Colorants, coloring compositions for color filters, cured films, color filters, liquid crystal display devices, and solid-state image sensors

Abstract

To provide a coloring agent including a methylated diketo-pyrrolo-pyrrole pigment, having an excellent spectral characteristic, a high contrast ratio, a viscosity stability, and a solvent resistance, and causes less generation of foreign materials due to defective dispersion and less generation of foreign material due to a heating process.SOLUTION: The present invention relates to a coloring agent containing a methylated diketo-pyrrolo-pyrrole pigment expressed by a chemical formula (1). The X-ray diffraction pattern of a CuKα-ray has its peak when the Bragg angle 2θ is 2θ(±0.3)=15.7° and 27.0°. The coloring agent has a crystal type in which the intensity ratio (H2 / H1) when the diffraction intensity of 15.7° is denoted by H1 and the diffraction intensity of 27.0° is denoted by H2 is in the range of 1.5 to 2.6, both inclusive.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a coloring agent, a coloring composition for a color filter, a cured film, a color filter, and a liquid crystal display device and a solid-state image sensor equipped therewith. [Background technology]

[0002] Liquid crystal display devices (LCDs) are devices that display images by controlling the amount of light passing through the second polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate, with a liquid crystal layer sandwiched between two polarizing plates. The most common type uses twisted nematic (TN) liquid crystals. By adding a color filter between these two polarizing plates, color display becomes possible, and as they have come into use in televisions and computer monitors in recent years, there has been an increasing demand for higher brightness, higher contrast, and higher color reproduction for color filters.

[0003] A color filter consists of two or more fine stripe-like filter segments of different hues arranged in parallel or intersecting patterns on the surface of a transparent substrate such as glass, or fine filter segments arranged in a fixed vertical and horizontal pattern. Generally, they are often formed from three colored filter segments: red, green, and blue. Each of these segments is very small, ranging from a few microns to several hundred microns, and is arranged neatly in a predetermined pattern for each hue.

[0004] Generally, in color liquid crystal displays, transparent electrodes for driving the liquid crystals are formed on a color filter by vapor deposition or sputtering, and an alignment film is further formed on top of that to orient the liquid crystals in a specific direction. To obtain sufficient performance from these transparent electrodes and alignment film, high-temperature processing of 200°C or higher, preferably 230°C or higher, is generally required in the manufacturing process of forming the color filter. For this reason, the pigment dispersion method, which uses pigments with excellent light resistance and heat resistance as colorants, is currently the mainstream method for producing color filters.

[0005] In pigment dispersion methods, the red filter segment typically uses pigments with excellent lightfastness and heat resistance, such as diketopyrrolopyrrole pigments, anthraquinone pigments, perylene pigments, or disazo pigments, either alone or in combination, as colorants. Among these, diketopyrrolopyrrole pigments are becoming increasingly important from the viewpoint of spectral characteristics. (Patent Documents 1 and 2)

[0006] Among diketopyrrolopyrrole pigments, methylated diketopyrrolopyrrole pigments have attracted attention due to their excellent spectral properties (transmittance and coloring power). While optimizing the crystal structure of the pigment is crucial for optimizing spectral properties, the design of an appropriate crystal structure for methylated diketopyrrolopyrrole pigments has been lacking, making it difficult to say that their spectral properties have been optimized. Furthermore, in recent years, there has been a strong demand for higher contrast and transmittance in color filters, which requires miniaturizing the primary particles of the pigment as much as possible. However, miniaturized diketopyrrolopyrrole pigments are difficult to maintain viscosity stability, and their intermolecular hydrogen bonding makes them prone to crystal growth. This leads to crystallization during the heating process when forming color filters, resulting in the generation of foreign matter, which is a problem. Additionally, miniaturized diketopyrrolopyrrole pigments also have issues with solvent resistance and dispersibility. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2018-145312 [Patent Document 2] International Publication No. 2016 / 103994 [Overview of the project] [Problems that the invention aims to solve]

[0008] The problem that the present invention aims to solve is to provide a coloring agent containing a methylated diketopyrrolopyrrole pigment that has good spectral characteristics, a high contrast ratio, viscosity stability, and solvent resistance, and that generates little foreign matter due to poor dispersion and heating processes, a coloring composition for color filters containing the coloring agent, a cured film, a color filter, and a liquid crystal display device and a solid-state image sensor equipped therewith. [Means for solving the problem]

[0009] As a result of diligent research, the present inventors have discovered that by using a colorant containing a methylated diketopyrrolopyrrole pigment having a specific crystal type, a colored composition for color filters can be obtained that exhibits good spectral characteristics, a high contrast ratio, and suppressed crystal precipitation during the heating process, leading to the present invention.

[0010] In other words, the present invention relates to a colorant (a) containing a methylated diketopyrrolopyrrole pigment represented by the following chemical formula (1), wherein the X-ray diffraction pattern by CuKα rays has diffraction peaks at Bragg angles 2θ(±0.3) = 15.7° and 27.0°, and the colorant (a) has a crystalline form in which the intensity ratio (H2 / H1) when the diffraction intensity at 15.7° is H1 and the diffraction intensity at 27.0° is H2 is 1.5 or more and 2.6 or less.

[0011] Chemical formula (1) [ka]

[0012] Furthermore, the present invention relates to the colorant (a) having a crystal type in which the intensity ratio (H2 / H1) in the X-ray diffraction pattern by CuKα rays is 1.5 or more and 1.9 or less.

[0013] The present invention relates to a coloring agent characterized in that, when a colored film is formed, the X-ray diffraction of the colored film using CuKα rays exhibits a maximum peak at a diffraction angle of 2θ(±0.3) = 27.0°.

[0014] The present invention also relates to a colored composition for a color filter containing a colorant (A), a resin-type dispersant (B), and an organic solvent (C), wherein the colorant (A) contains the colorant (a).

[0015] The present invention also relates to the colored composition for a color filter, wherein the colorant (A) further contains at least one pigment selected from the group consisting of C.I. Pigment Red 177, 254, 269, 291, C.I. Pigment Orange 71, 73, C.I. Pigment Yellow 138, 139, 150, 185, and 231. The present invention also relates to the colored composition for a color filter containing the pigment.

[0016] The present invention also relates to the colored composition for a color filter further containing a dye derivative (D).

[0017] The present invention also relates to the colored composition for a color filter, wherein the dye derivative (D) contains at least one dye derivative selected from the group consisting of diketopyrrolopyrrole-based, azo-based, quinophthalone-based, and thiazine-based derivatives The present invention also relates to the colored composition for a color filter containing the dye derivative.

[0018] The present invention also relates to the colored composition for a color filter, wherein the resin-type dispersant (B) is a reaction product obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a polymer having a hydroxyl group at at least one terminal and a tricarboxylic anhydride or tetracarboxylic dianhydride and / or a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride or tetracarboxylic dianhydride.

[0019] The present invention also relates to the colored composition for a color filter further containing a polymerizable compound (E) and / or a photopolymerization initiator (F).

[0020] The present invention also relates to the colored composition for a color filter, wherein the photopolymerization initiator (F) contains an oxime ester-based photopolymerization initiator.

[0021] Furthermore, the present invention relates to a coloring composition for color filters that contains a binder resin (G).

[0022] Furthermore, the present invention relates to a coloring composition for color filters in which the binder resin (G) contains an alkali-soluble resin having an ethylenically unsaturated double bond.

[0023] Furthermore, the present invention relates to a cured film obtained by curing the coloring composition for color filters.

[0024] Furthermore, the present invention relates to a color filter having the cured film.

[0025] Furthermore, the present invention relates to a liquid crystal display device comprising the aforementioned color filter.

[0026] Furthermore, the present invention relates to a solid-state image sensor comprising the aforementioned color filter. [Effects of the Invention]

[0027] The present invention provides a coloring agent that possesses good spectral characteristics, a high contrast ratio, viscosity stability, and solvent resistance, and that generates less foreign matter due to poor dispersion and heating processes; a coloring composition for color filters containing the coloring agent; a cured film; a color filter; and a liquid crystal display device and a solid-state image sensor equipped therewith. [Brief explanation of the drawing]

[0028] [Figure 1] Figure 1 is a schematic cross-sectional view of a liquid crystal display device. [Figure 2] Figure 2 is the X-ray diffraction pattern of the red coloring agent (a-2) prepared in Example 2. [Figure 3] Figure 3 shows the X-ray diffraction pattern of the synthesized methylated diketopyrrolopyrrole pigment (p-1). [Figure 4] Figure 4 shows the X-ray diffraction pattern of the prepared colored composition (RP-1). [Modes for carrying out the invention]

[0029] The following definitions are used in this specification. When "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamide" are used, unless otherwise specified, they refer to "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or methacrylamide," respectively. "CI" as used herein means Color Index (CI). Colorants include pigments and dyes.

[0030] <Coloring agent containing methylated diketopyrrolopyrrole pigment (a)> The colorant (a) of the present invention contains a methylated diketopyrrolopyrrole pigment represented by the following chemical formula (1), and has a crystalline form in which the X-ray diffraction pattern by CuKα rays has diffraction peaks at Bragg angles 2θ(±0.3) = 15.7° and 27.0°, and the intensity ratio (H2 / H1) when the diffraction intensity at 15.7° is H1 and the diffraction intensity at 27.0° is H2 is 0.1 or more and 2.6 or less.

[0031] General formula (1) [ka]

[0032] Furthermore, it is preferable to have a crystal type in which the intensity ratio (H2 / H1) in the X-ray diffraction pattern using CuKα rays is between 1.5 and 1.9. This range improves both the contrast ratio and transmittance.

[0033] <Coloring composition for color filters> The colored composition for color filters of the present invention contains a colorant (A), a resin-type dispersant (B), and an organic solvent (C).

[0034] <Coloring agent (A)> The coloring agent (A) contains the coloring agent (a) of the present invention. It may also contain pigments or dyes other than the coloring agent (a) of the present invention.

[0035] (Pigment) As pigments, organic or inorganic pigments can be used individually or in mixtures of two or more types. Pigments with high color development and high heat resistance, particularly those with high heat decomposition resistance, are preferred, and organic pigments are usually used. Specific examples of organic pigments usable in color filter coloring compositions are shown below by their color index numbers.

[0036] Examples of red pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245 Examples include pigments described in Japanese Patent Publication No. 2014-134712, pigments described in Japanese Patent Publication No. 6368844, etc. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, the preferred pigments are CI pigment red 48:1, 122, 177, 224, 242, 269, 254, 291, 295, 296, the pigment described in Japanese Patent Publication No. 2014-134712, and the pigment described in Japanese Patent Publication No. 6368844. More preferably, the preferred pigments are CI pigment red 177, 254, 291, 295, 296, the pigment described in Japanese Patent Publication No. 2014-134712, and the pigment described in Japanese Patent Publication No. 6368844.

[0037] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73.

[0038] Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6 is preferred, and CI Pigment Blue 15:6 is even more preferred.

[0039] Examples of purple pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, CI Pigment Violet 19 or 23 is preferred from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, and CI Pigment Violet 23 is more preferred.

[0040] Examples of green pigments include, but are not limited to, CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, and the pigments described in Japanese Patent Publication No. 2017-111398. Among these, from the viewpoint of transmittance, CI Pigment Green 36, 58, 59, 62, 63, and the pigments described in Japanese Patent Publication No. 2017-111398 are preferred.

[0041] For yellow pigments, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123 Examples include pigments described in Japanese Patent Publication No. 2012-226110, such as 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, and the pigments described in Japanese Patent Publication No. 2012-226110. Preferably, CI Pigment Yellow 138, 139, 150, 185, 231, 233, and This is a pigment described in Public Publication No. 2012-226110.

[0042] In addition, inorganic pigments include titanium dioxide, barium sulfate, zinc oxide, lead sulfate, lead yellow, zinc yellow, red iron(III) oxide, cadmium red, ultramarine, Prussian blue, chromium green, and cobalt. Examples include green, amber, and synthetic iron black. Inorganic pigments are used in combination with organic pigments to ensure good applicability, sensitivity, and developability while maintaining a balance between saturation and brightness.

[0043] Among the above pigments, at least one pigment selected from the group consisting of CI Pigment Red 177, 254, 269, 291, CI Pigment Orange 71, 73, CI Pigment Yellow 138, 139, 150, 185, and 231 is used. From a hue perspective, it is preferable.

[0044] (Pigment refinement) When using organic pigments as colorants, it is preferable to perform a micronization process before mixing them with other raw materials. Examples of micronization methods include wet grinding, dry grinding, and dissolution extraction. Among these, salt milling by the kneader method, a type of wet grinding, is preferred. The average primary particle size of the organic pigment after micronization is preferably 10 to 80 nm, and more preferably 15 to 70 nm. An appropriate particle size further improves dispersibility and enhances the contrast ratio of the coating. The average primary particle size is the average value of approximately 20 particles arbitrarily selected from a magnified image obtained using a TEM (transmission electron microscope). If the particle has both a vertical axis length and a horizontal axis length, the vertical axis length is used.

[0045] 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 batch or continuous kneading machines such as kneaders, two-roll mills, three-roll mills, ball mills, attritors, sand mills, and planetary mixers, 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.

[0046] Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate. Among these, sodium chloride (table salt) is preferred from the standpoint of cost. The amount of water-soluble inorganic salt used is preferably 50 to 2000 parts by mass, and more preferably 300 to 1000 parts by mass, per 100 parts by mass of pigment, considering both processing efficiency and production efficiency.

[0047] The water-soluble organic solvent wets the pigment and the water-soluble inorganic salt. The water-soluble organic solvent is a compound that dissolves (miscible) in water but substantially does not dissolve the water-soluble inorganic salt. The water-soluble organic solvent is preferably a high-boiling point solvent with a boiling point of 120°C or higher, as it does not easily volatilize due to the temperature rise during salt milling. Examples of water-soluble organic solvents include 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. The amount of water-soluble organic solvent used is preferably 5 to 1000 parts by mass, and more preferably 50 to 500 parts by mass, per 100 parts by mass of pigment.

[0048] During the salt milling process, resin can be added as needed. The resin can be, for example, a natural resin. Examples include modified natural resins, synthetic resins, and synthetic resins modified with natural resins. The resin is preferably solid at room temperature, insoluble in water, and more preferably partially soluble in water-soluble organic solvents. The amount of resin used is preferably 5 to 200 parts by mass per 100 parts by mass of pigment.

[0049] The coloring agent of the present invention preferably has a maximum peak at a diffraction angle of 2θ(±0.3) = 27.0° in the X-ray diffraction of the colored film using CuKα rays when a colored film is formed. In this case, the colored film may be adjusted to have a non-volatile content of 20% using a resin-type dispersant (B), a binder resin (G), and an organic solvent (C), and the film thickness may be 0.5 μm, but is not limited to these.

[0050] (dye) Examples of dyes include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. Also included are derivatives of dyes and lake pigments, which are dyes that have been transformed into lakes.

[0051] Furthermore, examples of dyes include acidic dyes having acidic groups such as sulfonic acid and carboxylic acid; in the case of direct dyes, inorganic salts of acidic dyes; salt-forming compounds of acidic dyes with quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, or primary amine compounds; and salt-forming compounds such as acidic dyes with resin components having amino groups. Salt-forming compounds of acidic dyes with compounds having an onium base are also preferred due to their excellent fastness. In addition, the compounds having an onium base are preferably resins having cationic groups in their side chains.

[0052] Basic dyes include salt-forming compounds made from organic acids, perchloric acid, or metal salts thereof. Among salt-forming compounds, salt-forming compounds of basic dyes are preferred because they have excellent resistance to various substances and compatibility with pigments.

[0053] The chemical structures of dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), and quinoneimine dyes (oxazine dyes). Examples include dyes such as thiazine dyes, azine dyes, polymethine dyes (oxonol dyes, merocyanine dyes, allylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and rhodamine dyes. Among these, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred from the viewpoint of color characteristics such as hue, color separation, and color unevenness, with xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, and phthalocyanine dyes being more preferred. The specific structures of the dyes are described in "New Edition Dye Handbook" (edited by the Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and colourists), and "Pigment Handbook" (edited by Okawara et al.; Kodansha, 1986), among others.

[0054] <Resin-type dispersant (B)> The resin-type dispersant (B) can be any dispersant that has a colorant affinity site that has the property of adsorbing to the added colorant and a site that is compatible with the colorant carrier, and that works to stabilize the dispersion on the colorant carrier by adsorbing to the added colorant. Specifically, this includes urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, 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 products thereof, oily dispersants such as amides and salts thereof formed by the reaction of poly(lower alkyleneimine) with polyester having free carboxyl groups, etc. Water-soluble resins and 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, as well as polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphate esters can be used, and these can be used individually or in combination of two or more.

[0055] Among the resin-type dispersants described above, it is preferable to include a resin-type dispersant that is a reaction product of a polymer having a hydroxyl group at least one terminal and a tricarboxylic acid anhydride or tetracarboxylic dianhydride (hereinafter referred to as resin-type dispersant (S1)) and / or a reaction product of polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and the acid anhydride group of a tricarboxylic acid anhydride or tetracarboxylic dianhydride (hereinafter referred to as resin-type dispersant (S2)).

[0056] (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 hydroxyl groups is preferably a polymer having hydroxyl groups at its terminals, 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 hydroxyl groups. The compound (q) having hydroxyl groups is preferably a compound having both hydroxyl and thiol groups in its molecule. Since it is preferable to have multiple hydroxyl groups at the terminals, a compound (q1) having two hydroxyl groups and one thiol group in its molecule is preferably used.

[0057] 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) obtained 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) 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.

[0058] (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.

[0059] 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.

[0060] Furthermore, although the above-mentioned resin-type dispersants (S1) and (S2) have a carboxyl group-containing polyester portion and a vinyl polymer portion, it is impossible or practical to specify and describe how these are bonded together; therefore, the description is provided by the manufacturing method.

[0061] Examples of resin-type dispersants having basic functional groups include nitrogen atom-containing graft copolymers, nitrogen atom-containing acrylic block copolymers, and urethane polymer dispersants having functional groups in their side chains that include tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc.

[0062] Furthermore, as disclosed in Japanese Patent Publication No. 2009-185277, a preferred example is the combined use of a resin-type dispersant having an aromatic carboxyl group and a vinyl resin having a tertiary amino group (which functions as a resin-type dispersant).

[0063] The resin-type dispersant (B) is preferably used in an amount of 3 to 200% by mass relative to the total amount of the colorant (A), and more preferably in an amount of 5 to 100% by mass from the viewpoint of film formation.

[0064] Among the above, using a resin-type dispersant having photocrosslinking groups or thermal crosslinking groups is preferable from the viewpoint of solvent resistance and heat resistance.

[0065] <Organic solvent (C)> The colored composition for color filters of the present invention contains an organic solvent (C) to facilitate the formation of a colored film by coating it onto a substrate such as glass to a dry film thickness of 0.2 to 5 μm. The organic solvent (C) is selected considering good coatability of the colored composition, as well as the solubility of each component of the colored composition and safety.

[0066] Examples of organic solvents (C) include ethyl lactate, benzyl alcohol, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, and m-xylene. m-diethylbenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-diethylbenzene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene Dipropylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl 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 Examples include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, cyclopentanone, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters. These organic solvents can be used individually or mixed in any ratio of two or more as needed.

[0067] In particular, it is preferable to use 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, alcohols such as benzyl alcohol, diacetone alcohol, 3-methoxybutanol, and propylene glycol monomethyl ether, and ketones such as cyclohexanone, because they have good dispersibility, penetration, and coatability of the coloring agent (A) and the coloring composition.

[0068] Furthermore, the organic solvent (C) is preferable to be used in an amount of 500 to 4000 parts by mass per 100 parts by mass of colorant (A), as it can adjust the viscosity of the coloring composition to an appropriate level and form a colored film of the desired uniform thickness.

[0069] <Dye derivative (D)> The colored composition for color filters of the present invention may optionally contain a dye derivative (D). The dye derivative (D) is a compound having an acidic group, a basic group, a neutral group, etc., in an organic dye residue. Examples of dye derivatives (D) include compounds having acidic substituents such as a sulfo group, a carboxyl group, or a phosphate group, as well as compounds having basic substituents such as amine salts thereof, sulfonamide groups, or tertiary amino groups at the terminal, and compounds having neutral substituents such as a phenyl group or a phthalimidoalkyl group. Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiaidine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, surene pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

[0070] Specifically, diketopyrrolopyrrole dye derivatives are described in Japanese Patent Publication No. 2001-220520, WO2009 / 081930, WO2011 / 052617, WO2012 / 102399, and Japanese Patent Publication No. 2017-156397, while phthalocyanine dye derivatives are described in Japanese Patent Publication No. 2007-226161, and WO2016 / Pamphlet No. 163351, Japanese Patent Publication No. 2017-165820, Japanese Patent No. 5753266, Anthraquinone-based dye derivatives are mentioned in Japanese Patent Publication No. 63-264674, Japanese Patent Publication No. 09-272812, Japanese Patent Publication No. 10-245501, Japanese Patent Publication No. 10-265697, Japanese Patent Publication No. 2007-079094, and Pamphlet No. WO2009 / 025325. Quinacridone-based dye derivatives are described in Japanese Patent Publication No. 48-54128, Japanese Patent Publication No. 03-9961, and Japanese Patent Publication No. 2000-273383; dioxazine-based dye derivatives are described in Japanese Patent Publication No. 2011-162662; thiaidine-indigo-based dye derivatives are described in Japanese Patent Publication No. 2007-314785; triazine-based dye derivatives are described in Japanese Patent Publication No. 61-246261 and Japanese Patent Publication No. 11 -Publication No. 199796, Japanese Patent Publication No. 2003-165922, Japanese Patent Publication No. 2003-168208, Japanese Patent Publication No. 2004-217842, Japanese Patent Publication No. 2007-314681, Benzoisoindole-based dye derivatives are described in Japanese Patent Publication No. 2009-57478, Quinophthalone-based dye derivatives are described in Japanese Patent Publication No. 2003-167112, Japanese Patent Publication No. 2006-291194 Examples of dye derivatives include those described in Japanese Patent Publication No. 2008-31281 and Japanese Patent Publication No. 2012-226110, naphthol-based dye derivatives are described in Japanese Patent Publication No. 2012-208329 and Japanese Patent Publication No. 2014-5439, azo-based dye derivatives are described in Japanese Patent Publication No. 2001-172520 and Japanese Patent Publication No. 2012-172092, acidic substituents are described in Japanese Patent Publication No. 2004-307854, and basic substituents are described in Japanese Patent Publication No. 2002-201377, Japanese Patent Publication No. 2003-171594, Japanese Patent Publication No. 2005-181383 and Japanese Patent Publication No. 2005-213404. In addition, these documents may refer to dye derivatives as derivatives, pigment derivatives, dispersants, pigment dispersants, or simply compounds, but compounds having substituents such as acidic groups, basic groups, or neutral groups on the aforementioned organic dye residues are synonymous with dye derivatives.

[0071] Among the above, from the viewpoint of the dispersibility of methylated diketopyrrolopyrrole pigments, diketopyrrolopyrrole, azo, quinophthalone, and thiazine-based pigment derivatives are preferred as the type of pigment derivative (D).

[0072] These pigment derivatives (D) can be used individually or in combination of two or more. It is preferable to add 1 to 100 parts by mass of pigment derivative (D) per 100 parts by mass of colorant (A), more preferably 3 to 70 parts by mass, and even more preferably 5 to 50 parts by mass.

[0073] By adding a pigment derivative (D) to a colorant (A) and performing pigmentation treatments such as acid basting, acid slurry, dry milling, salt milling, and solvent salt milling, the pigment derivative (D) is adsorbed onto the surface of the pigment in the colorant (A), making the primary particles of the pigment in the colorant (A) finer compared to when the pigment derivative (D) is not added.

[0074] By adding a dye derivative (D) to a colorant (A) and performing dispersion treatments such as wet dispersion using two-roll, three-roll, or beads, the dye derivative (D) is adsorbed onto the pigment surface in the colorant (A), giving the pigment surface polarity and promoting the adsorption of the resin-type dispersant (B). This improves the compatibility of the pigment, dye derivative (D), resin-type dispersant (B), organic solvent (C), and other additives in the colorant (A), resulting in improved dispersion stability and viscosity stability over time when used as a colored composition for color filters. Furthermore, the improved compatibility leads to excellent film stability over time when the colored composition for color filters is coated onto a glass substrate, etc., and improves the stability and property dependence of the pattern shape, etc., with respect to the waiting time from coating to exposure (PCD: Post Coating Delay) and the waiting time from exposure to heat treatment (PED: Post Exposure Delay), as well as line width sensitivity stability. Furthermore, by adsorbing and coating the pigment surface with the dye derivative (D) and resin-type dispersant (B), aggregation of the pigment and crystal precipitation due to sublimation during heating and firing of the coating film can be suppressed. In addition, variations in development time and development residue are also suppressed.

[0075] <Polymerizable compound (E)> The colored composition for color filters of the present invention can be a photosensitive colored composition for color filters by comprising a polymerizable compound (E) and / or a photopolymerization initiator (F). The polymerizable compound (E) includes monomers or oligomers that harden upon exposure to ultraviolet light or heat to produce a transparent resin.

[0076] Polymerizable compounds (E) include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and trimethylolpropane tri(meth)acrylate. Phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentylglyceride Examples include chol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)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, and the like.

[0077] (Polymerizable compounds containing acidic groups) Polymerizable compound (E) may contain polymerizable compounds having acidic groups. Examples of acidic groups include sulfonic acid groups, carboxyl groups, and phosphate groups.

[0078] Examples of polymerizable compounds having acidic groups include esters of polyhydric alcohols and (meth)acrylic acid poly(meth)acrylates containing free hydroxyl groups with dicarboxylic acids; and esters of polyhydric acids with monohydroxyalkyl (meth)acrylates. Specific examples include monoesterified compounds containing free carboxyl groups between monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate and dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; and oligoesterified compounds containing free carboxyl groups between tricarboxylic acids such as propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid and monohydroxymonoacrylates or monohydroxymonomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

[0079] (Polymerizable compound containing urethane bonds) Polymerizable compound (E) may contain monomers having ethylenically unsaturated bonds and urethane bonds. Examples of such monomers include polyfunctional urethane acrylates obtained by reacting a polyfunctional isocyanate with a hydroxyl group-containing (meth)acrylate, and polyfunctional urethane acrylates obtained by reacting an alcohol with a polyfunctional isocyanate and then reacting that with a hydroxyl group-containing (meth)acrylate.

[0080] Hydroxylated (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, and dipentaerythritol Examples include hydroxycaprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, and hydroxyl group-containing polyol polyacrylate.

[0081] Examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanates.

[0082] Polymerizable compound (E) can be used alone or in combination of two or more types.

[0083] The amount of polymerizable compound (E) is preferably 1 to 50% by mass, and more preferably 2 to 40 parts by mass, based on 100% by mass of the nonvolatile content of the colored composition for color filters. Adding an appropriate amount further improves curability and developability.

[0084] <Photopolymerization initiator (F)> The photopolymerization initiator (F) is, for example, 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)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4- Acetophenone compounds such as methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; 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- Benzophenone compounds such as butylperoxycarbonyl)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( Triazine compounds such as trichloromethyl-(4'-methoxystyryl)-6-triazine, 2-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;Examples include oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyl oxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime); phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds. Among these, oxime ester compounds are preferred.

[0085] The photopolymerization initiator (F) can be used alone or in combination of two or more types.

[0086] (Oxime ester compounds) Oxime ester compounds undergo cleavage of the oxime's NO bond upon absorption of ultraviolet light, generating iminyl radicals and alkyloxy radicals. These radicals further decompose to produce highly reactive radicals, allowing for pattern formation with minimal exposure. While high colorant concentrations in photosensitive coloring compositions can lead to low UV transmittance and reduced hardening of the coating film, oxime ester compounds are suitable for use due to their high quantum efficiency.

[0087] Examples of oxime ester compounds include oxime ester photopolymerization initiators described in Japanese Patent Publication No. 2007-210991, Japanese Patent Publication No. 2009-179619, Japanese Patent Publication No. 2010-037223, Japanese Patent Publication No. 2010-215575, Japanese Patent Publication No. 2011-020998, and the like.

[0088] The content of the photopolymerization initiator (F) is preferably 2 to 50 parts by mass, and more preferably 2 to 30 parts by mass, per 100 parts by mass of the colorant (A). Adding an appropriate amount further improves photocurability and developability.

[0089] <Binder resin (G)> The colored composition for color filters of the present invention may use a binder resin (G). The binder resin (G) disperses, dyes, or impregnates the colorant (A), and examples include thermoplastic resins. Furthermore, when used in the form of an alkali-developable colored resist material, it is preferable to use an alkali-soluble vinyl resin copolymerized with acidic group-containing ethylenically unsaturated monomers. In addition, to further improve light sensitivity, it is preferable to use an alkali-soluble resin having an ethylenically unsaturated double bond.

[0090] In particular, by using an alkali-soluble resin having ethylenically unsaturated double bonds in its side chains as an alkali-developable color resist material, the resin undergoes three-dimensional crosslinking when exposed to active energy rays to form a coating film. This fixes the colorant (A), resulting in improved heat resistance and suppression of thermal fading of the colorant (A) (deterioration of spectral properties). Furthermore, it also has the effect of suppressing aggregation and precipitation of the colorant (A) component during the development process.

[0091] The binder resin (G) is preferably a resin with a spectral transmittance of 80% or more, and more preferably 95% or more, across the entire wavelength range of 400 to 700 nm in the visible light region.

[0092] The weight-average molecular weight (Mw) of the binder resin (G) is preferably in the range of 2,000 to 80,000, and more preferably in the range of 3,000 to 40,000, in order to properly disperse the colorant (A). The number-average molecular weight (Mn) is preferably in the range of 3,000 to 40,000, and the Mw / Mn value is preferably 10 or less.

[0093] When using binder resin (G) in a colored composition for color filters, the balance between carboxyl groups that act as colorant adsorbents and alkali-soluble groups during development, and aliphatic and aromatic groups that act as affinity groups for colorant carriers and solvents, is important for the dispersibility, penetration, developability, and durability of the colorant (A). It is preferable to use a resin with an acid value of 20 to 300 mgKOH / g. If the acid value is less than 20 mgKOH / g, solubility in the developer is poor, and it may be difficult to form fine patterns. If it exceeds 300 mgKOH / g, fine patterns may not remain.

[0094] The binder resin (G) has good film-forming properties and various resistances, so it is preferable to use it in an amount of 20 parts by mass or more per 100 parts by mass of the total mass of the colorant (A). However, since a high colorant concentration can be achieved and good color characteristics can be expressed, it is preferable to use it in an amount of 1000 parts by mass or less.

[0095] Examples of thermoplastic resins used for the binder resin (G) 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. Among these, acrylic resin is preferred.

[0096] Examples of vinyl-based alkali-soluble resins copolymerized with acidic group-containing ethylenically unsaturated monomers include resins having acidic groups such as carboxyl groups and sulfo groups. Examples of alkali-soluble resins include acrylic resins having acidic groups, α-olefin / (maleic anhydride) copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, or isobutylene / (maleic anhydride) 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.

[0097] Examples of alkali-soluble resins having ethylenically unsaturated double bonds include resins in which unsaturated ethylenically unsaturated double bonds have been introduced by the methods (i) and (ii) shown below.

[0098] [Method (i)] Method (i) involves, for example, copolymerizing an unsaturated ethylenically polymerized an epoxy group-containing unsaturated monomer 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 double bond, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to introduce an unsaturated ethylenically double bond and a carboxyl group.

[0099] 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.

[0100] 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.

[0101] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These can be used individually or in combination of two or more. If necessary, such as to increase the number of carboxyl groups, tricarboxylic acid anhydrides such as trimellitic anhydride or tetracarboxylic dianhydrides such as pyromellitic dianhydride can be used to hydrolyze the remaining anhydride groups. Furthermore, if tetrahydrophthalic anhydride or maleic anhydride, which have unsaturated ethylenically double bonds, are used as polybasic acid anhydrides, the number of unsaturated ethylenically double bonds can be further increased. .

[0102] A similar method to method (i) 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.

[0103] [Method (ii)] Method (ii) 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.

[0104] Examples of unsaturated ethylenic monomers having hydroxyl groups include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate. These may be used individually 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 are preferred.

[0105] Examples of unsaturated ethylenic 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.

[0106] <Thermosetting compounds> In the present invention, a thermosetting compound can be further included in combination with a thermoplastic resin as the binder resin. When producing a color filter using the coloring composition for color filters of the present invention, the inclusion of a thermosetting compound reacts during the firing of the filter segment, increasing the crosslinking density of the coating film. This improves the heat resistance of the filter segment, suppresses pigment aggregation during the firing of the filter segment, and improves the contrast ratio.

[0107] The thermosetting compound may be a low-molecular-weight compound or a high-molecular-weight compound such as a resin. Examples of thermosetting compounds include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenolic compounds, but the present invention is not limited thereto. In the coloring compositions for color filters of the present invention, epoxy compounds and oxetane compounds are preferably used.

[0108] <Sensitizer> Furthermore, the coloring composition for color filters of the present invention may contain a sensitizer. Examples of sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, and xanthene derivatives. , polymethine dyes such as 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, tetrapyradinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxaliloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives Examples include cyanine derivatives, pyrylium derivatives, thiopyrillium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler ketone derivatives, biimidazole 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. These sensitizers can be used individually or mixed in any ratio as needed.

[0109] More specifically, examples of sensitizers include, but are not limited to, those described in "Pigment Handbook" (1986, Kodansha) edited by Shin Okawara et al., "Chemistry of Functional Pigments" (1981, CMC) edited by Shin Okawara et al., and "Special Functional Materials" (1986, CMC). In addition, sensitizers that exhibit absorption in the ultraviolet to near-infrared region can also be included.

[0110] The sensitizer content is preferably 3 to 60 parts by mass per 100 parts by mass of the photopolymerization initiator (F) contained in the coloring composition, and more preferably 5 to 50 parts by mass from the viewpoint of photocurability and developability.

[0111] <Thiol compounds> The coloring composition for color filters of the present invention may contain a thiol compound that acts as a chain transfer agent. Suitable thiol compounds include polyfunctional thiol compounds having two or more thiol groups, such as hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. These polyfunctional thiol compounds can be used individually or mixed in any ratio of two or more as needed.

[0112] The thiol compound content is preferably 0.1 to 30% by mass, and more preferably 0.1 to 20% by mass, based on the total solid content mass of the colored composition for the color filter (100% by mass). If the thiol compound content is less than 0.1% by mass, the effect of adding the thiol compound is insufficient, and if it exceeds 30% by mass, the sensitivity may be too high, which may conversely reduce the resolution.

[0113] <Antioxidant> The colored composition for color filters of the present invention may contain an antioxidant. The antioxidant prevents the photopolymerization initiator (F) and thermosetting compounds contained in the colored composition from oxidizing and yellowing due to the heat process during thermal curing and ITO annealing, thereby increasing the transmittance of the coating film. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a high transmittance of the coating film can be obtained.

[0114] In the present invention, the "antioxidant" can be any compound having ultraviolet absorption function, radical scavenging function, or peroxide decomposition function. Specifically, examples of antioxidants include hindered phenol, hindered amine, phosphorus, sulfur, benzotriazole, benzophenone, hydroxylamine, salicylic acid ester, and triazine compounds, and known ultraviolet absorbers, antioxidants, etc., can be used.

[0115] Among these antioxidants, preferred ones from the viewpoint of achieving both the permeability and sensitivity of the coating film include hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, or sulfur-based antioxidants. More preferably, hindered phenol-based antioxidants, hindered amine-based antioxidants, or phosphorus-based antioxidants are used.

[0116] These antioxidants can be used individually or mixed in any ratio as needed.

[0117] The antioxidant content is more preferable when it is between 0.1% and 5.0% by mass, based on the solid content mass of the coloring composition for color filters (100% by mass), because it provides good brightness and sensitivity.

[0118] <Amine compounds> Furthermore, the coloring composition for color filters of the present invention may contain an amine-based 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.

[0119] <Leveling agent> The colored filter coloring composition of the present invention may contain a leveling agent to improve the leveling properties of the composition on a transparent substrate. A dimethylsiloxane having a polyether or polyester structure in its main chain is preferred as the leveling agent. Specific examples of dimethylsiloxanes having a polyether structure in their main chain include FZ-2122 from Toray Dow Corning and BYK-333 from Vic Chemie. Specific examples of dimethylsiloxanes having a polyester structure in their main chain include BYK-310 and BYK-370 from Vic Chemie. Dimethylsiloxanes having a polyether structure and dimethylsiloxanes having a polyester structure can also be used in combination. The leveling agent content is usually preferably 0.003 to 0.5% by mass, based on the total mass of the coloring composition (100% by mass).

[0120] Particularly preferred leveling agents are those that are a type of surfactant having both hydrophobic and hydrophilic groups in their molecule, which have low solubility in water despite having hydrophilic groups, and which 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 which can sufficiently suppress electrostatic charge at an amount that does not cause defects in the coating film due to foaming. Dimethylpolysiloxane having polyalkylene oxide units can be 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.

[0121] 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.

[0122] Leveling agents may also contain anionic, cationic, nonionic, or amphoteric surfactants as auxiliary agents. Two or more surfactants may be used in combination. Examples of anionic surfactants added as auxiliary agents 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.

[0123] 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 polyoxyalkylene-based surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazolines, and fluorine-based and silicone-based surfactants.

[0124] <Hardening agents, curing accelerators> Furthermore, the coloring composition for color filters 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, and sulfonic acid compounds, but the invention is 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-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, The following can be used: 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, phosphorus compounds (e.g., triphenylphosphine), guanamine compounds (e.g., melamine, guanamine, acetoguanamine, benzoguanamine), 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 parts by mass per 100 parts by mass of thermosetting resin.

[0125] <Other additive ingredients> The colored composition for color filters of the present invention may contain a storage stabilizer to stabilize its viscosity over time. It may also contain an adhesion enhancer, such as a silane coupling agent, to improve adhesion to a transparent substrate.

[0126] 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 parts by mass per 100 parts by mass of the coloring agent.

[0127] 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, and γ-glycidoxypropyltriethoxysilane. Examples of silane coupling agents include epoxysilanes 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, N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion enhancer can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, per 100 parts by mass of the coloring agent in the coloring composition.

[0128] <Method for producing colored composition> The colored composition for color filters of the present invention can be manufactured by finely dispersing a colorant (A) in a colorant carrier such as a resin and / or a solvent, preferably together with a dispersing aid such as a dye derivative (D) or a resin-type dispersant (B), using various dispersion methods such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). At this time, two or more colorants may be dispersed simultaneously in the colorant carrier, or they may be dispersed separately in the colorant carrier and then mixed. If the colorant, such as a dye, has high solubility, specifically if it has high solubility in the solvent used, dissolves upon stirring, and no foreign matter is detected, then it is not necessary to manufacture it by fine dispersion as described above.

[0129] Furthermore, when used as a photosensitive colored composition (resist material), it is a solvent-developable type or It can be prepared as an alkali-developable colored composition. Solvent-developable or alkali-developable colored compositions can be prepared by mixing the colorant dispersion with a polymerizable compound (E) and / or a photopolymerization initiator (F), and optionally an organic solvent (C), other dispersants, and additives. The photopolymerization initiator (F) may be added during the preparation of the colored composition, or it may be added to the prepared colored composition afterward.

[0130] <Dispersing agent> When dispersing the colorant (A) in the colorant carrier, dispersing aids such as a dye derivative (D), a resin-type dispersant (B), and a surfactant may be included as appropriate. Since the dispersing aid has a significant effect in preventing the re-aggregation of the colorant (A) after dispersion, the colored composition obtained by dispersing the colorant (A) in the colorant carrier using a dispersing aid will have good brightness and viscosity stability. The dye derivative (D) and the resin-type dispersant (B) are as described above.

[0131] <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.

[0132] When adding a surfactant, the amount is preferably 0.1 to 55 parts by mass, and more preferably 0.1 to 45 parts by mass, per 100 parts by mass of colorant (A). If the amount of surfactant is less than 0.1 parts by mass, the effect of the addition is difficult to obtain, and if the content is more than 55 parts by mass, the dispersion may be affected by the excessive dispersant.

[0133] <Removal of coarse particles> The colored composition for color filters of the present invention is preferably subjected to centrifugation, sintering filter filtration, or membrane filter filtration to remove coarse particles of 5 μm or larger, preferably 1 μm or larger, and more preferably 0.5 μm or larger, as well as any impurities. Thus, it is preferable that the colored composition substantially contains no particles of 0.5 μm or larger. More preferably, the particles are 0.3 μm or smaller.

[0134] <Specific metal atomic weights in colored compositions> The colored composition for color filters of the present invention may contain small amounts of metallic components, including Li, Na, K, Cs, Mg, Ca, Fe, Cr, and Zr (hereinafter also referred to as specific metal atoms), in addition to the components of the colorant. If a large amount of these metallic components containing specific metal atoms is present, viscosity stability may be inhibited, heat resistance may decrease, and sensitivity may decrease when prepared in the form described above in the photosensitive colored composition. Furthermore, color filters made using colored compositions containing a large amount of metal components, including such specific metal atoms, may generate foreign matter, which can easily lead to a decrease in transmittance. The specific metal atoms in the metal components contained in the colored composition for color filters of the present invention The total content is preferably 500 ppm by mass or less relative to the entire coloring composition.

[0135] The total content of specific metal atoms in the colored composition for color filters of the present invention is more preferably 300 ppm by mass or less, and particularly preferably 200 ppm by mass or less, relative to the entire colored composition. Furthermore, while there is no particular lower limit to the total content of specific metal atoms, it is preferably 1 ppm by mass or more, and more preferably 5 ppm by mass or more, relative to the entire colored composition. Within the above range, a colored composition can be obtained that reduces costs, exhibits excellent viscosity stability, and forms a color filter with minimal generation of foreign matter and reduced transmittance.

[0136] The content of each specific metal atom in the colored composition for color filters of the present invention is preferably 100 ppm by mass or less, and more preferably 50 ppm by mass or less, relative to the entire colored composition.

[0137] Furthermore, if the colorant structure includes metal atoms such as Ni, Zn, Cu, Al, Fe, Pt, and Co, there may be some of these metal atoms that do not constitute part of the colorant structure. It is preferable to have as few of these metal atoms as possible, and they can be removed in the same way as specific metal atoms by the following method. In addition, it is preferable that the concentration of contaminants such as Mn, Cs, Ti, Si, and Pd, which may be introduced due to materials used in the manufacturing process of the various raw materials of the colorant composition (e.g., catalysts), be low.

[0138] Methods for removing metal atoms from various raw materials contained in the coloring composition or from equipment introduced during the manufacturing process include washing with water as described in Japanese Patent Publication No. 2010-83997, Japanese Patent Publication No. 2018-36521, Japanese Patent Publication No. Hei 7-198928, Japanese Patent Publication No. Hei 8-333521, Japanese Patent Publication No. 2009-7432, etc., and methods such as removing magnetic foreign matter with a magnet as described in Japanese Patent Publication No. 2011-48736, and these methods may be used individually or in combination as appropriate.

[0139] The content of specific metal atoms can be measured by inductively coupled plasma atomic emission spectroscopy (ICP).

[0140] <Moisture content in colored composition> The colored composition for color filters of the present invention preferably contains 0.1 to 2.0% by mass or less of water relative to the total amount of the colored composition. When the water content is within the above range, the colored composition exhibits excellent viscosity stability and sensitivity even after being stored over time. The water content is more preferably 0.1 to 1.8% by mass or less, and even more preferably 0.1 to 1.6% by mass or less, relative to the total amount of the coloring composition. If the water content is sufficiently low within this range, problems with viscosity stability and sensitivity are unlikely to occur even after storage over time.

[0141] There are no particular restrictions on the method for controlling the water content, and known methods can be used. For example, methods include manufacturing the colored composition while blowing in a dry inert gas, or adding molecular sieves after manufacturing to dehydrate it. Among these, the method of manufacturing while blowing in a dry inert gas is preferred.

[0142] The water content can be measured by known methods such as the Karl Fischer method.

[0143] <Amount of toluene in the colored composition> The coloring composition for color filters of the present invention may contain toluene, and if so, the toluene content is preferably 0.1 to 10 ppm by mass. The upper limit of the toluene content is preferably 9 ppm by mass or less, more preferably 8 ppm by mass or less, and even more preferably 7 ppm by mass or less. The lower limit is 0.2 ppm by mass or more. It is preferable that the concentration be 0.3 ppm by mass or more, and even more preferable that it be 0.4 ppm by mass or more.

[0144] <Color Filter> Next, the color filter of the present invention will be described. The color filter of the present invention comprises a red filter segment, a green filter segment, and a blue filter segment. The color filter may further comprise a magenta filter segment, a cyan filter segment, and a yellow filter segment. Preferably, the red filter segment of the color filter of the present invention is formed from the coloring composition for color filters of the present invention.

[0145] (How to manufacture color filters) In color filters, it is preferable to first form a black matrix on the substrate, and then form the filter segments. Alternatively, thin-film transistors (TFTs) can be formed on the substrate beforehand, and then the black matrix can be formed. Examples of black matrices include multilayer films of chromium or chromium / chromium oxide, inorganic films such as titanium nitride, and resin films in which light-shielding agents are dispersed.

[0146] Filter segments can be fabricated using methods such as printing, electrodeposition, transfer, inkjet, and photolithography. The printing method allows for pattern formation simply by repeatedly printing and drying a photosensitive colored composition prepared as a printing ink, making it a low-cost and highly productive method for manufacturing color filters. Furthermore, advancements 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.

[0147] The electrodeposition method uses a transparent conductive film formed on a transparent substrate to create color filters by electrodepositing each color filter segment onto the transparent conductive film using electrophoresis of colloidal particles. The transfer method, on the other hand, involves forming filter segments on the release surface of a release sheet. These filter segments are then transferred to a transparent substrate.

[0148] Photolithography involves, for example, applying a photosensitive colored composition containing a colorant of a certain hue onto a transparent substrate to form a film with a dry film thickness of approximately 0.2 to 5 μm. The resulting film (hereinafter referred to as the first film) is exposed (irradiated with light) through a mask having a predetermined pattern. Next, development is performed by immersion in a solvent or alkaline developer or by spraying the developer, removing uncured portions to obtain the desired pattern. By performing this process similarly with photosensitive colored compositions containing colorants of other hues, color filters having filter segments of each color can be manufactured. Furthermore, a second film (oxygen barrier film) can be formed on the first film before exposure using polyvinyl alcohol or a water-soluble acrylic resin. This prevents the first film from coming into contact with oxygen, thus improving its exposure sensitivity. The color filter can also be heated to cure any uncured polymerizable compounds in the filter segments. Photolithography is preferred because it can produce color filters with higher precision than printing.

[0149] Coating equipment includes, for example, spray coating, spin coating, slit coating, and roll coating. A drying process can be performed during coating. Drying equipment includes, for example, a hot air oven and an infrared heater.

[0150] The developer can be an alkaline developer, for example, an inorganic alkali such as sodium carbonate or sodium hydroxide; or an organic alkali such as dimethylbenzylamine or triethanolamine. Furthermore, the developer may contain defoaming agents or surfactants.

[0151] The color filter of the present invention is bonded to a counter substrate using a sealant, liquid crystal is injected through an injection port provided in the sealed portion, the injection port is sealed, and a polarizing film or phase difference film is bonded to the outside of the substrate as needed to manufacture a color liquid crystal display device. This color liquid crystal display device can be used in liquid crystal display modes that perform colorization using color filters such as twisted nematic (TN), super-twisted nematic (STN), in-plane switching (IPS), vertically aligned (VA), and optically convened bend (OCB).

[0152] The color filter of the present invention can be used in applications other than liquid crystal display devices, such as solid-state image sensors, organic EL display devices, quantum dot display devices, electronic paper, and head-mounted displays.

[0153] <Liquid crystal display device> A liquid crystal display device equipped with the color filter of the present invention will be described. The liquid crystal display device of the present invention comprises the color filter of the present invention and a light source. Examples of light sources include cold cathode fluorescent lamps (CCFLs) and white LEDs, but in the present invention, it is preferable to use a white LED because it expands the red color reproduction range. Figure 1 is a schematic cross-sectional view of a liquid crystal display device 10 equipped with the color filter of the present invention. The device 10 shown in Figure 1 comprises a pair of transparent substrates 11 and 21 arranged spaced apart and facing each other, with liquid crystal LC sealed between them.

[0154] Liquid crystal LCs are TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane switching), VA (Vertical Alignment), OCB (Optically Compensated). The orientation is determined according to the driving mode, such as birefringence. A TFT (thin-film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed on top of it. An orientation layer 14 is provided on top of the transparent electrode layer 13. In addition, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0155] On the other hand, the color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. The red, green, and blue filter segments constituting the color filter 22 are separated by a black matrix (not shown).

[0156] A transparent protective film (not shown) is formed over the color filter 22 as needed, and a transparent electrode layer 23 made of, for example, ITO is formed on top of that, and an alignment layer 24 is provided covering the transparent electrode layer 23.

[0157] Furthermore, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. A backlight unit 30 is provided below the polarizing plate 15.

[0158] White LED light sources include those with a fluorescent filter formed on the surface of a blue LED, and those with a phosphor contained in the resin package of a blue LED. These white LED light sources (LED1) have spectral characteristics such as having a wavelength (λ3) where the emission intensity is maximum in the range of 430nm to 485nm, a wavelength (λ4) where the emission intensity is maximum in the range of 530nm to 580nm, and a wavelength (λ5) where the emission intensity is maximum in the range of 600nm to 650nm, and the ratio of the emission intensity I3 at wavelength λ3 to the emission intensity I4 at wavelength λ4 (I4 / I3) is between 0.2 and 0.4, and the ratio of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 (I5 / I3) is between 0.1 and 1.3. A white LED light source (LED2) is preferred, which has spectral characteristics such as having a wavelength (λ1) at which the light intensity is maximum, a second peak wavelength (λ2) of emission intensity in the range of 530 nm to 580 nm, and a ratio (I2 / I1) of emission intensity I1 at wavelength λ1 to emission intensity I2 at wavelength λ2 of 0.2 or more and 0.7 or less.

[0159] Examples of LED1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation) and NSSW304D-HG-V1 (manufactured by Nichia Corporation).

[0160] Examples of LED2 include the NSSW440 (manufactured by Nichia Corporation) and the NSSW304D (manufactured by Nichia Corporation).

[0161] <Solid-state image sensor> The solid-state image sensor of the present invention is equipped with the color filter of the present invention. The configuration of the solid-state image sensor of the present invention is not particularly limited as long as it is equipped with the color filter for the solid-state image sensor of the present invention and functions as a solid-state image sensor, but for example, the following configuration can be given. Solid-state image sensors (CCD sensors, CMOS sensors, organic CMOS sensors, etc.) are mounted on a substrate. It has multiple photodiodes and transfer electrodes made of polysilicon or the like that constitute the light-receiving area, and only the light-receiving portion of the photodiode is open on the photodiode and the transfer electrodes. The device has a light-shielding film made of tungsten or the like, and a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving portion. The configuration includes a color filter for a solid-state image sensor of the present invention on a vice protective film. Furthermore, the configuration may include having a light-gathering means (for example, a microlens; the same applies hereinafter) on the device protection layer and below the color filter (on the side closer to the substrate), or a configuration in which the light-gathering means is on the color filter. The organic CMOS sensor is composed of a thin panchromatic photosensitive organic photoelectric conversion film as the photoelectric conversion layer and a CMOS signal readout substrate. It has a two-layer hybrid structure in which the organic material is responsible for capturing light and converting it into an electrical signal, and the inorganic material is responsible for extracting the electrical signal to the outside. In principle, it is possible to achieve a 100% aperture ratio for incident light. Organic photoelectric conversion films are structure-free continuous films that can be laid on CMOS signal readout substrates, thus eliminating the need for expensive microfabrication processes and making them suitable for miniaturizing filter segments. There are no particular restrictions on the arrangement of the color filter segments, and known methods can be used. [Examples]

[0162] The present invention will be described in detail below based on examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention. In the examples, "parts" and "%" represent "parts by mass" and "mass%", respectively. Also, "PGMAc" means propylene glycol monomethyl ether acetate.

[0163] <Weight-average molecular weight (Mw) of binder resins and resin-type dispersants> The binder resin and resin-type dispersant, as well as their weight-average molecular weight (Mw), were measured by gel permeation chromatography (GPC) equipped with a radioisotope detector. An HLC-8220GPC (manufactured by Tosoh Corporation) was used, with two separation columns connected in series. Both columns were packed with two TSK-GEL SUPER HZM-N columns. Measurements were performed at an oven temperature of 40°C, using THF solution as the eluent, and a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent, and 20 microliters were injected. All molecular weights are polystyrene equivalents.

[0164] <Acid value (mgKOH / g) of binder resins and resin-type dispersants> Add 80 ml of acetone to 0.5-1.0 g of binder resin and resin-type dispersant solution. The solution was dissolved uniformly by adding 10 ml of water and stirring. A 0.1 mol / L KOH aqueous solution was used as the titrant, and the solution was titrated using an automatic titrator ("COM-555," manufactured by Hiranuma Sangyo Co., Ltd.) to measure the acid value of the resin binder and resin-type dispersant solution. The acid value per unit solid content of the resin binder and resin-type dispersant was then calculated from the acid value and solid content concentration of the binder resin and resin-type dispersant solution.

[0165] <Synthesis of binder resin> (Preparation of Binder Resin Solution 1) A reaction vessel was prepared by fitting a thermometer, condenser, nitrogen gas inlet tube, and stirrer into a separable four-neck flask. 70.0 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 13.3 parts n-butyl methacrylate, 4.6 parts 2-hydroxyethyl methacrylate, 4.3 parts methacrylic acid, 7.4 parts paracumylphenol ethylene oxide modified acrylate (Toagosei Co., Ltd. "Aronics M110"), and 0.4 parts 2,2'-azobisisobutyronitrile was added dropwise over 2 hours using a dropping tube. After the dropwise addition was complete, the reaction was continued for another 3 hours to obtain a solution of acrylic resin with a weight-average molecular weight (Mw) of 26,000. After cooling to room temperature, approximately 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Binder resin solution 1 was then prepared by adding propylene glycol monoethyl ether acetate to the previously synthesized resin solution so that the non-volatile content was 20% by mass.

[0166] (Preparation of Binder Resin Solution 2) A separable four-necked flask equipped with a thermometer, condenser, nitrogen gas inlet tube, dropping tube, and stirring device was filled with 370 parts of cyclohexanone. The flask was heated to 80°C, and the inside of the flask was purged with nitrogen. Then, 18 parts of dicyclopentanyl methacrylate, 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2'-A were added via the dropping tube. A mixture of 2.0 parts azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition, the mixture was reacted at 100°C for 3 hours, then 1.0 part azobisisobutyronitrile dissolved in 50 parts cyclohexanone was added, and the reaction was continued at 100°C for 1 hour. Next, the container was replaced with an air purging system, and 9.3 parts acrylic acid (100% of the glycidyl groups), 0.5 parts trisdimethylaminophenol, and 0.1 parts hydroquinone were added to the container. The reaction was continued at 120°C for 6 hours until the solids acid value reached 0.5, at which point the reaction was terminated to obtain an acrylic resin solution. Subsequently, 19.5 parts tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts triethylamine were added, and the mixture was reacted at 120°C for 3.5 hours to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Binder resin solution 2 was then prepared by adding propylene glycol monomethyl ether acetate to the previously synthesized resin solution so that the non-volatile content was 20% by mass. The weight-average molecular weight (Mw) was 19000.

[0167] <Synthesis of methylated diketopyrrolopyrrole pigments> In a stainless steel reaction vessel fitted with reflux vents, 200 parts of tert-amyl alcohol dehydrated with molecular sieves and 140 parts of sodium tert-amyl alkoxide were added under a nitrogen atmosphere and heated to 100°C with stirring to prepare the alkoxide solution. Meanwhile, in a glass flask, 88 parts of diisopropyl succinate and 153.6 parts of 4-methylbenzonitrile were added and heated to 90°C with stirring to dissolve them and prepare a solution of these mixtures. This heated mixture was slowly added dropwise at a constant rate over 2 hours with vigorous stirring to the alkoxide solution heated to 100°C. After the addition was complete, heating and stirring were continued at 90°C for 2 hours to obtain the alkali metal salt of the diketopyrrolopyrrole compound. Furthermore, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to a glass jacketed reaction vessel and cooled to -10°C. This cooled mixture was then processed in a high-speed stirred disperser. Using a siphon, the alkali metal salt solution of the previously obtained diketopyrrolopyrrole compound, cooled to 75°C, was added in small amounts while rotating at 4000 rpm. During this process, the mixture of methanol, acetic acid, and water was kept at a temperature of -5°C or lower while cooling, and the rate of addition of the alkali metal salt of the 75°C diketopyrrolopyrrole compound was adjusted, and the solution was added in small amounts over approximately 120 minutes. After the addition of the alkali metal salt, red crystals precipitated, and a red suspension was formed. Subsequently, the obtained red suspension was washed with an ultrafiltration apparatus at 5°C and filtered to obtain an aqueous paste of methylated diketopyrrolopyrrole pigment represented by chemical formula (1). Subsequently, the obtained aqueous paste of methylated diketopyrrolopyrrole pigment was dried at 80°C for 24 hours and pulverized to obtain 150.2 parts of methylated diketopyrrolopyrrole pigment.

[0168] <Method for producing the dye derivative (D)> (Production of dye derivative (D-1)) Based on Synthesis Example 3 of Patent No. 5748665, a dye derivative (D-1) represented by the following structure was produced.

[0169] [ka]

[0170] (Production of dye derivative (D-2)) Based on Production Example 3 of Patent No. 1863188, a dye derivative (D-2) represented by the following structure was produced.

[0171] [ka]

[0172] (Production of dye derivative (D-3)) Based on Production Example 2 of Patent No. 5332132, a dye derivative (D-3) represented by the following structure was produced.

[0173] [ka]

[0174] (Production of dye derivative (D-4)) Based on Production Example 6 of Patent No. 4983061, a dye derivative (D-4) represented by the following structure was produced.

[0175] [ka]

[0176] (Production of dye derivative (D-5)) Based on Production Example 1 of Patent No. 4585781, a dye derivative (D-5) represented by the following structure was produced.

[0177] [ka]

[0178] (Manufacturing of dye derivative (D-6)) A dye derivative (D-6) represented by the following structure was produced with reference to production example B-1 of Japanese Patent Publication No. 2014-35351.

[0179] [ka]

[0180] <Method for manufacturing coloring agent (a)>

[0181] [Example 1] (Preparation of red coloring agent (a-1)) A mixture of 150 parts of synthesized methylated diketopyrrolopyrrole pigment, 1500 parts of sodium chloride, and 250 parts of diethylene glycol was kneaded at 80°C for 12 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was dried and pulverized to obtain 140 parts of red coloring agent (a-1).

[0182] [Example 2] (Preparation of red coloring agent (a-2)) A mixture of 142.5 parts of synthesized methylated diketopyrrolopyrrole pigment, 7.5 parts of dye derivative (D-1), 1500 parts of sodium chloride, and 250 parts of diethylene glycol was kneaded at 80°C for 12 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was dried and pulverized to obtain 141 parts of red coloring agent (a-2).

[0183] [Example 3] (Preparation of red coloring agent (a-3)) A mixture of 120 parts of synthesized methylated diketopyrrolopyrrole pigment, 30 parts of dye derivative (D-1), 1500 parts of sodium chloride, and 250 parts of diethylene glycol was kneaded at 80°C for 12 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was dried and pulverized to obtain 137 parts of red coloring agent (a-3).

[0184] [Example 4] (Preparation of red coloring agent (a-4)) A mixture of 142.5 parts of synthesized methylated diketopyrrolopyrrole pigment, 7.5 parts of dye derivative (D-2), 1500 parts of sodium chloride, and 250 parts of diethylene glycol was kneaded at 80°C for 12 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. The mixture was then filtered and washed with water to remove sodium chloride and diethylene glycol, after which it was dried and pulverized to obtain 138 parts of red coloring agent (a-4).

[0185] [Example 5] (Preparation of red coloring agent (a-5)) A mixture of 142.5 parts of synthesized methylated diketopyrrolopyrrole pigment, 7.5 parts of dye derivative (D-3), 1500 parts of sodium chloride, and 250 parts of diethylene glycol was kneaded at 80°C for 12 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was dried and pulverized to obtain 142 parts of red coloring agent (a-5).

[0186] [Example 6] (Preparation of red coloring agent (a-6)) A mixture of 142.5 parts of synthesized methylated diketopyrrolopyrrole pigment, 7.5 parts of dye derivative (D-4), 1500 parts of sodium chloride, and 250 parts of diethylene glycol was kneaded at 80°C for 12 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was dried and pulverized to obtain 140 parts of red coloring agent (a-6).

[0187] [Example 7] (Preparation of red coloring agent (a-7)) A mixture of 142.5 parts of synthesized methylated diketopyrrolopyrrole pigment, 7.5 parts of dye derivative (D-5), 1500 parts of sodium chloride, and 250 parts of diethylene glycol was kneaded at 80°C for 12 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was dried and pulverized to obtain 139 parts of red coloring agent (a-7).

[0188] [Example 8] (Preparation of red coloring agent (a-8)) 142.5 parts of synthesized methylated diketopyrrolopyrrole pigment, 7 parts of dye derivative (D-6). A mixture of 5 parts of sodium chloride, 1500 parts of diethylene glycol, and 250 parts of sodium chloride was kneaded at 80°C for 12 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After removing sodium chloride and diethylene glycol by repeated filtration and washing, the mixture was dried and pulverized to obtain 141 parts of red coloring agent (a-8).

[0189] [Comparative Example 1] (Preparation of red coloring agent (p-1)) A synthesized methylated diketopyrrolopyrrole pigment was used as the red coloring agent (p-1).

[0190] The obtained red coloring agent was subjected to powder X-ray diffraction measurements using the following method.

[0191] <Powder X-ray diffraction measurement> Powder X-ray diffraction measurement is performed in accordance with Japanese Industrial Standard JIS K0131 (General Rules for X-ray Diffraction Analysis). The diffraction angle (2θ) was measured in the range of 3° to 35°. Figures 1-3 show the X-ray diffraction pattern (pattern (Example)

[0192] The measurement conditions were as follows: • X-ray diffractometer: RIGAK RINT2100 • Sampling width: 0.02° • Scan speed: 2.0 • Divergence slit: 1° • Divergence vertical limiting slit: 10mm • Scattering slit: 2° • Light-receiving slit: 0.3mm ·Tube:Cu • Tube voltage: 30kV ·Tube current: 30mA

[0193] (Method for calculating peak intensity ratios H1 and H2) The obtained X-ray diffraction spectra were processed under the following conditions to determine intensities H1 and H2. H1 was defined as the maximum diffraction intensity at a Bragg angle of 2θ(±0.3) = 15.7°, and H2 was defined as the maximum diffraction intensity at a Bragg angle of 2θ(±0.3) = 27.0°. The intensity ratio (H2 / H1) was calculated by taking the maximum diffraction intensity (H2) as 1 when the maximum diffraction intensity (H1) was set to 1. The calculated intensity ratio (H2 / H1) for the obtained red colorant is shown in Table 1.

[0194] [Table 1]

[0195] <Other methods for producing pigments> (Preparation of coloring agent (A-1)) A mixture of 300 parts of diketopyrrolopyrrole red pigment (CI Pigment Red 254, BASF "IrgazinREDL3630"), 1500 parts of sodium chloride, and 150 parts of diethylene glycol was kneaded at 60°C for 6 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was dried and pulverized to obtain 291 parts of coloring agent (A-1).

[0196] (Preparation of coloring agent (A-2)) 300 parts of diantraquinone red pigment (CI Pigment Red 177, CINIC "Cinilex SR3C"), 1500 parts of sodium chloride, and diethylene glycol 150 parts of the mixture were kneaded at 60°C for 6 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). Next, this mixture was added to 5 liters of hot water and heated to 70°C. The mixture was stirred for 1 hour to form a slurry. After removing sodium chloride and diethylene glycol by repeated filtration and washing with water, it was dried and pulverized to obtain 286 parts of coloring agent (A-2).

[0197] (Preparation of coloring agent (A-3)) A mixture of 300 parts azo red pigment (CI Pigment Red 269, Sanyo Shikiso Co., Ltd., "Permanent Carmine 3810"), 1500 parts sodium chloride, and 150 parts diethylene glycol was kneaded at 60°C for 6 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was dried and pulverized to obtain 292 parts of coloring agent (A-3).

[0198] (Preparation of coloring agent (A-4)) A mixture of 300 parts of diketopyrrolopyrrole red pigment (CI Pigment Red 291, CINIC "Cinilex DPP MT-CF"), 1500 parts of sodium chloride, and 150 parts of diethylene glycol was kneaded at 60°C for 6 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was dried and pulverized to obtain 288 parts of coloring agent (A-4).

[0199] (Preparation of coloring agent (A-5)) A mixture of 300 parts of diketopyrrolopyrrole orange pigment (C.I. Pigment Orange 71, BASF "Irgazin Orange D2905"), 1500 parts of sodium chloride, and 150 parts of diethylene glycol was kneaded at 60°C for 6 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was dried and pulverized to obtain 289 parts of coloring agent (A-5).

[0200] (Preparation of coloring agent (A-6)) A mixture of 300 parts of diketopyrrolopyrrole orange pigment (C.I. Pigment Orange 73, CINIC "Cinilex DPP Orange SJ1C"), 1500 parts of sodium chloride, and 150 parts of diethylene glycol was kneaded at 60°C for 6 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was dried and pulverized to obtain 290 parts of coloring agent (A-6).

[0201] (Preparation of coloring agent (A-7)) 300 parts of quinophthalone yellow pigment (C.I. Pigment Yellow 138, BASF "Paliotoll Yellow K0960-HD"), 1500 parts of sodium chloride, and ji A mixture of 150 parts of ethylene glycol was kneaded at 60°C for 6 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was dried and pulverized to obtain 291 parts of coloring agent (A-7).

[0202] (Preparation of coloring agent (A-8)) Isoindoline yellow pigment (C.I. Pigment Yellow 139, BASF "Paris") 300 copies of "Otoll Yellow D1819", 1500 copies of sodium chloride, and Dieth A mixture of 150 parts of ethylene glycol was kneaded at 60°C for 6 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was dried and pulverized to obtain 287 parts of coloring agent (A-8).

[0203] (Preparation of coloring agent (A-9)) A mixture of 300 parts of azo yellow pigment (C.I. Pigment Yellow 150, Clariant's "Hostaperm Yellow HN4G"), 1500 parts of sodium chloride, and 150 parts of diethylene glycol was kneaded at 60°C for 6 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was dried and pulverized to obtain 292 parts of colorant (A-9).

[0204] (Preparation of coloring agent (A-10)) A mixture of 300 parts isoindoline yellow pigment (C.I. Pigment Yellow 185, BASF "Pariotol Yellow D1155"), 1500 parts sodium chloride, and 150 parts diethylene glycol was kneaded at 60°C for 6 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was dried and pulverized to obtain 286 parts of coloring agent (A-10).

[0205] (Preparation of coloring agent (A-11)) 200 parts methyl benzoate, 40 parts 8-aminoquinaldine, 150 parts 2,3-naphthalenedicarboxylic acid anhydride, and 154 parts benzoic acid were added and heated to 180°C, with stirring for 4 hours. After cooling to room temperature, the reaction mixture was added to 5440 parts acetone and stirred at room temperature for 1 hour. The product was filtered, washed with methanol, and dried to obtain 116 parts of quinophthalone compound (a). Mass spectrometry by TOF-MS identified the compound as quinophthalone compound (a), represented by the following structural formula.

[0206] Quinophthalone compound (a) [ka]

[0207] Using quinophthalone compound (a) as a raw material, compound (1) represented by the following structural formula was obtained with reference to Synthesis Example 1 described in Japanese Patent Publication No. 2008-81566.

[0208] Compound (1) [ka]

[0209] 300 parts methyl benzoate were mixed with 100 parts compound (1), 108 parts tetrachlorophthalic anhydride, and 143 parts benzoic acid. The mixture was heated to 180°C and reacted for 4 hours. TOF-MS confirmed the formation of quinophthalone compound (b) and the disappearance of the starting compound (1). After cooling to room temperature, the reaction mixture was added to 3510 parts acetone and stirred at room temperature for 1 hour. The product was filtered, washed with methanol, and dried to obtain 120 parts of quinophthalone compound (b). Mass spectrometry by TOF-MS identified the compound as quinophthalone compound (b), represented by the structure shown below.

[0210] Quinophthalone compound (b) [ka]

[0211] A mixture of 300 parts of a quinophthalone compound (b), 1500 parts of sodium chloride, and 150 parts of diethylene glycol was kneaded at 60 °C for 6 hours using a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho). Next, this kneaded product was put into 5 liters of warm water and stirred for 1 hour while heating to 70 °C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried and pulverized to obtain 291 parts of a colorant (A-11).

[0212] (Preparation of Colorant (A-12)) A mixture of 300 parts of a phthalocyanine green pigment C.I. Pigment Green 58 (manufactured by DIC, "FASTOGEN GREEN A110"), 1500 parts of sodium chloride, and 150 parts of diethylene glycol was kneaded at 60 °C for 6 hours using a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho). Next, this kneaded product was put into 5 liters of warm water and stirred for 1 hour while heating to 70 °C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried and pulverized to obtain 285 parts of a colorant (A-12).

[0213] (Preparation of Colorant (A-13)) A mixture of 300 parts of a phthalocyanine-based blue pigment C.I. Pigment Blue 15:6 (manufactured by Toyo Color Co., Ltd., "LIONOL BLUE ES"), 1500 parts of sodium chloride, and 150 parts of diethylene glycol was kneaded at 60 °C for 6 hours using a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho). Next, this kneaded product was put into 5 liters of warm water and stirred for 1 hour while heating to 70 °C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried and pulverized to obtain 286 parts of a colorant (A-13).

[0214] (Preparation of Colorant (A-14)) A mixture of 300 parts of dioxazine purple pigment CI Pigment Violet 23 (Toyo Color Co., Ltd. "LIONOGEN VIOLET RL"), 1500 parts of sodium chloride, and 150 parts of diethylene glycol was kneaded at 60°C for 6 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was dried and pulverized to obtain 292 parts of colorant (A-14).

[0215] <Method for producing resin-type dispersant (B)> (Preparation of resin-type dispersant (B-1) solution) In a reaction vessel equipped with a gas inlet tube, temperature control, condenser, and stirrer, 10 parts methacrylic acid, 90 parts methyl methacrylate, 50 parts ethyl acrylate, 50 parts tert-butyl acrylate, and 50 parts propylene glycol monomethyl ether acetate were charged, and the mixture was purged with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90°C, and the reaction was carried out for 7 hours while adding a solution of 0.1 parts of 2,2'-azobisisobutyronitrile added to 90 parts of propylene glycol monomethyl ether acetate. Solid content measurement confirmed that 95% had reacted. Nineteen parts of pyromellitic dianhydride, fifty parts of propylene glycol monomethyl ether acetate, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and the mixture was reacted at 100°C for 7 hours. After confirming that more than 98% of the acid anhydride had been half-esterified by measuring the acid value, the reaction was terminated. Propylene glycol monomethyl ether acetate was added to dilute the mixture to a solid content of 40% by measuring the solid content, and a solution of carboxylic acid-based resin-type dispersant (B-1) with an acid value of 70 and a weight-average molecular weight of 8500 was obtained.

[0216] (Preparation of resin-type dispersant (B-2~B-6) solutions) The resin-type dispersants (B-2 to B-6) were synthesized in the same manner as the resin-type dispersant (B-1) solution, except that the raw materials and amounts listed in Table 2 were used.

[0217] [Table 2]

[0218] Karenz MOI-BM: 2-([1'-methylpropyleneamino]carboxyamino)ethyl methacrylate (manufactured by Showa Denko) ETERNACOLLOXMA: ((3-ethyloxetan-3-yl)methyl methacrylate, manufactured by Ube Industries) BPAF: 9,9-Bis(3,4-dicarboxyphenyl)fluorenedioxide anhydride (manufactured by JFE Chemical Corporation) C-1015N: Bifunctional polycarbonate polyol, product name Kuraray Polyol C-1015N, (Hydroxyl value 112 mg KOH / g, manufactured by Kuraray Co., Ltd.)

[0219] (Preparation of resin-type dispersant (B-7) solution) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 108 parts of 3-mercapto-1,2-propanediol, 174 parts of pyromellitic dianhydride, 650 parts of propylene glycol monomethyl ether acetate, and 0.2 parts of monobutyltin oxide as a catalyst were charged. After purging with nitrogen gas, the reaction was carried out at 120°C for 5 hours (first step). Acid value measurement confirmed that more than 95% of the acid anhydride had undergone half-esterification. Next, 160 parts of the compound obtained in the first step (based on solid content), 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl methacrylate, 50 parts of methacrylic acid, and 663 parts of propylene glycol monomethyl ether acetate were charged. The reaction vessel was heated to 80°C, and 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) were added and the mixture was reacted for 12 hours (second step). Solid content measurement confirmed that 95% had reacted. Finally, 500 parts of a 50% propylene glycol monomethyl ether acetate solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 parts of hydroquinone were charged, and IR analysis revealed 2270 based on the isocyanate group. The reaction was carried out until the disappearance of the cm-1 peak was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the solid content was adjusted with propylene glycol monomethyl ether acetate to obtain a resin-type dispersant (B-7) with a solid content of 40%. The acid value of the obtained dispersant was 68, the unsaturated double bond equivalent was 1593, and the weight-average molecular weight was 13000.

[0220] (Preparation of resin-type dispersant (B-8) solution) Commercially available "Disperbyk-111" from Bic Chemie was diluted with propylene glycol monomethyl ether acetate to a solid content of 40% to prepare a solution of resin-type dispersant (B-8).

[0221] (Preparation of resin-type dispersant (B-9) solution) The commercially available "BYK-LPN21116" manufactured by BYK Chemie was diluted by adding propylene glycol monomethyl ether acetate so that the solid content became 40%, and a solution of a resin-type dispersant solution (B-9) was obtained.

[0222] <Method for producing coloring composition> Subsequently, a coloring composition was produced and evaluated.

[0223] [Example 9] (Preparation of coloring composition (RP-1)) After stirring and mixing the following mixture uniformly, it was dispersed using zirconia beads with a diameter of 0.5 mm for 5 hours in an Eiger mill ("Mini Model M-250MKII" manufactured by Eiger Japan Co., Ltd.), and then filtered through a 5.0 μm filter to prepare a coloring composition (RP-1). Red colorant (a-1): 10.8 parts Resin-type dispersant (B-1) solution: 7.5 parts Dye derivative (D-1): 1.2 parts Binder resin solution 1: 25.0 parts Propylene glycol monomethyl ether acetate: 55.5 parts

[0224] [Examples 10 to 26, Comparative Example 2] (Preparation of coloring compositions (RP-2 to 19)) Coloring compositions (RP-2 to 19) were prepared in the same manner as the coloring composition (RP-1), except that the red colorant (a-1), the resin-type dispersant (B-1) solution, and the dye derivative (D-1) were changed to the compositions shown in Table 3.

[0225] [Table 3]

[0226] <Method for producing other coloring compositions> (Preparation of PR254 coloring composition (RP-20)) After stirring and mixing the following mixture until homogeneous, it was dispersed for 3 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 colored composition (RP-20) with 20% by mass of nonvolatile components. Coloring agent (A-1): 12.0 parts Resin-type dispersant (B-1) solution: 7.5 parts Binder resin solution 1:25.0 parts Propylene glycol monomethyl ether acetate (PGMAc): 55.5 parts

[0227] Colored compositions (RP-21) to (VP-1) were prepared in the same manner as colored composition (RP-20), except that colorant (A-1) was changed to one of the colorants shown in Table 4.

[0228] [Table 4]

[0229] <Evaluation of colored compositions> The following evaluations were performed on the colored compositions (RP-1) to (RP-19). The results are shown in Table 5.

[0230] (Contrast ratio (CR) evaluation of the coating film) Light emitted from a liquid crystal display backlight unit is polarized after passing through polarizing plates, then passes through a coating of a colored composition applied to a glass substrate, and reaches the other polarizing plate. In this process, if the polarization planes of the polarizing plates are parallel, the light is transmitted through the polarizing plates, but if the polarization planes are perpendicular, the light is blocked by the polarizing plates. However, when the light polarized by the polarizing plates passes through the coating of the colored composition, scattering occurs due to the coloring agent particles, causing a shift in part of the polarization plane. In this case, when the polarizing plates are parallel, the amount of transmitted light decreases, and when the polarizing plates are perpendicular, some light is transmitted. This transmitted light was measured as luminance on the polarizing plates, and the ratio of the luminance when the polarizing plates are parallel to the luminance when they are perpendicular was calculated as the contrast ratio. (Contrast ratio) = (Brightness when parallel) / (Brightness when perpendicular) Therefore, when scattering occurs due to the colorants in the coating, the brightness decreases when the light is parallel and increases when it is perpendicular, resulting in a lower contrast ratio.

[0231] A colorimeter (Topcon BM-5A) was used as the luminance meter, and a polarizing plate (Nitto Denko NPF-G1220DUN) was used as the polarizing plate. During the measurement, measurements were taken using a black mask with a 1 cm square hole cut into the measurement area.

[0232] Each colored composition was applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater. The substrates were then dried at 70°C for 20 minutes, followed by heating at 230°C for 60 minutes and subsequent cooling to produce coated substrates. The contrast ratio (CR) of the obtained coated substrates was measured. After heat treatment at 230°C, the coated substrates were adjusted to a film thickness of 1.5 μm. The contrast ratio was determined according to the following criteria. ◎: 3000 or more: Excellent ○: 2000 or more, less than 3000: Good △: 1000 or more but less than 2000: Usable ×: Less than 1000: Poor

[0233] (Transmittance evaluation) The obtained colored composition was coated onto a 1.1 mm thick glass substrate using a spin coater, so that the wavelength at which the spectral transmittance was 50% was in the wavelength range of 570 nm to 580 nm. After drying at 60°C for 3 minutes, the substrate was further heated at 230°C for 20 minutes to obtain a coated substrate. The spectrum of the obtained substrate was measured using a micro-spectrophotometer (Olympus Optical Co., Ltd. "OSP-SP200"). The evaluation criteria are as follows. "Transmittance at 530nm" ◎ ··· Transmittance at 530nm is less than 1.0% ○ ··· Transmittance at 530nm is between 1.0% and less than 3.0% × ··· Transmittance of 530nm is 3.0% or higher "Transmittance at 600nm" ◎ ··· Transmittance of 90.0% or higher at 600nm ○ ··· Transmittance at 600nm is between 80.0% and less than 90.0% × ··· Transmittance at 600nm is less than 80.0%

[0234] (Viscosity stability evaluation) The viscosity of the colored composition was measured on the day of preparation using an E-type viscometer (ELD-type viscometer, manufactured by Toki Sangyo Co., Ltd.) at 25°C. Separately, 25g of the colored composition was left to stand in a sealed glass container at 40°C for 24 hours. After the sample temperature returned to 25°C, the viscosity was measured using the same method as above to obtain the viscosity over time. Viscosity stability was evaluated using the following criteria: Viscosity change rate = (Initial viscosity - Viscosity over time) / Initial viscosity × 100 (%). The evaluation criteria are shown below. ○ (Good in practical use): When the viscosity change rate is within ±10% and no sedimentation occurs. △ (Practical): When the viscosity change rate is ±10% to 20% and no sedimentation occurs. × (Not practical): If the viscosity change rate exceeds ±20%, or if sedimentation occurs even if the viscosity change rate is within ±20%.

[0235] (Foreign object detection) Next, we evaluated the generation of foreign matter due to poor dispersion. For the evaluation, we measured the number of foreign matter particles in the colored pixels using the substrate that had been dried at 60°C, which was prepared for the transmittance evaluation. The evaluation was performed by observing the surface using an Olympus Systems BX60 metal microscope. The magnification was set to 500x, and the number of foreign matter particles observable in any five fields of view under transmission was measured. ◎: Fewer than 3 foreign objects: Excellent ○: Number of foreign objects is 3 or more but less than 20: Good △: Number of foreign objects is 21 or more but less than 100: Usable ×: Number of foreign objects is 100 or more: Defective

[0236] [Table 5]

[0237] As shown in Table 5, the colored composition using the colorant (a) of the present invention showed excellent effects in contrast ratio, transmittance, viscosity stability, and foreign matter. The comparative example had problems with contrast ratio and transmittance.

[0238] <Method for producing a photosensitive colored composition> [Example 27] (Red photosensitive coloring composition (RR-1)) A mixture of the following compositions 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). Coloring composition (RP-1): 25.0 parts Coloring composition (RP-21): 25.0 parts Binder resin solution 1:7.5 parts Photopolymerizable monomer ("Arronix M-402" manufactured by Toagosei Co., Ltd.): 2.0 parts Photopolymerization initiator (BASF "Irgacure OXE-02"): 1.2 parts Sensitizer (EAB-F, manufactured by Hodogaya Chemical Co., Ltd.): 0.3 parts Cyclohexanone: 39.0 parts

[0239] [Examples 28-55, Comparative Example 3] (Red photosensitive coloring composition (RR-2~30)) Except for changing the components and parts by mass of the total 50 parts of the colored composition as shown in Table 6, and changing the type of binder resin, red photosensitive colored compositions (RR-2) to (RR-30) were prepared in the same manner as in Example 27.

[0240] <Evaluation of photosensitive colored compositions for color filters> The obtained red photosensitive colored compositions were evaluated as follows. The results are shown in Table 6.

[0241] (Evaluation of solvent resistance) The obtained red photosensitive coloring composition was applied onto a glass substrate on which a black matrix had been previously formed by a spin coating method, and then dried in a clean oven at 70 °C for 20 minutes. Next, after cooling this substrate to room temperature, ultraviolet light was irradiated through a photomask using an ultra-high pressure mercury lamp. Then, this substrate was spray-developed with a 0.2 mass% aqueous sodium carbonate solution at 23 °C for 30 seconds, washed with ion-exchanged water, and dried. Further, a heat treatment was performed in a clean oven at 230 °C for 30 minutes to form a striped colored pixel layer on the substrate. The prepared colored pixel layer was adjusted so that the film thickness became 2.0 μm after the heat treatment at 230 °C. Regarding the obtained striped colored pixels, a microspectrophotometer (「OSP-SP100」manufactured by Olympus Optical Co., Ltd.) was used to measure [L * (1), a * (1), b * (1)]. Then, it was immersed in N-methyl-2-pyrrolidone (NMP) or methanol (MeOH) for 15 minutes, and after immersion, the chromaticity [L * (2), a * (2), b * (2)] was measured, and the color difference ΔE * ab was determined according to the following formula. The solvent resistance was judged according to the following criteria. ΔE * ab = [[L * (2) - L * (1)] 2 + [a * (2) - a * (1)] 2 + [b * (2) - b * (1)] 2 1 / 2 ◎: ΔE * ab < 1: Extremely good ○: ΔE * ab ≥ 1 and < 3: Good △: ΔE * ab ≥ 3 and < 5: Practicable ×: ΔE * ​ab=5 or more: Bad

[0242] (Foreign object detection) For the evaluation of foreign matter, the number of foreign matter particles generated in the colored pixels was measured using substrates that had been heat-treated at 230°C, as prepared for solvent resistance evaluation. The evaluation was performed by surface observation using an Olympus Systems BX60 metal microscope. The magnification was set to 500x, and the number of foreign matter particles observable in any five fields of view was measured using transmission. ◎: Fewer than 3 foreign objects: Excellent ○: Number of foreign objects is 3 or more but less than 20: Good △: Number of foreign objects is 21 or more but less than 100: Usable ×: Number of foreign objects is 100 or more: Defective

[0243] (X-ray diffraction spectrum measurement of coating film) The obtained red photosensitive colored composition was applied to a 1.1 mm thick glass substrate using a spin coater to a film thickness of 0.5 μm. The coating film was then measured using a Bruker D8 ADVANCE. The data was baseline corrected and smoothed before peak detection.

[0244] [Table 6]

[0245] As shown in Table 6, using the colorant (a) of the present invention resulted in excellent solvent resistance and foreign matter content in the photosensitive colored composition. The comparative example showed poor results in terms of foreign matter content.

[0246] <Creating a color filter> A color filter was prepared using the red photosensitive coloring composition of the present invention. The green and blue photosensitive coloring compositions used were prepared as follows.

[0247] (Green photosensitive coloring composition (GR-1)) A mixture of the following compositions was stirred and mixed until homogeneous, and then filtered through a 1 μm pore size filter to prepare a green photosensitive colored composition (GR-1). PG58・Coloring composition (GP-1): 35.0 parts PY138・Coloring composition (YP-1): 15.0 parts Binder resin solution 1:7.5 parts Photopolymerizable monomer ("Arronix M-402" manufactured by Toagosei Co., Ltd.): 2.0 parts Photopolymerization initiator (BASF "Irgacure 907"): 1.2 parts Sensitizer (EAB-F, manufactured by Hodogaya Chemical Co., Ltd.): 0.3 parts Cyclohexanone: 39.0 parts

[0248] (Blue photosensitive coloring composition (BR-1)) A mixture of the following compositions 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). PB15:6・Coloring composition (BP-1): 45.0 parts PV23・Coloring composition (VP-1): 5.0 parts Binder resin solution 1:7.5 parts Photopolymerizable monomer ("Arronix M-402" manufactured by Toagosei Co., Ltd.): 2.0 parts Photopolymerization initiator (BASF "Irgacure 907"): 1.2 parts Sensitizer (EAB-F, manufactured by Hodogaya Chemical Co., Ltd.): 0.3 parts Cyclohexanone: 39.0 parts

[0249] [Example 56] A red photosensitive colored composition (RR-1) was applied to a glass substrate with a pre-formed black matrix by spin coating, and then dried in a clean oven at 70°C for 20 minutes. After the substrate was cooled to room temperature, it was exposed to ultraviolet light through a photomask using an ultra-high pressure mercury lamp. Subsequently, the substrate was spray-developed with a 0.2% by mass sodium carbonate aqueous solution at 23°C for 30 seconds, then washed with deionized water and dried. Furthermore, it was heat-treated in a clean oven at 230°C for 30 minutes to form a striped colored pixel layer on the substrate. Next, a green-colored pixel layer was formed using a green-sensitive coloring composition (GR-1) in the same manner as the red-colored pixel layer. Furthermore, a blue-colored pixel layer was formed using a blue-sensitive coloring composition (BR-1) in the same manner to obtain a color filter (CF-1). The film thickness of each colored pixel layer was 2.0 μm.

[0250] The obtained color filters were checked for the presence or absence of foreign matter on the pixels. The measurement method was the same as that used for evaluating the coloring composition. It was confirmed that the color filters using the photosensitive coloring composition containing the coloring agent (a) of the present invention were free of foreign matter.

[0251] <Manufacturing of photosensitive colored compositions for solid-state image sensors> [Example 57] (Red photosensitive coloring composition (RR-31)) A mixture of the following compositions was stirred and mixed until homogeneous, and then filtered through a 1 μm pore size filter to prepare a red photosensitive colored composition (RR-31). Coloring composition (RP-2): 39.0 parts Coloring composition (YP-2): 11.0 parts Binder resin solution 2:7.5 parts Photopolymerizable monomer ("Arronix M-402" manufactured by Toagosei Co., Ltd.): 2.0 parts Photopolymerization initiator (BASF "Irgacure OXE-02"): 1.2 parts Sensitizer (EAB-F, manufactured by Hodogaya Chemical Co., Ltd.): 0.3 parts Cyclohexanone: 39.0 parts

[0252] [Comparative Example 4] (Red photosensitive coloring composition (RR-32)) Red photosensitive colored compositions (RR-32) were prepared in the same manner as in Example 57, except that the breakdown of the total 50 parts of the colored composition, which is the coloring liquid, was changed to the components and parts by mass shown in Table 7.

[0253] <Evaluation of photosensitive colored compositions for solid-state image sensors> Next, the obtained red photosensitive colored compositions (RR-31~32) were evaluated as photosensitive colored compositions (spectral characteristics) for solid-state image sensors. The results are shown in Table 6.

[0254] (Spectroscopic characterization) The obtained red photosensitive colored composition was coated onto a 1.1 mm thick glass substrate using a spin coater, so that the wavelength at which the spectral transmittance was 50% was in the wavelength range of 580 nm to 590 nm. After drying at 70°C for 20 minutes, the substrate was further heated at 230°C for 60 minutes to obtain a coated substrate. The spectrum of the obtained substrate was measured using a micro-spectrophotometer (Olympus Optical Co., Ltd. "OSP-SP200"). The evaluation criteria are as follows. "Transmittance at 400nm" ◎ ··· Transmittance at 400nm is less than 15.0% ○ ··· Transmittance at 400nm is between 15.0% and less than 20.0% × ··· Transmittance of 400nm is 20.0% or higher "Transmittance at 530nm" ◎ ··· Transmittance at 530nm is less than 1.0% ○ ··· Transmittance at 530nm is between 1.0% and less than 3.0% × ··· Transmittance of 530nm is 3.0% or higher "Transmittance at 600nm" ◎ ··· Transmittance of 90.0% or higher at 600nm ○ ··· Transmittance at 600nm is between 80.0% and less than 90.0% × ··· Transmittance at 600nm is less than 80.0%

[0255] [Table 7]

[0256] As shown in Table 7, when using the colorant (a) of the present invention, it was possible to achieve both spectral characteristics at 400, 530, and 600 nm.

[0257] (Fabrication of color filters for solid-state image sensors) On a 6-inch silicon wafer, a resist solution for planarization (HL-18s: manufactured by Nippon Steel Chemical Co., Ltd.) is applied. The material was applied by spin coating, and as a pre-bake, it was heated on a hot plate at 100°C for 6 minutes. Furthermore, it was treated in an oven at 230°C for 1 hour to cure the coated film and form a 1.0 μm planarization film, obtaining a wafer with a planarization film.

[0258] A green photosensitive coloring composition (GR-1) was applied to a silicon wafer with a planarization film using a spin coater, and then pre-baked by heating on a hot plate at 100°C for 1 minute. The film thickness after pre-baking was adjusted to 0.9 μm.

[0259] Next, using an i-line stepper exposure system FPA-3000i5+ (manufactured by Canon Corporation), an exposure dose of 150 mJ / cm² was applied through a photomask to form 1.0 μm square red pixels at a wavelength of 365 nm. 2 Pattern exposure was performed.

[0260] The paint film after exposure was paddle-developed with an organic alkaline developer for 1 minute. After paddle development, 2 The hair was rinsed with pure water using a spin shower for 0 seconds, and then rinsed again with pure water for 20 seconds. Subsequently, any remaining water droplets on the wafer were blown away with high-pressure air, the substrate was allowed to air dry, and then it was heated on a hot plate at a surface temperature of 230°C for 5 minutes to form a square pixel pattern. The film thickness of the green pattern after heat treatment was 0.80 μm.

[0261] Next, a red-colored pixel layer was formed using a red-sensitive coloring composition (RR-31) in the same manner as the green-colored pixel layer. Furthermore, a blue-colored pixel layer was formed using a blue-sensitive coloring composition (BR-1) to obtain a color filter (CF-2).

[0262] The solid-state image sensor color filters fabricated in this manner exhibited excellent spectral characteristics. In particular, the red filter showed excellent transmission around 600 nm and superior heat resistance. As a result, solid-state image sensors using these color filters exhibited particularly excellent skin tone reproduction. [Explanation of Symbols]

[0263] 10 LCD display device 11 Transparent substrate 12 TFT arrays 13 Transparent electrode layer 14. Orientation layer 15 Polarizing plates 21 Transparent substrate 22 Color Filters 23 Transparent electrode layer 24 orientation layer 25 Polarizing plates 30 backlight units 31 White LED light source LC LCD

Claims

1. A colorant (a) containing a methylated diketopyrrolopyrrole pigment represented by the following chemical formula (1), wherein the X-ray diffraction pattern by CuKα rays is such that the Bragg angle 2θ (±0.3) = A colorant (a) having diffraction peaks at 15.7° and 27.0°, and having a crystal type in which the intensity ratio (H2 / H1) when the diffraction intensity at 15.7° is H1 and the diffraction intensity at 27.0° is H2 is between 1.5 and 2.

6. Chemical formula (1) 【Chemistry 1】

2. The colorant (a) according to claim 1, having a crystal type in which the intensity ratio (H2 / H1) in the X-ray diffraction pattern by CuKα rays is 1.5 or more and 1.9 or less.

3. When a colored film is formed, in the X-ray diffraction of the colored film using CuKα rays, the diffraction angle 2θ (±0.3) = The coloring agent according to claim 1 or 2, characterized by having a maximum peak at 27.0°.

4. Color filter containing a coloring agent (A), a resin-type dispersant (B), and an organic solvent (C). A coloring composition for color filters, wherein the coloring agent (A) contains the coloring agent (a) described in claim 1.

5. The coloring agent (A) further contains at least one pigment selected from the group consisting of C.I. Pigment Red 177, 254, 269, 291, C.I. Pigment Orange 71, 73, C.I. Pigment Yellow 138, 139, 150, 185, and 231. The coloring composition for color filters according to claim 4.

6. The coloring composition for color filters according to claim 4, further containing a dye derivative (D).

7. The dye derivative (D) is a diketopyrrolopyrrole, azo, quinophthalone, and thia Claim 6 contains at least one dye derivative selected from the group consisting of din-based derivatives. The coloring composition for color filters described above.

8. The resin-type dispersant (B) comprises a polymer having at least one hydroxyl group at one end and tricarbon A coloring composition for color filters according to any one of claims 4 to 7, wherein the reaction product is obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product with an acidic anhydride or tetracarboxylic dianhydride and / or a reaction product between the hydroxyl group of a compound having a hydroxyl group and the acid anhydride group of a tricarboxylic anhydride or tetracarboxylic dianhydride.

9. Furthermore, the coloring composition for color filters according to claim 4 further contains a polymerizable compound (E) and / or a photopolymerization initiator (F).

10. The photopolymerization initiator (F) contains an oxime ester-based photopolymerization initiator, as described in claim 9. A coloring composition for color filters.

11. Furthermore, the coloring composition for color filters according to any one of claims 4, 6, or 9, further comprising a binder resin (G).

12. The binder resin (G) contains an alkali-soluble resin having an ethylenically unsaturated double bond. A coloring composition for color filters according to claim 11.

13. A cured film obtained by curing a coloring composition for color filters according to any one of claims 4, 6, or 9.

14. A color filter having the cured film described in claim 13.

15. A liquid crystal display device comprising the color filter described in claim 14.

16. A solid-state image sensor comprising the color filter described in claim 14.

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