Colored composition and color filter

Abstract

To provide a coloring composition which offers superior coloring power, transmittance, and heat resistance, and to provide a color filter using the same.SOLUTION: A coloring composition is provided, containing a quinophthalone pigment (A) represented by a general formula (1) below and a resin. In the general formula (1), X1 represents a hydroxyl group, -NH-CO-R113, or -NH-SO2-R114, and R113 and R114 represent an alkyl group having 1 to 4 carbon atoms and aryl group that may have a substituent and has 6 to 12 carbon atoms.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a coloring composition containing a quinophthalone pigment, and more particularly to a coloring composition and color filter suitable for manufacturing color filters used in color liquid crystal display devices, color image sensors, and organic EL display devices. [Background technology]

[0002] C-MOS(Complementary Metal Oxide Semiconductor) Color image sensors, such as uctors (complementary metal-oxide-semiconductor) and CCDs (Charge-Coupled Devices), typically separate colors by arranging color filters on their light-receiving elements. These filters consist of additively mixed primary color segments: a red filter layer (R), a green filter layer (G), and a blue filter layer (B). Color filters with complementary colors—cyan, magenta, and yellow (CMY)—are also commonly used because they offer higher sensitivity than primary color filters. Complementary color filters are often employed in video cameras and other devices where auxiliary light sources such as flashes are difficult to use.

[0003] In recent years, in order to achieve more beautiful images and videos, the area of ​​filter segments in color filters has been reduced, and consequently, thinner films have also become necessary. This is because, for the same film thickness, the smaller the size of the filter segment, the less light is received, so it is necessary to reduce the film thickness to allow more light to be received. In particular, the demand for thinner color filters in modern color image sensors has become increasingly stringent. However, the same color characteristics are still required. Therefore, when using the same pigment, the amount of pigment per unit area in the filter segment must remain unchanged, and thinning must be achieved by reducing only the other components. In this case, the concentration of pigment in the solid content of the coloring composition used to form the filter segment becomes higher. However, when manufacturing color filters, if the pigment concentration is too high when applying the coloring composition coating solution, the viscosity of the coating solution increases, making uniform application impossible. Therefore, there is a need for pigments with high coloring power that can exhibit sufficient color characteristics even in small quantities. Furthermore, these pigments must also have high transmittance to receive more light and heat resistance to withstand the processes involved in manufacturing color filters.

[0004] In the manufacture of green filter segments, yellow pigments are used as colorants for toning, with CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, and CI Pigment Yellow 185 being the most commonly used. CI Pigment Yellow 138 has relatively good transmittance, but its coloring power is weak as described above, making it unsuitable for thin films. On the other hand, CI Pigment Yellow 139, CI Pigment Yellow 150, and CI Pigment Yellow 185 have some coloring power, but their transmittance is insufficient.

[0005] To address these problems, various developments have been made regarding quinophthalone compounds that exhibit a yellow color. For example, Patent Document 1 discloses a novel quinophthalone compound with excellent coloring ability and a structure that provides high brightness and contrast ratio. Patent Document 2 also describes a quinophthalone compound containing a fluorine atom. However, these colorants containing quinophthalone compounds have not been satisfactory in terms of heat resistance and coloring ability. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2012-226110 [Patent Document 2] Japanese Patent Publication No. 2016-145282 [Overview of the Initiative]

Problems to be Solved by the Invention

[0007] An object of the present invention is to provide a coloring composition excellent in coloring power, transmittance, and heat resistance, which contributes to the thinning of a color filter.

Means for Solving the Problems

[0008] As a result of intensive studies, the present inventors have found that a coloring composition for a color filter containing a quinophthalone compound having a specific structure can solve the above problems, and have thus arrived at the present invention.

[0009] That is, the present invention relates to a coloring composition containing a quinophthalone pigment (A) represented by the following general formula (1) and a resin.

[0010] General formula (1)

Chemical formula

[0011] Further, the present invention relates to a colored composition in which the quinophthalone pigment (A) is composed of 40% by mass of the quinophthalone pigment (A) in the total solid content and a resin having a spectral transmittance of 95% or more in the entire wavelength range of 400 to 700 nm, and when a film having a film thickness of 1 μm is formed, the maximum value of the absorbance at 450 to 500 nm is 1.7 or more.

[0012] Further, the present invention relates to the above colored composition, wherein the average primary particle diameter of the quinophthalone pigment (A) is 5 to 400 nm.

[0013] Further, the present invention relates to the above colored composition containing a green pigment.

[0014] Further, the present invention relates to the above colored composition containing a photoinitiator.

[0015] Further, the present invention relates to the above colored composition containing a photopolymerizable monomer.

[0016] Further, the present invention relates to a color filter including a filter segment containing the above colored composition.

Advantages of the Invention

[0017] According to the present invention, by using the quinophthalone compound represented by the above general formula (1) as a colorant, it is possible to provide a colored composition excellent in coloring power, transmittance, and heat resistance, and a color filter using the same.

Embodiments for Carrying Out the Invention

Modes for Carrying Out the Invention

[0018] Hereinafter, the present invention will be described in detail. In this specification, "C.I." means Color Index.

[0019] <Quinophthalone Pigment (A)> (Structure) The quinophthalone pigment (A) in the present invention has a structure represented by the following general formula (1) . General formula (1) [ka] (R 11 ~R 17 Each of these independently consists of a hydrogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a sulfo group, a C1-C4 alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarboxyl group, a halogen atom, a C2-C4 alkenyl group, an alkenyloxy group, a C6-C12 aryl group, and -SO2-OR. 111 , -SO2-NH-R 112 This represents a ring formed by two of these atoms, each excluding a hydrogen atom, and another group of atoms may be inserted between them when the ring is formed. 111 , R 112 This represents an alkyl group with 1 to 4 carbon atoms. X1 is a hydroxyl group, -NH-CO-R 113 , -NH-SO2-R 114 Represents R 113 , R 114 (This represents an alkyl group having 1 to 4 carbon atoms, or an aryl group or heteroaryl group having 6 to 20 carbon atoms, which may have substituents.)

[0020] Examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl groups. Examples of alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, isobutyloxy, and t-butyloxy groups. Examples of alkenyl groups having 2 to 4 carbon atoms include ethyleneyl, propenyl, and butyrenyl groups. Examples of aryl or heteroaryl groups having 6 to 20 carbon atoms include phenyl, benzyl, naphthyl, anthracenyl, pyrenyl, indoleyl, benzothiazoleyl, quinaldidineyl, xanthenyl, fluorenyl, carbazoleyl, fluorenonyl, diphenylaminophenyl, bromonaphthyl, chloronaphthyl, bromoanthracenyl, and chloroanthracenyl groups.

[0021] By having a quinophthalone pigment (A) with a structure represented by general formula (1), a colored composition with excellent coloring power, transmittance, and heat resistance can be obtained. In particular, from the standpoint of coloring ability, X1 is -NH-CO-R 113 Or -NH-SO2-R 114 It is represented as R 113 or R 114 It is preferable that the structure is represented by an aryl group or heteroaryl group having 6 to 20 carbon atoms, which may have substituents.

[0022] The film formed by the colored composition of the present invention preferably exhibits high absorbance in the wavelength range of 450 to 500 nm. More specifically, when a colored composition consisting of 40% by mass of the quinophthalone pigment (A) in the total solid content and a resin with a spectral transmittance of 95% or more in the entire wavelength range of 400 to 700 nm forms a film with a thickness of 1 μm, it is preferable that the maximum absorbance at 450 to 500 nm is 1.7 or higher, more preferably 2.0 or higher, and even more preferably 2.3 or higher. Higher values ​​indicate higher coloring power of the pigment, and since the desired color characteristics can be achieved even with a small amount of pigment per unit area in the filter segment of the color filter, it can contribute to the thinning of color filters.

[0023] The absorbance of the above film is greatly influenced not only by the absorbance of the quinophthalone compound itself, but also by the crystalline form when it is used as a pigment. In the case of CI Pigment Yellow 138, a quinophthalone pigment, two crystalline forms, α-type and β-type, have been confirmed to exist, and their absorption spectra differ significantly. The α-type crystalline form has an absorption peak in the ultraviolet region and shows a broad shape with no peaks in the 400-450 nm range, while the β-type crystalline form has two sharp absorption peaks in the 400-500 nm range, one of which is located in the 450-500 nm range. This phenomenon is also observed in quinophthalone pigments other than CI Pigment Yellow 138. Even with quinophthalone pigment (A), the same molecular structure can exist in multiple crystalline forms, and the preferred crystalline form differs depending on the molecular structure. Similar to CI Pigment Yellow 138, even with the same molecular structure, different crystalline forms of the pigment result in significantly different absorption spectra when the above film is formed. Some exhibit an absorption peak in the ultraviolet region and a broad shape with no peaks in the 400-450 nm range (the crystalline form exhibiting this absorption spectrum will be referred to as "α-type" below), while others exhibit two sharp absorption peaks in the 400-500 nm range, one of which is... In some cases, the absorption peaks are located at 450-500 nm (the crystal form exhibiting this absorption spectrum will be referred to as "β-type" below). In order to contribute to the thinning of color filters and to obtain sufficient coloring power that exhibits good color characteristics even with a small amount of pigment, it is preferable for the pigment to take on a β-type crystalline form, that is, it is preferable for the pigment to have a molecular structure that makes it easy to take on such a crystalline form. The inventors have discovered that this molecular structure is indeed the molecular structure represented by general formula (1). Although the reason is not entirely clear, it is thought that when the phthalate-modified site at position 2 of the quinoline ring is a naphthalene skeleton and a hydrogen-bonding substituent is present at position 8, it is easier to adopt a crystalline form that exhibits the desired absorption spectrum from the standpoint of steric hindrance and molecular association.

[0024] Furthermore, sufficient transmittance can be obtained when the quinophthalone pigment (A) has the molecular structure represented by general formula (1). This is thought to be due to the high transmittance of the quinophthalone structure. Specifically, the transmittance at 550 nm of a film formed using a colored composition containing quinophthalone pigment (A), with the film thickness adjusted so that the minimum transmittance at 450-500 nm is 1%, serves as an indicator.

[0025] Furthermore, when the quinophthalone pigment (A) has the molecular structure represented by general formula (1), sufficient heat resistance can be obtained. Although the reason for this is not entirely clear, it is presumed that this is due to the naphthalene skeleton having a certain degree of heat resistance and the hydrogen-bonding substituent at position 8 of the quinoline ring improving heat resistance.

[0026] Since the quinophthalone pigment (A) in the present invention is used as a yellow pigment, it is important that it exhibits sufficient color characteristics as a yellow pigment. To this end, it is preferable that the film formed by the colored composition of the present invention generally blocks light in the 400-450 nm range and generally transmits light in the 550-700 nm range. Here, "generally block" means that the transmittance is about 1% or less, and "generally transmit" means that the transmittance is about 92% or more. When the colored composition of the present invention is used in the manufacture of a color image sensor, it is conceivable that the quinophthalone pigment (A) may be used in combination with a green pigment in a green filter segment, or in combination with a red pigment in a red filter segment. By generally blocking light in the 400-450 nm range of the segment, the area that transmits light will not overlap with that of the blue filter segment, thereby maintaining the accuracy of the image sensor. Furthermore, by generally transmitting light in the 550-700 nm range of the segment, the sensitivity of the image sensor can be improved.

[0027] (Solvent treatment of quinophthalone pigment (A)) As mentioned above, quinophthalone pigment (A) may take on multiple crystalline forms, but to obtain higher coloring power, it is preferable to take on the β-type crystalline structure. These crystal forms can be controlled by solvent treatment. Solvent treatment involves mixing the pigment with a solvent and stirring it for a certain period of time, sometimes while heating or cooling. This allows the crystal form to be changed, and depending on the conditions, the particle size can also be altered. The pigment does not need to be completely dissolved; it is thought that if even a part of the component is dissolved, new crystal growth will begin. Any solvent can be used, but a solvent that readily dissolves the quinophthalone pigment (A) is preferred, such as N-methylpyrrolidone, xylene, or toluene.

[0028] When the quinophthalone pigment (A) has a hydroxyl group at the 8th position of the quinoline ring, solvent treatment is preferable. In this case, the pigment initially takes on an α-type crystalline structure, but treatment with a solvent such as N-methylpyrrolidone or xylene causes it to take on a β-type crystalline structure.

[0029] On the other hand, if the quinophthalone pigment (A) has a benzamide group or a benzenesulfonamide group at the 8th position of the quinoline ring, it adopts a β-type crystalline structure immediately after synthesis. In this case, it is preferable to refine it by salt milling without solvent treatment.

[0030] Thus, while solvent treatment may or may not be necessary for the quinophthalone pigment (A) to adopt a desirable crystalline structure, in either case, a film with a desirable absorption spectrum can be obtained, resulting in high coloring power that contributes to the thinning of color filters.

[0031] Examples of quinophthalone pigments (A) include the following structures. [ka] [ka] [ka] [ka] [ka]

[0032] <Combination with other colorants> The colored composition of the present invention may optionally contain various conventionally known pigments and dyes as colorants, in addition to the quinophthalone pigment (A). Representative pigments and dyes that can be used in the present invention are listed below.

[0033] The red pigments that can be used in this invention include, for example, CI 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, Examples include, but are not limited to, the diketopyrrolopyrrole pigments described in JP 2011-523433, JP 2011-173971, JP 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, 282, 283, 284, 285, 286, 287, or the azo dyes described in JP 2011-523433. Red dyes such as xanthene, azo, disazo, and anthraquinone dyes can also be used. Specifically, examples include salt-forming compounds of xanthene-based acid dyes such as CI Acid Red 52, 87, 92, 289, and 338.

[0034] Examples of orange pigments that can be used in the present invention include, but are not limited to, CI Pigment Orange 38, 43, 71, and 73.

[0035] Yellow pigments that can be used in this invention include, for example, CI 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 Examples include, but are not limited to, the quinophthalone pigments described in Japanese Patent Publication No. 4993026, 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, 221, and the quinophthalone pigments described in Japanese Patent Publication No. 4993026. Additionally, yellow dyes such as quinoline, azo, disazo, and methine can also be used.

[0036] Examples of green pigments that can be used in the present invention include, but are not limited to, CI Pigment Green 7, 10, 36, 37, 58, and zinc phthalocyanine pigments described in Japanese Patent Publication No. 2008-19383, Japanese Patent Publication No. 2007-320986, and Japanese Patent Publication No. 2004-70342.

[0037] Examples of blue pigments that can be used in the present invention include, but are not limited to, CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, and aluminum phthalocyanine pigments described in Japanese Patent Publication No. 2004-333817 and Japanese Patent Publication No. 4893859.

[0038] In addition to the quinophthalone pigment (A), other yellow pigments can also be used in combination. Preferred yellow pigments include quinophthalone-based pigments, isoindoline-based pigments, and azo-based pigments.

[0039] As the isoindoline pigments mentioned above, CI Pigment Yellow 139 and 185 are preferred, and as the azo pigment mentioned above, CI Pigment Yellow 150 is preferred.

[0040] Quinophthalone pigment (A) can be used as a green coloring composition by combining any one phthalocyanine pigment alone or in combination of two or more. This can be used to produce green filter segments.

[0041] Preferred phthalocyanine pigments include copper phthalocyanine halide pigments, zinc phthalocyanine halide pigments, or aluminum phthalocyanine pigments. More preferably, aluminum phthalocyanine pigments are used, as described in CI Pigment Green 7, 36, 58, Japanese Patent No. 4893859, Japanese Patent Application Publication No. 2016-153481, Japanese Patent Application Publication No. 2017-197685, etc.

[0042] Quinophthalone pigment (A) can also be used in combination with a red pigment to form a red colored composition. Preferred red pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, and azo pigments. This can be used to produce red filter segments.

[0043] Preferred diketopyrrolopyrrole pigments include CI Pigment Red 254 and the brominated diketopyrrolopyrrole pigment described in Japanese Patent Publication No. 2011-523433; preferred anthraquinone pigments include CI Pigment Red 177; and preferred azo pigments include CI Pigment Orange 38, CI Pigment Red 176, CI Pigment Red 242, CI Pigment Red 269, and the azo compounds described in Japanese Patent Publication No. 2011-173971 and Japanese Patent Publication No. 2012-229344.

[0044] <Pigment miniaturization> It is preferable to use the quinophthalone pigment (A) in a finely milled form. The milling method is not particularly limited, and any known method such as wet milling, dry milling, or dissolution extraction can be used. From the viewpoint of ease of control over milling and degree of milling, it is preferable to mill the pigment by salt milling treatment using the kneader method, which is a type of wet milling, as described later.

[0045] (Particle size) The average primary particle size of the quinophthalone pigment (A), as determined by TEM (transmission electron microscopy), is preferably in the range of 5 to 400 nm. From the viewpoint of dispersion in an organic solvent, a more preferable average primary particle size is in the range of 10 to 200 nm, and particularly preferably in the range of 20 to 100 nm. An average primary particle size of 400 nm or less ensures the transmittance of the color filter without excessive light scattering. On the other hand, an average primary particle size of 5 nm or more provides better heat resistance and dispersibility.

[0046] Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt, and water-soluble organic solvent is mechanically kneaded while heated using a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, etc., and then washed with water to remove the water-soluble inorganic salt and water-soluble organic solvent. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain pigments with a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

[0047] As water-soluble inorganic salts, sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc., can be used, but from a cost standpoint, sodium chloride (table salt) is preferred. From the perspective of both processing efficiency and production efficiency, it is preferable to use 50 to 2000% by mass of the total weight of the pigment, and most preferably 300 to 1000% by mass.

[0048] The water-soluble organic solvent serves to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (miscible) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent is prone to evaporation, a high-boiling-point solvent with a boiling point of 120°C or higher is preferred from a safety standpoint. 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, and liquid polypropylene glycol can be used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by mass, and most preferably 50 to 500% by mass, based on the total weight of the pigment (100% by mass).

[0049] When the pigment is subjected to salt milling, a resin may be added as needed. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc., can be used. The resin used is preferably solid at room temperature, insoluble in water, and more preferably partially soluble in the above organic solvent. The amount of resin used is preferably in the range of 5 to 200% by mass, based on the total weight of the pigment (100% by mass).

[0050] <Binder resin> The binder resin is used to disperse the pigment and includes thermoplastic resins, thermosetting resins, and the like.

[0051] Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclic rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

[0052] Examples of thermosetting resins include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenolic resins.

[0053] The binder resin preferably has a spectral transmittance of 80% or more across the entire wavelength range of 400 to 700 nm in the visible light region, and more preferably a resin with a spectral transmittance of 95% or more. Furthermore, since the colored composition of the present invention is suitably used as an alkali-developable colored resist material, it is preferable to use an alkali-soluble vinyl resin copolymerized with an acidic group-containing ethylenically unsaturated monomer.

[0054] Alkali-soluble resins copolymerized with acidic group-containing ethylenically unsaturated monomers include, for example, resins having acidic groups such as carboxyl groups and sulfone groups. Specifically, alkali-soluble resins include acrylic resins having acidic groups, α-olefin / (anhydride) maleic acid copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, or isobutylene / (anhydride) maleic acid copolymers. Among these, at least one resin selected from acrylic resins having acidic groups and styrene / styrene sulfonic acid copolymers, particularly acrylic resins having acidic groups, are preferred due to their high heat resistance and transparency.

[0055] To improve the photosensitivity of alkali-soluble resins copolymerized with acidic group-containing ethylenically unmonomers, energy-ray curable resins having ethylenically unsaturated active double bonds can also be used. Furthermore, using an active energy-ray curable resin having ethylenically unsaturated double bonds in its side chains is preferable because it improves the solvent resistance of the resist material.

[0056] Examples of active energy ray curable resins having ethylenically unsaturated double bonds include resins in which unsaturated ethylenically double bonds have been introduced by the methods (a) and (b) shown below.

[0057] [Method (a)] Method (a) involves copolymerizing an unsaturated ethylenically occurring monomer having an epoxy group with one or more other monomers to obtain a copolymer. The side chain epoxy group of this copolymer is then subjected to an addition reaction with the carboxyl group of an unsaturated monobasic acid having an unsaturated ethylenically occurring double bond. Furthermore, the resulting hydroxyl group is reacted with a polybasic acid anhydride to introduce an unsaturated ethylenically occurring double bond and a carboxyl group.

[0058] Examples of unsaturated ethylenic monomers having an epoxy group include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate, which may be used individually 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.

[0059] Examples of unsaturated monobasic acids include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and monocarboxylic acids such as α-haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted derivatives of (meth)acrylic acid. These can be used individually or in combination of two or more types.

[0060] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride, which may be used individually or in combination of two or more. If necessary, tricarboxylic acid anhydrides such as trimellitic anhydride or tetracarboxylic dianhydrides such as pyromellitic dianhydride may be used to hydrolyze the remaining anhydride groups. Furthermore, by using tetrahydrophthalic anhydride or maleic anhydride, which have unsaturated ethylenic double bonds, as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased further.

[0061] A method similar to method (a) is, for example, a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group with one or more other monomers, to which an unsaturated ethylenic monomer having an epoxy group is added to some of the side-chain carboxyl groups of the copolymer, thereby introducing an unsaturated ethylenic double bond and a carboxyl group.

[0062] [Method (b)] Method (b) involves using an unsaturated ethylenic monomer having a hydroxyl group and reacting the side-chain hydroxyl group of a copolymer obtained by copolymerizing it with another unsaturated monobasic acid monomer having a carboxyl group or with another monomer, with the isocyanate group of an unsaturated ethylenic monomer having an isocyanate group.

[0063] 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 (meth)acrylate. Examples include acrylates or hydroxyalkyl (meth)acrylates such as cyclohexanedimethanol mono(meth)acrylate, which may be used alone or in combination of two or more. In addition, polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide, etc., to the above hydroxyalkyl (meth)acrylates, or (poly)ester mono(meth)acrylates obtained by adding (poly)γ-valerolactone, (poly)ε-caprolactone, and / or (poly)12-hydroxystearic acid, etc., can also be used. From the viewpoint of suppressing foreign matter in the coating film, 2-hydroxyethyl (meth)acrylate or glycerol (meth)acrylate is preferred.

[0064] Examples of unsaturated ethylenically active monomers having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate or 1,1-bis[(meth)acryloyloxy]ethyl isocyanate, but the composition is not limited to these, and two or more types can be used in combination.

[0065] The weight-average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, and more preferably in the range of 10,000 to 80,000, in order to sufficiently disperse the colorant. The number-average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the Mw / Mn value is preferably 10 or less.

[0066] From the viewpoint of pigment dispersibility, penetration, developability, and heat resistance, the balance of carboxyl groups that act as colorant adsorbent groups and alkali-soluble groups during development, and aliphatic and aromatic groups that act as affinity groups for colorant carriers and solvents other than the binder resin, is important for the dispersibility, penetration, developability, and durability of the pigment and salt-forming compound, and it is preferable to use a resin with an acid value of 20 to 300 mg KOH / g. If the acid value is less than 20 mg KOH / g, solubility in the developer is poor, and it is difficult to form fine patterns. If it exceeds 300 mg KOH / g, fine patterns will not remain. Here, a colorant carrier refers to a resin or other low-molecular-weight component that supports or adsorbs a colorant.

[0067] From the viewpoint of film-forming properties and various resistances, the binder resin is preferably used in an amount of 30% by mass or more, based on the total weight of the colorant (100% by mass), and from the viewpoint of increasing the colorant concentration and exhibiting good color characteristics, it is preferable to use it in an amount of 500% by mass or less.

[0068] <Organic solvents> The colored composition of the present invention may contain an organic solvent in order to facilitate the dispersion and penetration of the colorant into the colorant carrier and the application to a substrate such as a glass substrate to form a filter segment.

[0069] Examples of organic solvents include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 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, m-Dichlorobenzene, N,N-Dimethylacetamide, N,N-Dimethylformamide, n-Butyl alcohol, n-Butylbenzene, n-Propyl acetate, o-Xylene, o-Chlorotoluene, o-Diethylbenzene, o-Dichlorobenzene, p-Chlorotoluene, p-Diethylbenzene, sec-Butylbenzene, tert-Butylbenzene, γ-Butyrolactone, Isobutyl alcohol, Isophorone, Ethylene glycol Diethylene glycol 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 monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether,Examples include dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

[0070] In particular, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone are preferred due to their good dispersion and dissolution of pigments. Especially from the viewpoint of safety and hygiene and achieving low viscosity, propylene glycol monomethyl ether acetate is more preferable.

[0071] These organic solvents can be used individually or in combination of two or more. When using a mixture of two or more solvents, it is preferable that the mixture contains 65 to 95% by mass of the preferred organic solvents mentioned above.

[0072] Furthermore, since the organic solvent can adjust the viscosity of the coloring composition to an appropriate level and form filter segments with the desired uniform film thickness, it is preferable to use it in an amount of 800 to 4000% by mass, based on the total weight of the coloring agent (100% by mass).

[0073] <Dispersion> The pigment composition of the present invention can be manufactured by finely dispersing the pigment in a colorant carrier made of a binder resin or the like, preferably together with a dispersion aid such as a dye derivative, using various dispersion methods such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. Alternatively, the colored composition of the present invention can also be manufactured by mixing pigments, dyes, other colorants, etc., that have been separately dispersed in a colorant carrier.

[0074] (Dispersing agent) When dispersing a colorant in a colorant carrier, dispersing aids such as dye derivatives, resin-type dispersants, and surfactants can be used as appropriate. Dispersing aids are excellent at dispersing colorants and have a significant effect in preventing the re-aggregation of the colorant after dispersion. Therefore, when a colored composition is used in which a colorant is dispersed in a colorant carrier using a dispersing aid, a film with high transmittance can be obtained.

[0075] Dye derivatives Examples of dye derivatives include compounds obtained by introducing a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group to an organic pigment, anthraquinone, acridone, or triazine. For example, those described in Japanese Patent Publication No. 63-305173, Japanese Patent Publication No. 57-15620, Japanese Patent Publication No. 59-40172, Japanese Patent Publication No. 63-17102, and Japanese Patent Publication No. 5-9469 can be used, and these can be used individually or in combination of two or more types. In the colored composition of the present invention, from the viewpoint of affinity with quinophthalone pigment (A), it is preferable to use a compound obtained by introducing a basic substituent or an acidic substituent to the quinophthalone pigment as the dye derivative.

[0076] From the viewpoint of improving the dispersibility of the added pigment, the amount of pigment derivative is preferably 0.5% by mass or more, more preferably 1% by mass or more, and most preferably 3% by mass or more, based on the total amount of added pigment (100% by mass). Furthermore, from the viewpoint of heat resistance and light resistance, the amount is preferably 40% by mass or less, and more preferably 35% by mass or less, based on the total amount of added pigment (100% by mass).

[0077] Resin-type dispersants Resin-type dispersants have a pigment affinity site that has the property of adsorbing to the added pigment and a site that is compatible with the colorant carrier, and function to stabilize the dispersion on the colorant carrier by adsorbing to the added pigment. Specifically, resin-type dispersants include polyurethane, polyacrylates and other polycarboxylic acid esters, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial)amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified versions thereof, oily dispersants such as amides and salts formed by the reaction of poly(lower alkyleneimines) with polyesters having free carboxyl groups, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide adduct compounds, and phosphate ester-based dispersants. These can be used individually or in combination of two or more, but are not necessarily limited to these.

[0078] Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 from BIC Chemie Japan. This includes Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS, or Bykumen, etc., as well as SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, manufactured by Lubrizol Japan. 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., and BASF Japan EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 440 Examples include 2, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., as well as Ajisper PA111, PB711, PB821, PB822, PB824, etc., manufactured by Ajinomoto Fine Techno Co., Ltd.

[0079] The resin-type dispersant preferably contains, for example, a resin-type dispersant having a carboxyl group, as described below (S1) or (S2). (S1) A resin-type dispersant which is a reaction product between the hydroxyl group of a polymer having a hydroxyl group and the acid anhydride group of a tricarboxylic acid anhydride and / or tetracarboxylic dianhydride. (S2) A resin-type dispersant which is a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product between the hydroxyl group of a compound having a hydroxyl group and the acid anhydride group of a tricarboxylic acid anhydride and / or a tetracarboxylic dianhydride.

[0080] [Resin-type dispersant (S1)] The resin-type dispersant (S1) can be produced by known methods such as those described in WO2008 / 007776, JP 2008-029901, and JP 2009-155406. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at its terminal end, and can be obtained, for example, as a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) in the presence of a compound (q) having a hydroxyl group. The compound (q) having a hydroxyl group is preferably a compound having both a hydroxyl group and a thiol group in its molecule. Since it is preferable to have multiple terminal hydroxyl groups, a compound (q1) having two hydroxyl groups and one thiol group in its molecule is particularly suitable.

[0081] In other words, a more preferred example is a polymer having two hydroxyl groups at one end, which can be obtained as a polymer (p1) by polymerizing an ethylenically unsaturated monomer (r) containing monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in its molecule. The hydroxyl groups of the polymer (p) with hydroxyl groups react with the acid anhydride groups of tricarboxylic acid anhydrides and / or tetracarboxylic dianhydrides to form ester bonds, while the anhydride ring opens to produce a carboxylic acid.

[0082] [Resin-type dispersant (S2)] The resin-type dispersant (S2) can be produced by known methods such as those described in Japanese Patent Publication No. 2009-155406, Japanese Patent Publication No. 2010-185934, and Japanese Patent Publication No. 2011-157416. For example, it can be obtained by polymerizing an ethylenically unsaturated monomer (r) in the presence of a reaction product between the hydroxyl group of a compound (q) having a hydroxyl group and the acid anhydride group of a tricarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride. In particular, it is preferable that the polymer is obtained by polymerizing an ethylenically unsaturated monomer (r) containing monomer (r1) in the presence of a reaction product between the hydroxyl group of a compound (q1) having two hydroxyl groups and one thiol group in its molecule and the acid anhydride group of a tricarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride.

[0083] The difference between (S1) and (S2) lies in whether the polymerized polymer moiety, formed by polymerizing the ethylenically unsaturated monomer (r), is introduced before or after the reaction. While molecular weight and other properties may differ slightly depending on various conditions, theoretically, the same product can be produced if the raw materials and reaction conditions are the same.

[0084] The amount of resin-type dispersant used is preferably 5 to 200 parts by mass, and more preferably 10 to 100 parts by mass, per 100 parts by mass of colorant. Using an appropriate amount further improves film formation.

[0085] Surfactants Examples of surfactants include anionic surfactants such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate; nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; and amphoteric surfactants such as alkyl betaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines. These can be used individually or in combination of two or more, but are not necessarily limited to these.

[0086] When adding resin-type dispersants and surfactants, the amount to be added is preferably 0.1 to 55% by mass, and more preferably 0.1 to 45% by mass, based on the total amount of added pigment (100% by mass). If the amount of resin-type dispersant and surfactant added is less than 0.1% by mass, the effect of the addition will not be easily obtained, and if the amount is greater than 55% by mass, the excessive amount of dispersant may adversely affect the dispersion.

[0087] <Photopolymerizable monomers> The colored composition of the present invention can be used as a photosensitive colored composition by further adding a photopolymerizable monomer and / or a photopolymerization initiator. The photopolymerizable monomer of the present invention includes monomers or oligomers that harden upon exposure to ultraviolet light or heat to produce a transparent resin, and these can be used alone or in combination of two or more. The amount of monomer added is preferably 5 to 50% by mass, based on the total weight of the colorant (100% by mass), and more preferably 10 to 30% by mass, from the viewpoint of photocurability and developability.

[0088] Examples of monomers and oligomers that harden upon exposure to ultraviolet light or heat to produce transparent resin include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, and bisphenol A diglycidyl Examples include, but are not limited to, ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, ester acrylate, (meth)acrylic acid esters of methylolated melamine, epoxy(meth)acrylate, urethane acrylate, and various other acrylic acid esters and methacrylic acid esters, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, acrylonitrile, etc.

[0089] <Photopolymerization initiator> The colored composition of the present invention can be prepared in the form of a solvent-developable or alkali-developable colored resist material by curing the composition by ultraviolet irradiation and forming filter segments by photolithography, by adding a photopolymerization initiator or the like. When using a photopolymerization initiator, the amount added is preferably 5 to 200% by mass, based on the total amount of colorant, and more preferably 10 to 150% by mass, from the viewpoint of photocurability and developability.

[0090] Examples of photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[ 4-(4-morpholinyl)phenyl]-1-butanone, or 2-benzyl-2-dimethyl Acetophenone compounds such as tylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl ) Benzophenone compounds such as benzophenone; thioxanthone compounds such as thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2- Triazine compounds such as piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio) Oxime ester compounds such as -,2-(O-benzoyl oxime) or O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxynaphthyl)ethylidene)hydroxylamine; phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds;Titanocene compounds, etc., are used.

[0091] These photopolymerization initiators can be used individually or mixed in any ratio of two or more as needed. Preferably, the amount is 5 to 200% by mass, and from the viewpoint of photocurability and developability... It is more preferable that the amount be between 10 and 150% by mass.

[0092] <Sensitizer> Furthermore, the coloring composition of the present invention may contain a sensitizer. Examples of sensitizers include polymethine dyes such as chalcone derivatives, unsaturated ketones represented by dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridine derivatives, azine derivatives, thiaidine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyradinoporphyrazine derivatives. Examples include phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxaliloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrillium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospilopyran derivatives, metal arene complexes, organoruthenium complexes, or Michler ketone derivatives, α-acyloxyesters, acylphosphine oxides, methylphenylglyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-diethylaminobenzophenone, and the like.

[0093] More specifically, examples include, but are not limited to, the sensitizers described in "Pigment Handbook" edited by Shin Okawara et al. (1986, Kodansha), "Chemistry of Functional Pigments" edited by Shin Okawara et al. (1981, CMC), and "Special Functional Materials" edited by Chuzaburo Ikemori et al. (1986, CMC). In addition, other sensitizers that exhibit absorption in the ultraviolet to near-infrared region can also be included.

[0094] Two or more sensitizers may be used in any ratio as needed. When using sensitizers, the amount added is preferably 3 to 60% by mass, based on the total weight (100% by mass) of the photopolymerization initiator contained in the coloring composition, and more preferably 5 to 50% by mass, from the viewpoint of photocurability and developability.

[0095] <Amine compounds> Furthermore, the coloring composition of the present invention may contain an amine compound that has the function of reducing dissolved oxygen. Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and N,N-dimethylparatoluidine.

[0096] <Leveling agent> In order to improve the leveling properties of the colored composition on a 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 polyester structure in the main chain is preferred. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning and BYK-333 manufactured by Bic Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by Bic Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can also be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by mass based on the total weight (100% by mass) of the colored composition.

[0097] Particularly preferred leveling agents are those that are a type of surfactant having both hydrophobic and hydrophilic groups in their molecule, and that have low solubility in water despite having hydrophilic groups, and have low surface tension reduction ability when added to a coloring composition, and furthermore, have good wettability to glass plates despite their low surface tension reduction ability, and that can sufficiently suppress electrostatic charge at an amount that does not cause defects in the coating film due to foaming, are preferably used. Dimethylpolysiloxane having polyalkylene oxide units is preferably used as a leveling agent having such desirable properties. Polyalkylene oxide units include polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxane may have both polyethylene oxide units and polypropylene oxide units.

[0098] Furthermore, the bonding configuration of the polyalkylene oxide units to dimethylpolysiloxane may be any of the following: a pendant type in which the polyalkylene oxide units are bonded to the repeating units of dimethylpolysiloxane; a terminally modified type in which they are bonded to the ends of dimethylpolysiloxane; or a linear block copolymer type in which they are alternately bonded to dimethylpolysiloxane in repeating units. Dimethylpolysiloxane having polyalkylene oxide units is commercially available from Toray Dow Corning Co., Ltd., and examples include, but is not limited to, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, and FZ-2207.

[0099] Leveling agents may also contain anionic, cationic, nonionic, or amphoteric surfactants as auxiliary agents. Two or more surfactants may be used in combination.

[0100] Examples of anionic surfactants added auxiliaryly to leveling agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate esters.

[0101] Cationic surfactants added as auxiliary components to leveling agents include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added as auxiliary components to leveling agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazolines, and fluorine-based and silicone-based surfactants.

[0102] <Hardening agents, curing accelerators> Furthermore, the colored composition of the present invention may optionally contain a curing agent, a curing accelerator, etc., to assist in the curing of the thermosetting resin. Effective curing agents include phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc., but are not limited to these, and any curing agent that can react with the thermosetting resin may be used. Among these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are particularly preferred. Examples of the curing accelerators include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenyl You can use midazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc., phosphorus compounds (e.g., triphenylphosphine, etc.), guanamine compounds (e.g., melamine, guanamine, acetoguanamine, benzoguanamine, etc.), or S-triazine derivatives (e.g., 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.). These may be used individually or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15% by mass relative to the total amount of thermosetting resin.

[0103] <Other additive ingredients> The colored composition of the present invention may contain a storage stabilizer to stabilize the viscosity of the composition over time. It may also contain an adhesion enhancer, such as a silane coupling agent, to improve adhesion to a transparent substrate.

[0104] Examples of storage stabilizers include benzyl trimethyl chloride, quaternary ammonium chlorides such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butyl pyrocatechol, tetraethylphosphine, and tetraphenylphosphine, and phosphates. The storage stabilizer can be used in an amount of 0.1 to 10% by mass, based on the total amount of the coloring agent (100% by mass).

[0105] Examples of adhesion enhancers include vinylsilanes such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, and vinyltrimethoxysilane; (meth)acryloxysilanes such as γ-methacryloxypropyltrimethoxysilane; β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; β-(3,4-epoxycyclohexyl)methyltrimethoxysilane; β-(3,4-epoxycyclohexyl)ethyltriethoxysilane; β-(3,4-epoxycyclohexyl)methyltriethoxysilane; γ-glycidoxypropyltrimethoxysilane; γ-glycidoxypropyltriethoxy Examples of silane coupling agents include epoxysilanes such as silane, aminosilanes such as N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and N-phenyl-γ-aminopropyltriethoxysilane, as well as thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion enhancer can be used in an amount of 0.01 to 10% by mass, preferably 0.05 to 5% by mass, based on the total amount of colorant in the colored composition (100% by mass).

[0106] <Removal of coarse particles> The colored composition of the present invention is preferably subjected to the removal of coarse particles of 5 μm or larger, preferably 1 μm or larger, and more preferably 0.5 μm or larger, as well as any mixed dust, by means of centrifugation, sintering filters, membrane filters, etc. Thus, the colored composition is preferably substantially free of particles of 0.5 μm or larger. More preferably, the particles are 0.3 μm or smaller.

[0107] <Color Filter> The color filter comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment. Furthermore, in addition to the above three color filter segments, it may also comprise a yellow filter segment. At least one of the red filter segment, the green filter segment, and the yellow filter segment is formed using the coloring composition of the present invention.

[0108] The blue filter segment can be formed using a conventional blue coloring composition containing a blue colorant and a colorant carrier. Examples of blue colorants include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, and aluminum phthalocyanine pigments described in Japanese Patent Publication No. 2004-333817 and Japanese Patent No. 4893859. In addition, a purple colorant can be used in combination with the blue coloring composition. Examples of purple colorants that can be used in combination include CI 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, 37, 39, 40, 42, 44, 47, 49, and 50. Additionally, salt-forming compounds of basic dyes and acid dyes that exhibit blue or purple colors can be used. When using dyes, triarylmethane dyes or xanthene dyes are preferred in terms of brightness.

[0109] <How to manufacture color filters> A color filter containing the coloring composition of the present invention can be manufactured by printing or photolithography.

[0110] The formation of filter segments by the printing method is low-cost and highly productive for mass production of color filters, as it allows for patterning simply by repeatedly printing and drying a colored composition containing the colored composition of the present invention, which has been prepared as a printing ink. Furthermore, advances in printing technology enable the printing of fine patterns with high dimensional accuracy and smoothness. For printing, it is preferable to have a composition that prevents the ink from drying or solidifying on the printing plate or blanket. Controlling the fluidity of the ink on the printing press is also important, and the ink viscosity can be adjusted using dispersants or extender pigments.

[0111] When forming filter segments by photolithography, a photosensitive colored composition containing a blue colored composition prepared as a solvent-developable or alkali-developable colored resist is applied to a transparent substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating, so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern, either in contact with or without contact with the film. After that, the uncured areas are removed by immersion in a solvent or alkaline developer or by spraying the developer, and the desired pattern is formed. The same operation can then be repeated for other colors to manufacture color filters. Furthermore, heating can be applied as necessary to promote polymerization of the colored resist material. Photolithography allows for the manufacture of color filters with higher precision than the printing method described above.

[0112] For development, aqueous solutions of sodium carbonate, sodium hydroxide, etc., are used as alkaline developers, and organic base compounds such as dimethylbenzylamine and triethanolamine can also be used. Furthermore, defoaming agents and surfactants may be added to the developer. In order to increase the sensitivity to ultraviolet exposure, after coating and drying the above-mentioned colored resist material, a water-soluble or alkaline water-soluble resin, such as polyvinyl alcohol or water-soluble acrylic resin, may be coated and dried to form a film that prevents polymerization inhibition by oxygen, and then ultraviolet exposure may be performed.

[0113] Color filters containing the colored composition of the present invention can also be manufactured by methods other than those described above, such as electrodeposition and transfer. The electrodeposition method involves using a transparent conductive film formed on a substrate to electrodeposit each color filter segment onto the transparent conductive film by electrophoresis of colloidal particles. The transfer method involves forming filter segments on the surface of a peelable transfer base sheet in advance and then transferring these filter segments to a desired substrate.

[0114] A black matrix can be formed before each color filter segment is formed on a transparent or reflective substrate. The black matrix can be, but is not limited to, a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film with a dispersed light-shielding agent. Alternatively, thin-film transistors (TFTs) can be formed on the transparent or reflective substrate before each color filter segment is formed. Furthermore, an overcoat film or a transparent conductive film may be formed on the color filter as needed. [Examples]

[0115] The present invention will be described below based on examples, but the present invention is not limited to these examples. In the examples, "parts" and "%" represent "parts by mass" and "mass%", respectively.

[0116] (Mass-average molecular weight (Mw) of the resin) The mass-average molecular weight (Mw) of the resin is the polystyrene-represented mass-average molecular weight (Mw) measured using a TSKgel column (Tosoh Corporation) and a GPC (Tosoh Corporation, HLC-8120GPC) equipped with an RI detector, with THF as the developing solvent.

[0117] <Method for producing binder resin solution> (Preparation of acrylic resin 1) A reaction vessel was prepared by fitting a thermometer, condenser, nitrogen gas inlet, dropping tube, and stirrer into a separable four-neck flask. 196 parts of cyclohexanone were charged into the vessel, and the temperature was raised to 80°C. After purging the reaction vessel with nitrogen, a mixture of 37.2 parts n-butyl methacrylate, 12.9 parts 2-hydroxyethyl methacrylate, 12.0 parts methacrylic acid, 20.7 parts paracumylphenol ethylene oxide modified acrylate (Toagosei Co., Ltd. "Aronics M110"), and 1.1 parts 2,2'-azobisisobutyronitrile was added dropwise over 2 hours via the dropping tube. After the addition was complete, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution were sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Methoxypropyl acetate was added to the previously synthesized resin solution to achieve a non-volatile content of 20% to prepare acrylic resin 1. The mass-average molecular weight (Mw) was 26,000.

[0118] (Preparation of acrylic resin 2) A reaction vessel was prepared by fitting a thermometer, condenser, nitrogen gas inlet, dropping tube, and stirrer into a separable four-neck flask. 207 parts of cyclohexanone were charged into this vessel, and the temperature was raised to 80°C. After purging the reaction vessel with nitrogen, a mixture of 20 parts methacrylic acid, 20 parts paracumylphenol ethylene oxide-modified acrylate (Aronics M110, manufactured by Toagosei Co., Ltd.), 45 parts methyl methacrylate, 8.5 parts 2-hydroxyethyl methacrylate, and 1.33 parts 2,2'-azobisisobutyronitrile was added dropwise over 2 hours via the dropping tube. After the dropwise addition was complete, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the entire copolymer solution was stirred while injecting dry air for 1 hour after stopping the nitrogen gas supply. After cooling to room temperature, a mixture of 6.5 parts 2-methacryloyloxyethyl isocyanate (Kalenz MOI, Showa Denko Co., Ltd.), 0.08 parts dibutyltin laurate, and 26 parts cyclohexanone was added dropwise at 70°C for 3 hours. After the dropwise addition was complete, the reaction was continued for another hour to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution were sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Cyclohexanone was then added to the previously synthesized resin solution to prepare acrylic resin 2, with a non-volatile content of 20%. The mass-average molecular weight (Mw) was 18000.

[0119] <Manufacturing of resin-type dispersants> (Preparation of Dispersant 1) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 70 parts methyl methacrylate, 20 parts t-butyl methacrylate, and 10 parts methacrylic acid were charged and purged with nitrogen gas. The reaction vessel was heated to 80°C, 6.0 parts 1-thioglycerol were added, and the mixture was reacted for 12 hours. Solid content measurement confirmed that 95% had reacted. Next, 8.5 parts pyromellitic anhydride, 115 parts propylene glycol monomethyl ether acetate (PGMAc), and 0.20 parts 1,8-diazabicyclo-[5.4.0]-7-undecene (DBU) as a catalyst were added, and the mixture was reacted at 100°C for 7 hours. Acid value measurement confirmed 98 After confirming that more than % of the acid anhydride has been half-esterified, terminate the reaction, and dilute with propylene glycol monomethyl ether acetate to a non-volatile content of 40%. Dispersant 1 with an acid value of 100 mg KOH / g and a weight-average molecular weight of 9000 was obtained.

[0120] (Preparation of Dispersant 2) In a flask equipped with a condenser and a stirrer, 1.0 part by mass of AIBN (2,2'-azobisisobutyronitrile) and 186 parts by mass of propylene glycol monomethyl ether acetate were charged. Subsequently, 27 parts by mass of methyl methacrylate, 27 parts by mass of butyl methacrylate, 21 parts by mass of 2-ethylhexyl methacrylate, 18 parts by mass of benzyl methacrylate, and 3.6 parts by mass of cumyl dithiobenzoate were charged, and the mixture was purged with nitrogen for 30 minutes. The mixture was then gently stirred to raise the temperature of the reaction solution to 60°C, and this temperature was maintained for 24 hours to carry out living radical polymerization. Next, to this reaction solution, a solution in which 1.0 part by mass of AIBN and 35 parts by mass of dimethylaminoethyl methacrylate were dissolved in 70 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen for 30 minutes was added, and living radical polymerization was carried out at 60°C for 24 hours to obtain a block copolymer solution. To the obtained block copolymer solution, add 25 parts by mass of benzyl chloride and 50 parts by mass of propylene glycol monomethyl ether, and react at 80°C for 2 hours to adjust the solid content concentration to 40%. Dispersant 2 was obtained by this method. Resin-type dispersant 2 is a block copolymer consisting of block A having repeating units derived from methacryloyloxyethylbenzyldimethylammonium chloride and dimethylaminoethyl methacrylate, and block B having repeating units derived from methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and benzyl methacrylate. Proton NMR measurement revealed that the copolymerization ratio of each repeating unit was methacryloyloxyethylbenzyldimethylammonium chloride / dimethylaminoethyl methacrylate / methyl methacrylate / butyl methacrylate / 2-ethylhexyl methacrylate / benzyl methacrylate = 34 / 4 / 18 / 18 / 14 / 12 (mass ratio).

[0121] <Manufacturing of quinophthalone pigment (A)> (Synthesis of quinophthalone pigment (A-1)) 15.9 parts of 8-hydroxy-2-methylquinoline, 21.6 parts of 2,3-naphthalenedicarboxylic acid, 30 parts of benzoic acid, and 7.5 parts of methyl benzoate were mixed and heated to 200°C. After heating and stirring for 3 hours, the mixture was allowed to cool to 70°C and 100 parts of methanol were added. After stirring at room temperature for 30 minutes, the mixture was filtered and washed with methanol. The mixture was dried under reduced pressure overnight to obtain 23 parts of the following quinophthalone pigment (A-1).

[0122] (Synthesis of quinophthalone pigment (A-2)) Quinophthalone pigment (A-2) was synthesized in 24 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 20.0 parts of 8-acetamido-2-methylquinoline.

[0123] (Synthesis of quinophthalone pigment (A-3)) Quinophthalone pigment (A-3) was synthesized in 27.3 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 26.2 parts of 8-benzamido-2-methylquinoline.

[0124] (Synthesis of quinophthalone pigment (A-4)) Quinophthalone pigment (A-4) was synthesized in 30.2 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 29.7 parts of 5-chloro-8-benzamide-2-methylquinoline.

[0125] (Synthesis of quinophthalone pigment (A-5)) Quinophthalone pigment (A-5) was synthesized in 29.7 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 26.2 parts of 8-benzamido-2-methylquinoline and 21.6 parts of 2,3-naphthalenedicarboxylic acid were replaced with 23.3 parts of 6-chloro-2,3-naphthalenedicarboxylic acid.

[0126] (Synthesis of quinophthalone pigment (A-6)) Quinophthalone pigment (A-6) was synthesized in 38.2 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 40.0 parts of 8-(2,3,4,5-tetrachlorobenzamide)-2-methylquinoline.

[0127] (Synthesis of quinophthalone pigment (A-7)) Quinophthalone pigment (A-7) was synthesized in 29.7 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 30.7 parts of 8-(4-nitrobenzamide)-2-methylquinoline.

[0128] [ka]

[0129] (Synthesis of quinophthalone pigment (A-8)) Quinophthalone pigment (A-8) was synthesized in 26.2 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 23.6 parts of 8-methanesulfonamide-2-methylquinoline.

[0130] (Synthesis of quinophthalone pigment (A-9)) Quinophthalone pigment (A-9) was synthesized in 27.8 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 29.8 parts of 8-phenylsulfonamide-2-methylquinoline.

[0131] (Synthesis of quinophthalone pigment (A-10)) Quinophthalone pigment (A-10) was synthesized in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 34.3 parts of 8-(4-nitrophenyl)methanesulfonamide-2-methylquinoline.

[0132] (Synthesis of quinophthalone pigment (A-11)) Quinophthalone pigment (A-11) was synthesized in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 40.1 parts of 8-(2,4,5-trichlorophenyl)sulfonamide-2-methylquinoline.

[0133] [ka]

[0134] (Synthesis of quinophthalone pigment (A-12)) Quinophthalone pigment (A-12) was synthesized in 30.3 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 29.6 parts of 8-(4-chlorobenzamide)-2-methylquinoline.

[0135] (Synthesis of quinophthalone pigment (A-13)) Quinophthalone pigment (A-13) was synthesized in 34 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 34.1 parts of 8-(4-bromobenzamide)-2-methylquinoline.

[0136] (Synthesis of quinophthalone pigment (A-14)) Quinophthalone pigment (A-14) was synthesized in 36.9 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 35.2 parts of 8-(3,5-dinitrobenzamide)-2-methylquinoline.

[0137] (Synthesis of quinophthalone pigment (A-15)) Quinophthalone pigment (A-15) was synthesized in 33 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 31.2 parts of 8-(1-naphthoylamino)-2-methylquinoline.

[0138] (Synthesis of quinophthalone pigment (A-16)) Quinophthalone pigment (A-16) was synthesized in 38.8 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 39.1 parts of 5-bromo-8-(1-naphthoylamino)-2-methylquinoline.

[0139] (Synthesis of quinophthalone pigment (A-17)) Quinophthalone pigment (A-17) was synthesized in 34.8 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 34.7 parts of 5-chloro-8-(1-naphthoylamino)-2-methylquinoline.

[0140] (Synthesis of quinophthalone pigment (A-18)) Quinophthalone pigment (A-18) was synthesized in 33.8 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 31.2 parts of 8-(2-naphthoylamino)-2-methylquinoline.

[0141] (Synthesis of quinophthalone pigment (A-19)) 35 parts of the following quinophthalone pigment (A-19) were synthesized in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 39.1 parts of 8-(2-(6-bromonaphthoylamino))-2-methylquinoline.

[0142] (Synthesis of quinophthalone pigment (A-20)) Quinophthalone pigment (A-20) was synthesized in 33.2 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 34.7 parts of 8-(2-(6-chloronaphthoylamino))-2-methylquinoline.

[0143] (Synthesis of quinophthalone pigment (A-21)) Quinophthalone pigment (A-21) was synthesized in 34.6 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 38.6 parts of 8-(1-pyrenoylamino)-2-methylquinoline.

[0144] (Synthesis of quinophthalone pigment (A-22)) 37 parts of the following quinophthalone pigment (A-22) were synthesized in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 36.2 parts of 8-(9-anthracenylamino)-2-methylquinoline.

[0145] (Synthesis of quinophthalone pigment (A-23)) Quinophthalone pigment (A-23) was synthesized in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 43 parts of 8-(4-(N,N-diphenyl)benzamide)-2-methylquinoline.

[0146] (Synthesis of quinophthalone pigment (A-24)) Quinophthalone pigment (A-24) was synthesized in 33.7 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 35 parts of 8-(9-fluorenylcarbonylamino)-2-methylquinoline.

[0147] (Synthesis of quinophthalone pigment (A-25)) Quinophthalone pigment (A-25) was synthesized in 35.9 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 35.1 parts of 8-(9-carbazoloylamino)-2-methylquinoline.

[0148] (Synthesis of quinophthalone pigment (A-26)) Quinophthalone pigment (A-26) was synthesized in 34.6 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 36.6 parts of 8-(9-xanthenoylamino)-2-methylquinoline.

[0149] (Synthesis of quinophthalone pigment (A-27)) Quinophthalone pigment (A-27) was synthesized in 36.2 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 36.4 parts of 8-(2-(9-fluorenone carbonylamino))-2-methylquinoline.

[0150] (Synthesis of quinophthalone pigment (A-28)) Quinophthalone pigment (A-28) was synthesized in 37.2 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 36.4 parts of 8-(1-(9-fluorenone carbonylamino))-2-methylquinoline.

[0151] (Synthesis of quinophthalone pigment (A-29)) Quinophthalone pigment (A-29) was synthesized in 30.3 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 31.3 parts of 8-(2-quinolylcarbonylamino)-2-methylquinoline.

[0152] (Synthesis of quinophthalone pigment (A-30)) Quinophthalone pigment (A-30) was synthesized in 31.8 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 31.9 parts of 8-(5-benzothiazolylcarbonylamino)-2-methylquinoline.

[0153] (Synthesis of quinophthalone pigment (A-31)) Quinophthalone pigment (A-31) was synthesized in 30.4 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 30.1 parts of 8-(3-indolylcarbonylamino)-2-methylquinoline.

[0154] (Synthesis of quinophthalone pigment (A-32)) Quinophthalone pigment (A-32) was synthesized in 42.7 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 44.1 parts of 5-bromo-8-(9-anthracenylamino)-2-methylquinoline.

[0155] (Synthesis of quinophthalone pigment (A-33)) Quinophthalone pigment (A-33) was synthesized in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 42.9 parts of 8-(2,2,2-triphenylacetamide)-2-methylquinoline.

[0156] (Synthesis of quinophthalone pigment (A-34)) Quinophthalone pigment (A-34) was synthesized in 38.2 parts in the same manner as quinophthalone pigment (A-24), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 39.1 parts of 5-bromo-8-(1-naphthoylamino)-2-methylquinoline.

[0157] (Synthesis of quinophthalone pigment (A-35)) Quinophthalone pigment (A-34) was synthesized in 38.2 parts in the same manner as quinophthalone pigment (A-24), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 34.7 parts of 5-chloro-8-(1-naphthoylamino)-2-methylquinoline.

[0158] [ka] [ka] [ka] [ka]

[0159] <Manufacturing of comparative quinophthalone pigment (AA)> (Synthesis of quinophthalone pigment (AA-1)) Quinophthalone pigment (AA-1) was synthesized in 23.1 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 17.3 parts of 8-methoxy-2-methylquinoline.

[0160] (Synthesis of quinophthalone pigment (AA-2)) Quinophthalone pigment (AA-2) 31.3 parts were synthesized in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 26.2 parts of 8-benzamido-2-methylquinoline and 21.6 parts of 2,3-naphthalenedicarboxylic acid were replaced with 18.3 parts of phthalic anhydride.

[0161] (Synthesis of quinophthalone pigment (AA-3)) Quinophthalone pigment (AA-3) was synthesized in 30.3 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 26.2 parts of 8-benzamido-2-methylquinoline and 21.6 parts of 2,3-naphthalenedicarboxylic acid were replaced with 14.8 parts of 3-chlorophthalic anhydride.

[0162] (Synthesis of quinophthalone pigment (AA-4)) Quinophthalone pigment (AA-4) was synthesized in 32.9 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 26.2 parts of 8-benzamido-2-methylquinoline and 21.6 parts of 2,3-naphthalenedicarboxylic acid were replaced with 28.6 parts of 3,4,5,6-tetrachlorophthalic anhydride.

[0163] (Synthesis of quinophthalone pigment (AA-5)) Quinophthalone pigment (AA-5) was synthesized in 38.2 parts in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 26.2 parts of 8-(4-nitrobenzamide)-2-methylquinoline and 21.6 parts of 2,3-naphthalenedicarboxylic acid were replaced with 28.6 parts of 3,4,5,6-tetrachlorophthalic anhydride.

[0164] (Synthesis of quinophthalone pigment (AA-6)) Quinophthalone pigment (AA-6) was synthesized in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 29.8 parts of 8-phenylsulfonamide-2-methylquinoline and 21.6 parts of 2,3-naphthalenedicarboxylic acid were replaced with 28.6 parts of 3,4,5,6-tetrachlorophthalic anhydride.

[0165] (Synthesis of quinophthalone pigment (AA-7)) Quinophthalone pigment (AA-7) was synthesized in the same manner as quinophthalone pigment (A-1), except that 15.9 parts of 8-hydroxy-2-methylquinoline were replaced with 34.3 parts of 8-(4-nitrophenyl)sulfonamide-2-methylquinoline and 21.6 parts of 2,3-naphthalenedicarboxylic acid were replaced with 28.6 parts of 3,4,5,6-tetrachlorophthalic anhydride.

[0166] [ka]

[0167] (Manufacturing of quinophthalone micronized pigment (A-1K)) 100 parts of quinophthalone pigment (A-1), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 8 hours. Next, this mixture was added to warm water and stirred for 1 hour while heating to approximately 70°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight to obtain 97 parts of finely ground quinophthalone pigment (A-1K).

[0168] (Manufacturing of finely milled quinophthalone pigments (A-1K) to (A-35K), and comparative finely milled quinophthalone pigments (AA-1K) to (AA-7K)) Except for changing the quinophthalone pigment used to those shown in Table 1, quinophthalone micronized pigments (A-2K) to (A-35K) and comparative quinophthalone micronized pigments (AA-1K) to (AA-7K) were obtained in the same manner as for quinophthalone micronized pigment (A-1K).

[0169] [Table 1]

[0170] (Manufacturing of quinophthalone micronized pigment (A-1S)) 100 parts of quinophthalone pigment (A-1) and 5000 parts of xylene were placed in a flask and kneaded at room temperature for 8 hours. Next, this mixture was added to water and stirred for 1 hour to form a slurry. After removing the xylene by repeated filtration and washing with water, it was dried at 80°C overnight to obtain 97 parts of finely ground quinophthalone pigment (A-1S).

[0171] (Particle size measurement) The average primary particle size of quinophthalone pigments (A-3), (A-7), finely milled quinophthalone pigments (A-1K) to (A-35K), (A-1S), and comparative finely milled quinophthalone pigments (AA-1K) to (AA-7K) was determined by TEM (transmission electron microscopy). The values ​​are shown in Table 2. Quinophthalone pigments (A-3) and (A-7) are crude pigments obtained during the synthesis process.

[0172] Here, the average primary particle size of the pigment is measured using a transmission electron microscope (JEOL Ltd. "JEM-1200"). Using an EX (Extraction Generator), the primary particle diameter of all pigment particles in the observed sample at 50,000x magnification was measured, and the average value was calculated. If the particle shape was not spherical, the major and minor axes were measured, and the value obtained by (major axis + minor axis) / 2 was used as the particle diameter.

[0173] [Table 2]

[0174] <Manufacturing of quinophthalone derivatives> (Synthesis of quinophthalone derivative (DA-1)) 26 parts of quinophthalone pigment (A-3) were dissolved in a mixture of 214 parts of 98% sulfuric acid and 236 parts of 25% fuming sulfuric acid, and the mixture was stirred at 85°C for 2 hours to carry out the sulfonation reaction. Next, this reaction solution was added dropwise to 3000 parts of ice water, and the precipitated compound was filtered off and washed with water to obtain a paste. The obtained paste was redispersed in 8000 parts of water and stirred at room temperature for 1 hour. After filtration and washing with water, it was dried at 80°C overnight to obtain 26 parts of quinophthalone derivative (DA-1) (yield: 89%). Mass spectrometry and elemental analysis by TOF-MS identified the compound as quinophthalone derivative (DA-1).

[0175] (Synthesis of quinophthalone derivative (DB-1)) 25 parts of quinophthalone derivative (DA-1) were added to 300 parts of chloroform, and under ice cooling, 4.4 parts of oxalyl chloride and 1 part of N,N-dimethylformamide were added and the mixture was stirred at 50°C for 2 hours. The reaction mixture was added to 500 parts of water in an ice bath, and the precipitated crystals were filtered to obtain 23 parts of the following quinophthalone compound (DA-1C) (yield: 91%).

[0176] Next, 18 parts of the quinophthalone compound (DA-1C) were added to 200 parts of chloroform, and 3.3 parts of diethylaminoethylamine were added under ice cooling. The mixture was stirred at room temperature for 2 hours. The reaction mixture was added to 350 parts of water, the precipitated crystals were filtered and washed with water, and dried at 80°C overnight to obtain 18 parts of the quinophthalone derivative (DB-1) (yield: 89%). Mass spectrometry and elemental analysis by TOF-MS identified the following quinophthalone derivative (DB-1).

[0177] [ka]

[0178] <Manufacturing of finely milled yellow pigment> (Manufacturing of yellow fine pigment (PY-1)) Isoindoline-based yellow pigment CI Pigment Yellow 138 (BASF "Paliotol Yellow K 0961HD") 200 units, sodium chloride 140 0 parts of sodium chloride and 360 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. Next, this mixture was added to 8 liters of warm water and stirred for 2 hours while heating to 80°C to form a slurry. After filtering and repeatedly washing with water to remove sodium chloride and diethylene glycol, the slurry was dried at 85°C overnight to obtain a yellow fine pigment (PY-1).

[0179] (Manufacturing of yellow fine pigment (PY-2)) 200 parts of isoindoline-based yellow pigment CI Pigment Yellow 150 (CLARIANT's "Hostaperm Yellow HN4G"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. Next, this mixture was added to 8 liters of warm water and stirred for 2 hours while heating to 80°C to form a slurry. After filtering and repeatedly washing with water to remove sodium chloride and diethylene glycol, the slurry was dried at 85°C overnight to obtain finely milled yellow pigment (PY-2).

[0180] (Manufacturing of yellow fine pigment (PY-3)) 200 parts of isoindoline-based yellow pigment CI Pigment Yellow 185 (BASF's "Paliotol Yellow D 1155"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. Next, this mixture was added to 8 liters of warm water and stirred for 2 hours while heating to 80°C to form a slurry. After filtering and repeatedly washing with water to remove sodium chloride and diethylene glycol, the slurry was dried at 85°C overnight to obtain finely milled yellow pigment (PY-3).

[0181] (Manufacturing of yellow fine pigment (PY-4)) 200 parts of isoindoline-based yellow pigment CI Pigment Yellow 139 (BASF's "Paliotol Yellow L 2146HD"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. Next, this mixture was added to 8 liters of warm water and stirred for 2 hours while heating to 80°C to form a slurry. After filtering and repeatedly washing with water to remove sodium chloride and diethylene glycol, the slurry was dried at 85°C overnight to obtain finely milled yellow pigment (PY-4).

[0182] <Manufacturing of green micronized pigment> (Manufacturing of green micropigment (PG-1)) 200 parts of phthalocyanine-based green pigment CI Pigment Green 36 (CLARIANT's "Green8G"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. Next, this mixture was added to 8000 parts of warm water and stirred for 2 hours while heating to 80°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 85°C overnight to obtain finely ground green pigment (PG-1).

[0183] (Manufacturing of green micropigment (PG-2)) 200 parts of phthalocyanine-based green pigment CI Pigment Green 58 (DIC Corporation's "FASTOGEN GREEN A110"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. Next, this mixture was added to 8000 parts of warm water and stirred for 2 hours while heating to 80°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 85°C overnight to obtain finely ground green pigment (PG-2).

[0184] <Manufacturing of coloring compositions> (Example 1) After stirring and mixing the mixture with the following composition until homogeneous, the mixture was dispersed for 5 hours using 0.5 mm diameter zirconia beads in an Eiger mill (Eiger Japan's "Mini Model M-250 MKII"), and then filtered through a 5.0 μm pore size filter to prepare a yellow colored composition (Y-1). Quinophthalone micronized pigment (A-1K) 21.6 parts Quinophthalone derivative (DB-1) 2.4 parts Dispersant 1 36.0 parts Acrylic resin 1 8.0 parts Propylene glycol monomethyl ether acetate (PGMAc) 132.0 parts

[0185] (Examples 2-40, Comparative Examples 1-11) Yellow colored compositions (Y-2) to (Y-51) were obtained in the same manner as in Example 1, as shown in Table 3. The pigment concentration of the yellow coloring compositions (Y-1) to (Y-51) is 60%. The yellow colored compositions (Y-15) and (Y-16) used quinophthalone pigments (A-3) and (A-7), respectively, which are crude pigments obtained during the synthesis stage. Furthermore, since the quinophthalone pigment (A-1) has a hydroxyl group at the 8th position of the quinoline ring, it is preferable to treat it with a solvent. In its newly synthesized state, it adopts an α-type crystalline structure, but treatment with a solvent such as N-methylpyrrolidone or xylene causes it to adopt a β-type crystalline structure. Therefore, (A-1K) in Example 1 has been treated with salt milling and adopts an α-type crystalline structure, while the quinophthalone micronized pigment (A-1S) in Example 2 has been treated with a solvent and adopts a β-type crystalline structure.

[0186] [Table 3] [Table 3]

[0187] Next, acrylic resin 2 was added to the yellow coloring compositions (Y-1) to (Y-51) as shown below to dilute them and prepare a coating solution. Yellow coloring composition 100.0 parts Acrylic resin 2 50.0 parts

[0188] The coating solution obtained by diluting the yellow coloring compositions (Y-1) to (Y-51) was applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater under conditions that resulted in a film thickness of 1.0 μm. The film was then dried at 70°C for 20 minutes, and its absorption spectrum was measured using a spectrophotometer (Hitachi "U-4100").

[0189] (Evaluation of coloring power) For the above film, the maximum absorbance in the 450-500 nm range (simply referred to as "maximum absorbance" in Table 3) was determined. The criteria for evaluation are as follows. 2.3 or higher: ○++ 2.0 or higher and less than 2.3: ○+ 1.7 or higher and less than 2.0: ○ 1.6 or higher but less than 1.7: △ Less than 1.6: ×

[0190] (Evaluation of heat resistance) The above film was subjected to a heat treatment at 230°C for 20 minutes, and a heat resistance test was conducted. The change in the maximum absorbance value between 450 and 500 nm was determined as follows. A decrease of less than 10%: ○+ A decrease rate of 10% or more but less than 20%: ○ Decrease rate of 20% or more: ×

[0191] (Evaluation of transmittance) Next, the yellow coloring compositions (Y-1) to (Y-51) were applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater under the condition that the maximum absorbance at 450 to 500 nm was 2.0, and then dried at 70°C for 20 minutes. The transmittance spectrum was measured with a spectrophotometer (Hitachi's "U-4100"), and the transmittance at 550 nm was determined. The criteria for judgment are as follows. 97% or more: 〇+ 95% or more and less than 97%: 〇 Less than 95%: × Note that the following equation holds for the absorbance Trs(%) and transmittance Abs of the coating film. Trs / 100 = 0.1 (Abs) In a certain wavelength range, at the wavelength where the absorbance is maximum, the transmittance at that wavelength is the minimum within that range. That is, when the absorbance value is 2.0 at the wavelength X where the absorbance is maximum at 450 to 500 nm then the transmittance at that wavelength X is the minimum value within the range of 450 to 500 nm and is 1%. <Method for producing green coloring composition> (Example 41) After stirring and mixing the mixture of the following composition to be uniform, it was dispersed for 5 hours using zirconia beads with a diameter of 0.5 mm in an attritor mill (Mini Model M-250 MKII manufactured by Eiger Japan Co., Ltd.), and then filtered through a filter with a pore size of 5.0 μm to prepare a green coloring composition (G-1). Quinophthalone micronized pigment (A-1K) 5.4 parts Quinophthalone derivative (DA-1) 0.6 parts Green micronized pigment (PG-1) 18.0 parts Dispersant 2 36.0 parts Acrylic resin 1 8.0 parts Propylene glycol monomethyl ether acetate (PGMAc) 132.0 parts The pigment concentration of the green coloring composition (G-1) was set to 60%.

[0192] (Examples 42 to 75, Comparative Examples 12 to 22) In the same manner as in Example 1, as shown in Table 4, green coloring compositions (G-2) to (G-48) were obtained. The pigment concentration of the green coloring compositions (G-2) to (G-48) was set to 60%.

[0193]

Table 4

Table 4

[0194] Next, Acrylic Resin 2 was added to the green coloring compositions (G-1) to (G-48) and diluted as follows to prepare coating liquids. Green coloring composition: 100.0 parts Acrylic Resin 2: 50.0 parts The pigment concentration of the obtained coating liquid was 40%.

[0195] The coating liquids obtained by diluting the green coloring compositions (G-1) to (G-48) were applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater under the condition that the maximum absorbance at 450 - 500 nm was 2.0, and then dried at 70 °C for 20 minutes to obtain films.

[0196] (Evaluation of coloring power by film thickness measurement) The film thickness of the obtained films was measured to determine the coloring power. Since the maximum absorbance at 450 - 500 nm of each film was 2.0, the thinner the film thickness, the better the coloring power with a small amount of pigment. Less than 2.9 μm: 〇++ 2.9 μm or more and less than 3.2 μm: 〇+ 3.2 μm or more and less than 3.7 μm: 〇 3.7 μm or more and less than 3.8 μm: △ 3.8 μm or more: ×

[0197] (Evaluation of heat resistance) The above substrate was heat-treated at 230°C for 20 minutes, and a heat resistance test was conducted. Judgment was made on the change in the maximum value of the absorbance at 450 nm to 500 nm. Reduction rate less than 10%: 〇+ Reduction rate 10% or more and less than 20%: 〇 Reduction rate 20% or more: ×

[0198] (Evaluation of transmittance) The transmittance of the above substrate at 550 nm was measured by the same method as above, and judgment was made. 93% or more: 〇+ 92% or more and less than 93%: 〇 Less than 92%: ×

[0199] (Preparation of photosensitive green coloring composition) (Example 76) After stirring and mixing the mixture of the following composition to be uniform, it was filtered through a filter with a pore size of 1 μm to prepare a photosensitive coloring composition (GR-1). Green coloring composition (G-1) 100.0 parts Acrylic resin solution 2 10.0 parts Photopolymerizable monomer ("Aronix M402" manufactured by Toagosei Co., Ltd.) 5.5 parts Photoinitiator ("Irgacure OXE02" manufactured by BASF) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.5 parts Propylene glycol monomethyl ether acetate 32.0 parts

[0200] (Examples 77 to 112, Comparative Examples 23 to 25) As shown in Table 5, photosensitive coloring compositions (GR-2 to 16, GR-25 to 48) were prepared in the same manner as the photosensitive coloring composition (GR-1).

[0201]

Table 5

Table 5

[0202] A photosensitive green colored composition was applied to a 100mm x 100mm, 1.1mm thick glass substrate using a spin coater under conditions that resulted in a maximum absorbance of 2.0 between 450nm and 500nm. The substrate was then dried at 70°C for 20 minutes, and a high-pressure mercury lamp was used to apply 300mJ / cm² of mercury. 2 The images were exposed to ultraviolet light and developed using an alkaline developer at 23°C. The solution used consisted of 1.5% by mass of sodium carbonate, 0.5% by mass of sodium bicarbonate, 8.0% by mass of an anionic surfactant (Perilex NBL, manufactured by Kao Corporation), and 90% by mass of water. Furthermore, a dried film was obtained by heating at 230°C for 30 minutes.

[0203] (Evaluation of coloring strength by measuring film thickness) The film thickness of the obtained films was measured, and their coloring ability was determined. Since all films had a maximum absorbance of 2.0 at 450-500 nm, thinner films exhibited superior coloring ability with smaller amounts of pigment. Less than 2.6 μm: ○++ 2.6 μm or more and less than 2.9 μm: ○+ 2.9 μm or more and less than 3.2 μm: ○ 3.2 μm or larger and less than 3.3 μm: △ 3.3μm or more; ×

[0204] (Evaluation of transmittance) The transmittance of the above substrate at 550 nm was measured and determined using the same method as described above. 93% or higher: ○+ 92% or more: ○ Less than 92%: ×

[0205] <Creating a color filter> First, a blue photosensitive colored composition was prepared for use in the fabrication of color filters.

[0206] (Preparation of blue photosensitive colored composition (BR-1)) After stirring and mixing the following mixture until homogeneous, it was dispersed for 5 hours using 0.5 mm diameter zirconia beads in an Eiger mill (Eiger Japan's "Mini Model M-250 MKII"), and then filtered through a 5.0 μm pore size filter to prepare a blue colored composition (BP-1). Blue pigment (CI Pigment Blue 15:6) 7.2 parts Purple pigment (CI Pigment Violet 23) 4.8 parts Resin-type dispersant (BASF Japan "EFKA4300") 1.0 part Acrylic resin 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

[0207] Next, the mixture of the following composition was stirred and mixed until homogeneous, and then filtered through a 1 μm pore size filter to prepare a blue photosensitive colored composition (BR-1). Blue coloring composition (BP-1) 34.0 parts Acrylic resin 2 15.2 parts Photopolymerizable monomer (Arronix M400, manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (BASF Japan's "Irgacure 907") 2.0 parts Sensitizer (EAB-F, manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Propylene glycol monomethyl ether acetate 45.1 parts

[0208] (Preparation of red photosensitive colored composition (RR-1)) After stirring and mixing the following mixture until homogeneous, it was dispersed for 5 hours using 0.5 mm diameter zirconia beads in an Eiger mill (Eiger Japan's "Mini Model M-250 MKII"), and then filtered through a 5.0 μm pore size filter to prepare a red colored composition (RP-1). Red pigment (CI Pigment Red 254) 7.2 parts Red pigment (CI Pigment Red 177) 4.8 parts Resin-type dispersant (BASF Japan "EFKA4300") 1.0 part Acrylic resin 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

[0209] Next, the mixture of the following composition was stirred and mixed until homogeneous, and then filtered through a 1 μm pore size filter to prepare a red photosensitive colored composition (RR-1). Red coloring composition (RP-1) 34.0 parts Acrylic resin 2 15.2 parts Photopolymerizable monomer (Arronix M400, manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (BASF Japan's "Irgacure 907") 2.0 parts Sensitizer (EAB-F, manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Propylene glycol monomethyl ether acetate 45.1 parts

[0210] (Creating a color filter) A black matrix was patterned onto a glass substrate, and a red photosensitive coloring composition (RR-1) was applied to the substrate using a spin coater to a thickness such that x = 0.640 to form a colored film. The film was then subjected to a high-pressure mercury lamp at 200 mJ / cm² via a photomask. 2 The substrate was irradiated with ultraviolet light. Next, it was spray-developed with an alkaline developer consisting of 0.2% by mass sodium carbonate aqueous solution to remove the unexposed areas, washed with deionized water, and the substrate was heated at 230°C for 30 minutes to form a red filter segment. Similarly, the green filter segment was made using the green photosensitive coloring composition (GR-4) of the present invention to match a chromaticity of y=0.660, and the blue filter segment was made using the blue photosensitive coloring composition (BR-1) to a film thickness such that y=0.060, thereby forming each filter segment and obtaining a color filter. Note that x and y represent the chromaticity of the XYZ color system.

[0211] By using the green photosensitive coloring composition (GR-3) of the present invention, it was possible to obtain the desired coloring strength and transmittance at a high level, and furthermore, it could be used suitably without any problems with other physical properties.

Claims

1. A colored composition comprising a quinophthalone pigment (A) represented by the following general formula (1), and a resin. General formula (1) 【Chemistry 1】 (R １１ ~R １７ Each of these independently consists of a hydrogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a sulfo group, a C1-C4 alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarboxyl group, a halogen atom, a C2-C4 alkenyl group, an alkenyloxy group, a C6-C12 aryl group, and -SO ２ -O-R １１１ , -SO ２ -NH-R １１２ This represents a ring formed by two of these atoms, each excluding a hydrogen atom, and another group of atoms may be inserted between them when the ring is formed. １１１ , R １１２ This represents an alkyl group with 1 to 4 carbon atoms. X １ represents -NH-CO-R １１３ , -NH-SO ２ -R １１４ ; R １１３ represents an aryl group or a heteroaryl group having 6 to 20 carbon atoms which may have a substituent, and the aryl group or heteroaryl group represents a phenyl group, a naphthyl group, a benzothiazolyl group, or an indolyl group. R １１４ represents a phenyl group having 6 to 20 carbon atoms which may have a substituent.)

2. The coloring composition according to claim 1, wherein the coloring composition comprises 40% by mass of the quinophthalone pigment (A) in the total solid content and a resin having a spectral transmittance of 95% or more in the entire wavelength range of 400 to 700 nm, and when the coloring composition forms a film with a thickness of 1 μm, the maximum absorbance at 450 to 500 nm is 1.7 or more.

3. The colored composition according to claim 1 or 2, wherein the average primary particle size of the quinophthalone pigment (A) is 5 to 400 nm.

4. The coloring composition according to claim 1 or 2, further comprising a green pigment.

5. The colored composition according to claim 1 or 2, further comprising a photopolymerization initiator.

6. The coloring composition according to claim 1 or 2, further comprising a photopolymerizable monomer.

7. A color filter comprising a filter segment containing the coloring composition according to claim 1 or 2.

Images