 parts of 36% hydrochloric acid was added dropwise. The precipitated crystals were separated by filtration, further washed with water, and dried under reduced pressure to obtain 152 parts of quinophthalone compound (B-1) (yield: 96%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a quinophthalone compound (B-1). The infrared absorption spectrum of the quinophthalone compound (B-1) is shown in FIG.

[Example 2]
(Production of quinophthalone compound (B-2))
The same operation as in Example 1 was performed except that 45 parts of phthalic anhydride was used instead of 87 parts of tetrachlorophthalic anhydride used in Example 1, and 112 parts of the quinophthalone compound (B-2) (yield) : 91%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a quinophthalone compound (B-2). The infrared absorption spectrum of the quinophthalone compound (B-2) is shown in FIG.

[Example 3]
(Production of quinophthalone compound (B-3))
A quinophthalone compound (B-3) was prepared in the same manner as in Example 1 except that 149 parts of 4-sulfophthalic acid (50% aqueous solution) was used instead of 87 parts of tetrachlorophthalic anhydride used in Example 1. ) 126 parts (yield: 88%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a quinophthalone compound (B-3). The infrared absorption spectrum of the quinophthalone compound (B-3) is shown in FIG.

[Example 4]
(Production of quinophthalone compound (B-4))
To 100 parts of methyl benzoate, add 40 parts of 8-aminoquinaldine, 115 parts of 2,3-naphthalenedicarboxylic anhydride and 154 parts of benzoic acid, heat to 180 ° C., and stir for 6 hours while distilling off water. went. After cooling to room temperature, the reaction mixture was added to 1200 parts of methanol and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure. Subsequently, 900 parts of water and 150 parts of potassium hydroxide were added to the product, heated to 90 ° C., and stirred for 16 hours. After cooling to room temperature, 200 parts of 36% hydrochloric acid was added dropwise. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure. Subsequently, the product was added to 300 parts of methyl benzoate, 87 parts of tetrachlorophthalic anhydride and 123 parts of benzoic acid were further added, heated to 180 ° C., and stirred for 5 hours while distilling off water. After cooling to room temperature, the reaction mixture was added to 1200 parts of methanol and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure. Subsequently, the product was dissolved in 1400 parts of 100% sulfuric acid and stirred at 80 ° C. for 4 hours. After cooling to room temperature, the reaction mixture was added to 14000 parts of water and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration and further washed with water. Subsequently, 3000 parts of water and 75 parts of sodium hydroxide were added to the product, heated to 40 ° C., and stirred for 3 hours. After cooling to room temperature, 200 parts of 36% hydrochloric acid was added dropwise. The precipitated crystals were separated by filtration, further washed with water, and dried under reduced pressure to obtain 166 parts of quinophthalone compound (B-4) (yield: 93%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a quinophthalone compound (B-4). The infrared absorption spectrum of the quinophthalone compound (B-4) is shown in FIG.

[Example 5]
(Production of quinophthalone compound (B-5))
To 100 parts of methyl benzoate, add 40 parts of 8-aminoquinaldine, 115 parts of 2,3-naphthalenedicarboxylic anhydride and 154 parts of benzoic acid, heat to 180 ° C., and stir for 6 hours while distilling off water. went. After cooling to room temperature, the reaction mixture was added to 1200 parts of methanol and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure. Subsequently, the product was dissolved in 1400 parts of 100% sulfuric acid and stirred at 80 ° C. for 4 hours. The reaction mixture was added to 14000 parts of water and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration and further washed with water. Subsequently, 3000 parts of water and 75 parts of sodium hydroxide were added to the product, heated to 40 ° C., and stirred for 3 hours. After cooling to room temperature, 200 parts of 36% hydrochloric acid was added dropwise. The precipitated crystals were separated by filtration, washed with water, and dried under reduced pressure to obtain 147 parts (yield: 94%) of the quinophthalone compound (B-5). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a quinophthalone compound (B-5).

[Example 6]
(Production of quinophthalone compound (B-6))
A quinophthalone compound (B-6) was prepared in the same manner as in Example 4 except that 149 parts of 4-sulfophthalic acid (50% aqueous solution) was used instead of 87 parts of tetrachlorophthalic anhydride used in Example 4. 142 parts (yield: 87%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a quinophthalone compound (B-6).

[Example 7]
(Production of quinophthalone compound (B-7))
Instead of 40 parts of 8-aminoquinaldine and 87 parts of tetrachlorophthalic anhydride used in Example 1, 59 parts of 6-phenyl-8-aminoquinaldine and 78 parts of 5-methoxy-4-sulfophthalic acid were used. The procedure was the same as in Example 1, except that 155 parts of quinophthalone compound (B-7) (yield: 91%) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a quinophthalone compound (B-7).

[Example 8]
(Production of quinophthalone compound (B-8))
The same as Example 3 except that 207 parts of 6,7-dibromo-2,3-naphthalenedicarboxylic anhydride was used instead of 115 parts of 2,3-naphthalenedicarboxylic anhydride used in Example 3. Operation was performed to obtain 163 parts (yield: 89%) of the quinophthalone compound (B-8). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a quinophthalone compound (B-8).

[Example 9]
(Production of quinophthalone compound (B-9))
To 100 parts of methyl benzoate, add 40 parts of 8-aminoquinaldine, 115 parts of 2,3-naphthalenedicarboxylic anhydride and 154 parts of benzoic acid, heat to 180 ° C., and stir for 6 hours while distilling off water. went. After cooling to room temperature, the reaction mixture was added to 1200 parts of methanol and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure. Subsequently, 900 parts of water and 150 parts of potassium hydroxide were added to the product, heated to 90 ° C., and stirred for 16 hours. After cooling to room temperature, 200 parts of 36% hydrochloric acid was added dropwise. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure. Subsequently, the product was added to 800 parts of N, N-dimethylformamide, 47 parts of N-bromosuccinimide was further added, and the mixture was stirred at 60 ° C. for 6 hours. After cooling to room temperature, the reaction mixture was added to 1500 parts of methanol, 1500 parts of water was added, and the mixture was stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure. Subsequently, the above product was added to 300 parts of methyl benzoate, 149 parts of 4-sulfophthalic acid (50% aqueous solution) and 123 parts of benzoic acid were added, and the mixture was heated to 180 ° C. and stirred for 5 hours while distilling off water. Went. After cooling to room temperature, the reaction mixture was added to 1200 parts of methanol and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration and further washed with methanol. Subsequently, 3000 parts of water and 75 parts of sodium hydroxide were added to the product, heated to 40 ° C., and stirred for 3 hours. After cooling to room temperature, 200 parts of 36% hydrochloric acid was added dropwise. The precipitated crystals were separated by filtration, further washed with water, and dried under reduced pressure to obtain 147 parts (yield: 90%) of the quinophthalone compound (B-9). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a quinophthalone compound (B-9).

[Example 10]
(Production of quinophthalone compound (B-10))
To 100 parts of methyl benzoate, add 40 parts of 8-aminoquinaldine, 115 parts of 2,3-naphthalenedicarboxylic anhydride and 154 parts of benzoic acid, heat to 180 ° C., and stir for 6 hours while distilling off water. went. After cooling to room temperature, the reaction mixture was added to 1200 parts of methanol and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure. Subsequently, 900 parts of water and 150 parts of potassium hydroxide were added to the product, heated to 90 ° C., and stirred for 16 hours. After cooling to room temperature, 200 parts of 36% hydrochloric acid was added dropwise. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure. Subsequently, the product was dissolved in 1000 parts of 100% sulfuric acid and stirred at 80 ° C. for 4 hours. After cooling to room temperature, the reaction mixture was added to 10,000 parts of water and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, further washed with water, and dried under reduced pressure. Subsequently, the product was added to 500 parts of N, N-dimethylformamide and stirred at room temperature for 1 hour. To the above mixture, 50 parts of terephthalic acid was dissolved in 300 parts of N, N-dimethylformamide, and a mixture added with 30 parts of thionyl chloride was gradually added dropwise, followed by further stirring for 3 hours. The reaction mixture was added to 3000 parts of water, cooled to room temperature, and 200 parts of 36% hydrochloric acid was added dropwise. The precipitated crystals were separated by filtration, further washed with water, and dried under reduced pressure to obtain 126 parts (yield: 88%) of the quinophthalone compound (B-10). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a quinophthalone compound (B-10).

[Example 11]
(Production of quinophthalone compound (B-11))
Instead of 40 parts of 8-aminoquinaldine and 115 parts of 2,3-naphthalenedicarboxylic anhydride used in Example 4, 44 parts of 3-hydroxy-8-aminoquinaldine and 6-methyl-2,3-naphthalene The same operation as in Example 3 was carried out except that 123 parts of dicarboxylic anhydride was used to obtain 140 parts (yield: 93%) of the quinophthalone compound (B-11). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a quinophthalone compound (B-11).

[Example 12]
(Production of quinophthalone compound (B-12))
The same operation as in Example 10 was carried out except that 69 parts of 4-trifluoromethylbenzenesulfonic acid was used instead of 50 parts of terephthalic acid used in Example 10, and 144 parts of a quinophthalone compound (B-12) ( Yield: 91%) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a quinophthalone compound (B-12).

[Example 13]
(Production of quinophthalone compound (B-13))
The same operation as in Example 10 was carried out except that 72 parts of benzene-1,3-disulfonic acid was used instead of 50 parts of terephthalic acid used in Example 10, and 147 parts of quinophthalone compound (B-13) ( Yield: 91%) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a quinophthalone compound (B-13).

[Example 14]
(Production of quinophthalone compound (B-14))
To 100 parts of methyl benzoate, add 40 parts of 8-aminoquinaldine, 115 parts of 2,3-naphthalenedicarboxylic anhydride and 154 parts of benzoic acid, heat to 180 ° C., and stir for 6 hours while distilling off water. went. After cooling to room temperature, the reaction mixture was added to 1200 parts of methanol and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure. Subsequently, 900 parts of water and 150 parts of potassium hydroxide were added to the product, heated to 90 ° C., and stirred for 16 hours. After cooling to room temperature, 200 parts of 36% hydrochloric acid was added dropwise. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure. Subsequently, the product was added to 500 parts of N, N-dimethylformamide and stirred at room temperature for 1 hour. To the above mixture, 75 parts of 5-sulfoisophthalic acid was dissolved in 300 parts of N, N-dimethylformamide, a mixture added with 30 parts of thionyl chloride was gradually added dropwise, and the mixture was further stirred for 3 hours. The reaction mixture was added to 3000 parts of water, cooled to room temperature, and 200 parts of 36% hydrochloric acid was added dropwise. The precipitated crystals were separated by filtration, further washed with water, and dried under reduced pressure to obtain 126 parts (yield: 88%) of the quinophthalone compound (B-14). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a quinophthalone compound (B-14).

[Example 15]
(Production of quinophthalone compound (B-15))
With reference to JP 2012-193318 A, quinophthalone, which is an ammonium salt of octylamine, is obtained by counter-exchanging the quinophthalone compound (B-3) using Farmin 08D (manufactured by Kao) under alkaline conditions. Compound (B-15) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a quinophthalone compound (B-15).

[Example 16]
(Production of quinophthalone compound (B-16))
143 parts of the quinophthalone compound (B-10) was added to 500 parts of N, N-dimethylformamide and stirred at room temperature for 1 hour. To the above mixture, 29 parts of phenol was dissolved in 300 parts of N, N-dimethylformamide, and a mixture added with 30 parts of thionyl chloride was gradually added dropwise, followed by further stirring for 3 hours. The reaction mixture was added to 3000 parts of water, cooled to room temperature, and 200 parts of 36% hydrochloric acid was added dropwise. The precipitated crystals were separated by filtration, further washed with water, and dried under reduced pressure to obtain 144 parts (yield: 89%) of the quinophthalone compound (B-16). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a quinophthalone compound (B-16).

  Tables 1 and 2 show the results of mass spectrometry and elemental analysis performed on the quinophthalone compounds synthesized in Examples 1-16.

<Manufacturing method of other quinophthalone compounds>
(Production of quinophthalone compound (C-1))
According to the synthesis method described in Japanese Patent No. 4585781, a quinophthalone compound (C-1) was obtained.

(Production of quinophthalone compound (C-2))
According to the synthesis method described in JP-A-2007-156395, a quinophthalone compound (C-2) was obtained.

<Method for producing colored composition for color filter>
[Example 17]
(Production of colored composition (D-1))
A mixture having the following composition 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. It filtered with a 0.0 micrometer filter and the coloring composition (D-1) was produced.
Colorant (A-1) 8.8 parts Dye derivative Quinophthalone compound (B-1) 2.2 parts Resin type dispersant ("BYK-21116" manufactured by BYK Chemie) 6.9 parts Acrylic resin solution 1 31.2 parts Propylene glycol monomethyl ether acetate 50.9 parts

[Examples 18 to 54, Comparative Examples 1 to 13]
(Production of colored composition (D-2 to 51))
The total content of the colorant and the quinophthalone compound was all fixed at 11.0 parts, and the type and weight ratio of the colorant and the quinophthalone compound were changed as described in Table 3, as in Example 17, A colored composition (D-2 to 51) was obtained.

<Evaluation of coloring composition>
The contrast, initial viscosity, storage stability, and heat resistance of the obtained colored composition (D-1 to 51) were evaluated by the following methods. Table 4 shows the evaluation results.
(Contrast evaluation)
The obtained colored composition was formed on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, and the film thickness after heat treatment at 220 ° C. was changed to about 1.5 μm by changing the number of rotations. Three coated substrates were prepared so as to be. Drying conditions were 20 minutes at 70 ° C. and 30 minutes at 220 ° C. after coating, respectively, and the film thickness and contrast ratio were measured, and the contrast at a film thickness of 1.5 μm was determined from the three-point data by the primary correlation method. It was.

(Evaluation of initial viscosity)
The viscosity of the coloring composition was measured by using an E type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.) at an initial viscosity at 25 ° C.
(Evaluation of storage stability)
The obtained colored composition was stored in a thermostat at 40 ° C. for 1 week and accelerated over time, and then the viscosity of the colored composition after aging was measured by the same method as the viscosity measurement, and stored at 40 ° C. for 1 week. The change rate of the viscosity before and after the calculation was calculated and evaluated in two stages according to the following criteria.
○: When the viscosity change rate is within ± 20% and no sediment is formed (good)
X: When the viscosity change rate exceeds ± 20%, or when a precipitate is formed even if the viscosity change rate is within ± 20% (defective)

(Evaluation of heat resistance)
The coloring composition (D-1 to 51) is applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, and then at 220 ° C. for 30 minutes. The coated substrate was prepared by heating and allowing to cool. The prepared coated substrate was adjusted to a thickness of 1.5 μm after heat treatment at 220 ° C. 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. Further, as a heat resistance test, the sample was heated at 230 ° 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 three stages.
ΔEab * = √ ((L * (2) −L * (1)) ² + (a * (2) −a * (1)) ² + (b * (2) −b * (1)) ² )
○: ΔEab * is less than 3.0 (good)
Δ: ΔEab * is 3.0 or more and less than 5.0 (defect)
×: ΔEab * is 5.0 or more (very poor)

  As shown in Table 4, the coloring composition containing the quinophthalone compound [B] represented by the general formula (1) and the colorant [A], which is a feature of the present invention, has contrast, initial viscosity, storage stability, And the heat resistance was good.

On the other hand, coloring compositions (D-20, 21, 25, 26, 29, 32, 38, 39, 42, 45, 48) of Comparative Examples 1-2, 4-13 containing conventionally used pigment derivatives. 51) was a result in which the contrast, initial viscosity, and heat resistance were inferior to those of the examples of the present invention.
Moreover, the comparative example 3 (D-22) which does not use a coloring agent [A] was a result in which all the characteristics were inferior to the Example of this invention.

<Method for producing photosensitive coloring composition>
[Example 55]
(Production of photosensitive coloring composition (R-1))
A mixture having the following composition was stirred and mixed uniformly, and then filtered through a 1.0 μm filter to obtain a green photosensitive coloring composition (R-1).
Colored composition (D-3) 29.0 parts Colored composition (D-33) 18.8 parts Acrylic resin solution 2 7.1 parts Photopolymerizable monomer ("Aronix M402" manufactured by Toagosei Co., Ltd.) 3.3 Part Photopolymerization initiator (“Irgacure OXE02” manufactured by BASF Japan Ltd.) 0.8 part Propylene glycol monomethyl ether acetate 41.0 parts

[Examples 56 to 61, Comparative Examples 14 to 16]
(Production of photosensitive coloring composition (R-2 to 10))
The photosensitive coloring composition was the same as in Example 55 except that the total content of the coloring composition was fixed at 47.8 parts and the type and blending amount of the coloring composition were changed as described in Table 5. The thing (R-2-10) was obtained.

<Evaluation of photosensitive coloring composition>
Evaluation of the brightness, contrast, initial viscosity, storage stability, and heat resistance of the obtained photosensitive coloring composition (R-1 to 10) was performed by the following methods. Table 5 shows the evaluation results.
(Evaluation of brightness)
The photosensitive coloring composition (R-1 to 10) is applied onto a glass substrate having a size of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, and then dried at 70 ° C. for 20 minutes. Was used for ultraviolet light exposure with an integrated light amount of 150 mJ / cm ² and developed with an alkaline developer at 23 ° C. to obtain a coated substrate. Then, after heating at 220 ° C. for 30 minutes and allowing to cool, the brightness Y (C) of the obtained coating film substrate was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). In the case of a green coated substrate, it matches the chromaticity of x = 0.245, y = 0.650, or x = 0.290, y = 0.600 with a C light source after heat treatment at 220 ° C. I did it. In the case of a red coated substrate, after the heat treatment at 220 ° C., the chromaticity of x = 0.640 and y = 0.330 was matched with the C light source. As the alkali developer, sodium carbonate 1.5% by weight, sodium hydrogen carbonate 0.5% by weight, an anionic surfactant ("PERIREL NBL" manufactured by Kao Corporation) 8.0% by weight and water 90% by weight Was used. Regarding brightness Y (C), it can be said that there is a clear difference if it is 0.2 points or more.

(Contrast evaluation)
Contrast measurement was performed using the substrate used in the brightness evaluation.

(Evaluation of initial viscosity)
The viscosity of the photosensitive coloring composition was determined by measuring the initial viscosity at 25 ° C. using an E-type viscometer (“ELD viscometer” manufactured by Toki Sangyo Co., Ltd.).
(Evaluation of storage stability)
About the obtained photosensitive coloring composition, after storing for one week in a 40 degreeC thermostat and accelerating with time, the viscosity of the photosensitive coloring composition after time-lapse | temporality is measured by the same method as the said viscosity measurement, and 40 degreeC. The rate of change in viscosity before and after storage for 1 week was calculated and evaluated in two stages according to the following criteria.
○: When the viscosity change rate is within ± 20% and no sediment is formed (good)
X: When the viscosity change rate exceeds ± 20%, or when a precipitate is formed even if the viscosity change rate is within ± 20% (defective)

(Evaluation of heat resistance)
The photosensitive coloring composition (R-1 to 10) is applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, and then at 220 ° C. A coating film substrate was prepared by heating and cooling for 30 minutes. The prepared coated substrate was adjusted to a thickness of 1.5 μm after heat treatment at 220 ° C. 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. Further, as a heat resistance test, the sample was heated at 230 ° 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 three stages.
ΔEab * = √ ((L * (2) −L * (1)) ² + (a * (2) −a * (1)) ² + (b * (2) −b * (1)) ² )
○: ΔEab * is less than 3.0 (good)
Δ: ΔEab * is 3.0 or more and less than 5.0 (defect)
×: ΔEab * is 5.0 or more (very poor)

  As shown in Table 5, the colored composition containing the quinophthalone compound [B] having a naphthalene skeleton and the colorant [A], which is a feature of the present invention, has brightness, contrast, initial viscosity, storage stability, and heat resistance. Was a good result.

  On the other hand, the colored compositions (R-4, 7, 10) of Comparative Examples 14 to 16 using conventionally known pigment derivatives were inferior in brightness and contrast to the examples of the present invention.

<Production of color filter>
First, the blue photosensitive coloring composition used for preparation of a color filter was produced.

(Preparation of blue photosensitive coloring composition (R-11))
A mixture having the following composition 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. It filtered with a 0.0 micrometer filter, and produced the blue coloring composition (D-52).
Blue pigment (CI Pigment Blue 15: 6) 7.2 parts Purple pigment (CI Pigment Violet 23) 4.8 parts Resin-type dispersant ("EFKA4300" manufactured by BASF Japan Ltd.) 1.0 part Acrylic Resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

Then, after stirring and mixing the mixture of the following composition so that it might become uniform, it filtered with a 1.0 micrometer filter, and produced the blue photosensitive coloring composition (R-11).
Blue coloring composition (D-52) 34.0 parts Acrylic resin solution 2 15.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (BASF Japan) "Irgacure 907") 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Ethylene glycol monomethyl ether acetate 45.1 parts

(Production of color filter)
A black matrix was patterned on a glass substrate, and the red photosensitive coloring composition (R-8) of the present invention was applied onto the substrate with a spin coater to form a colored film. The film was irradiated with ultraviolet rays of 150 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 220 ° C. for 30 minutes to obtain a red filter segment. Formed. Here, the red filter segment was adjusted to a chromaticity of x = 0.640 and y = 0.330 in a C light source (hereinafter also used for green and blue) after heat treatment at 220 ° C. In the same manner, the green filter segment is matched with the chromaticity of x = 0.290, y = 0.600 using the green photosensitive coloring composition (R-5) of the present invention, and blue The filter segment was adjusted to chromaticity of x = 0.150 and y = 0.060 using the blue photosensitive coloring composition (R-11), and each filter segment was formed to obtain a color filter. .

  By using the photosensitive coloring composition (R-8, R-5) of the present invention for the formation of red and green filter segments, the brightness of the color filter can be increased, and other physical properties are suitable without any problems. Could be used.

Claims (6)

Coloring agent [A] (excluding cases where it is a dye derivative described later) , a coloring composition comprising a dye derivative, a binder resin, and an organic solvent, wherein the dye derivative is represented by the following general formula (1) A coloring composition, which is a quinophthalone compound [B].

[In General Formula (1), R _{1 to} R ₅ and R _{6 to} R ₁₁ each independently have a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group that may have a substituent, or a substituent. which may alkoxyl group, an optionally substituted aryl group, an ester group, a sulfo group; a carboxyl group; and monovalent to trivalent metal salt thereof acidic group; an alkyl ammonium salt, Z ₁ is - SO ₂ — or —CO—, wherein Z ₂ is an aromatic ring residue that may have a substituent, and the substituent is a halogen atom, a hydroxyl group, an alkyl group that may have a substituent, An alkoxyl group which may have a substituent, an aryl group which may have a substituent, an ester group, a sulfo group; a carboxyl group; and a monovalent to trivalent metal salt of these acidic groups; A substituent selected from the group consisting of
However, among the _{R 1 ~R 5, R 6 ~R} 11, Z 2, at least one includes a sulfo group, a sulfo group metal salts and sulfoalkyl ammonium salts or Ranaru a group selected from the group of radicals . ] The coloring composition according to claim 1, wherein Z ₁ is —CO—. The colorant [A] is any one or more selected from the group consisting of quinophthalone pigments, metal phthalocyanine pigments, isoindoline pigments, azo metal complex pigments, diketopyrrolopyrrole pigments, and anthraquinone pigments. The coloring composition according to claim 1 or 2 . Furthermore, the coloring composition of any one of Claims 1-3 formed by containing a photopolymerizable monomer and / or a photoinitiator. A color filter comprising a filter segment formed from the colored composition according to any one of claims 1 to 4 on a substrate. A quinophthalone compound represented by the general formula (1).

[In General Formula (1), R _{1 to} R ₅ and R _{6 to} R ₁₁ each independently have a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group that may have a substituent, or a substituent. which may alkoxyl group, an optionally substituted aryl group, an ester group, a sulfo group; a carboxyl group; and monovalent to trivalent metal salt thereof acidic group; an alkyl ammonium salt, Z ₁ is - SO ₂ — or —CO—, wherein Z ₂ is an aromatic ring residue that may have a substituent, and the substituent is a halogen atom, a hydroxyl group, an alkyl group that may have a substituent, An alkoxyl group which may have a substituent, an aryl group which may have a substituent, an ester group, a sulfo group; a carboxyl group; and a monovalent to trivalent metal salt of these acidic groups; A substituent selected from the group consisting of
However, at least one of R _{1 to} R ₅ , R _{6 to} R ₁₁ , and Z ₂ includes a group selected from the group consisting of a sulfo group, a metal salt of the sulfo group, and an alkyl ammonium salt of the sulfo group. ]

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