Colored compositions, cured films, optical filters, image display devices, solid-state image sensors, and infrared sensors

Abstract

The present invention aims to provide a colored composition that exhibits high visible light shielding properties due to its high coloring power and also has near-infrared transmittance, as well as a cured film, optical filter, image display device, solid-state image sensor, and infrared sensor using the same. [Solution] The problem can be solved by a coloring composition in which, when a film with a thickness of 0.7 μm is formed, the average transmittance of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 650 nm is 2.5% or less, and the average transmittance of the light transmittance in the thickness direction of the film in the wavelength range of 800 to 1000 nm is 90% or more, and the composition contains a coloring agent (A) containing CI pigment violet 37 and CI pigment yellow 139, and a resin-type dispersant (B), and is characterized in that, with a total pigment of 100 parts by mass, CI pigment violet 37 is 25 to 75 parts by mass and CI pigment yellow 139 is 25 to 45 parts by mass.

Description

[Technical Field]

[0001] The present invention relates to a colored composition, a cured film, an optical filter, an image display device, a solid-state image sensor, and an infrared sensor. [Background technology]

[0002] Currently, touch panels are widely used as input means for various liquid crystal display devices that incorporate display panels such as liquid crystal display panels, such as ticket vending machines and ATMs. Touch panels can detect when a detected object (detected object), such as the operator's fingers or a dedicated input device, touches or approaches the display surface of the display device, and can also identify the position on the display surface where the detected object touches or approaches. For this reason, touch panels are used as a means of inputting information related to the display content of the display device in a very direct manner.

[0003] Furthermore, in recent years, various biometric authentication methods have been adopted in various information terminals such as smartphones and tablet PCs to enhance security. In addition to conventional fingerprint authentication, facial recognition and iris recognition are being considered, and near-infrared sensors and near-infrared cameras are used for facial recognition and iris recognition. In automobiles, near-infrared sensors are used for motion sensors in in-car displays, near-infrared cameras are used for driver surveillance cameras, and infrared laser sensors are used for driving space sensors.

[0004] Furthermore, in order to form a black frame that transmits infrared rays, it has been considered to use a material that is pseudo-blackened by mixing red and blue pigments (see, for example, Patent Documents 1 and 2). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2012 / 157222 [Patent Document 2] Japanese Patent Publication No. 2018-169539 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] The present invention aims to provide a colored composition that exhibits high visible light shielding properties due to its high coloring power and also has near-infrared transmittance, as well as a cured film, optical filter, image display device, solid-state image sensor, and infrared sensor using the same. [Means for solving the problem]

[0007] As a result of diligent research, the present inventors have solved the above problem by using a coloring composition in which, when a film with a thickness of 0.7 μm is formed, the average transmittance of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 650 nm is 2.5% or less, and the average transmittance of the light transmittance in the thickness direction of the film in the wavelength range of 800 to 1000 nm is 90% or more, and the composition contains a coloring agent (A) containing CI pigment violet 37 and CI pigment yellow 139, and a resin-type dispersant (B), wherein the total pigment is 100 parts by mass, and the composition contains 25 to 75 parts by mass of CI pigment violet 37 and 25 to 45 parts by mass of CI pigment yellow 139. To achieve visible light blocking, it is effective to reduce the transmittance in the 400-700nm wavelength range to the absolute minimum. Even when using a combination of organic pigments instead of black pigments, it is necessary to reduce the transmittance in the 400-700nm wavelength range to the absolute minimum, that is, to bring the transmittance across the entire wavelength range close to zero. However, conventionally, because there is a maximum transmittance value between 400 and 700nm wavelengths, the transmittance in this range could not be reduced sufficiently, and adequate visible light blocking could not be obtained. In this invention, by adjusting the pigment types and their proportions, it was found that even when the values ​​are slightly higher due to the presence of maximum or maximum values ​​near one of the wavelengths 400, 450, 500, 550, 600, or 650 nm, maintaining an average transmittance of 2.5% or less in the 400-650 nm wavelength range is effective for light shielding in the visible light region. By using a colored composition characterized by containing 100 parts by mass of total pigments, 25-75 parts by mass of CI Pigment Violet 37, and 25-45 parts by mass of CI Pigment Yellow 139, the problem of visible light shielding, which is the issue of this invention, has been solved. [Effects of the Invention]

[0008] In the present invention, by using a coloring composition containing a coloring agent (A) containing CI pigment violet 37 and CI pigment yellow 139, and a resin-type dispersant (B), wherein the total pigment is 100 parts by mass, CI pigment violet 37 is 25 to 75 parts by mass and CI pigment yellow 139 is 25 to 45 parts by mass, a cured film can be obtained in which, when a film thickness of 0.7 μm is formed, the average transmittance of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 650 nm is 2.5% or less, and the average transmittance of the light transmittance in the thickness direction of the film in the wavelength range of 800 to 1000 nm is 90% or more, and a high-performance optical filter, image display device, solid-state image sensor, and infrared sensor can be provided using this. [Brief explanation of the drawing]

[0009] [Figure 1] Figure 1 is a schematic cross-sectional view of an image display device. [Figure 2] Figure 2 is a schematic cross-sectional view of an infrared sensor. [Modes for carrying out the invention]

[0010] 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.

[0011] <Coloring agent (A)> The coloring composition of the present invention contains a coloring agent (A) comprising CI Pigment Violet 37 and CI Pigment Yellow 139.

[0012] When a film with a thickness of 0.7 μm is formed, in order for the average light transmittance in the thickness direction of the film in the wavelength range of 400 to 650 nm to be 2.5% or less, and the average light transmittance in the thickness direction of the film in the wavelength range of 800 to 1000 nm to be 90% or more, it is necessary to include 25 to 75 parts by mass of CI Pigment Violet 37 and 25 to 45 parts by mass of CI Pigment Yellow 139, with a total pigment of 100 parts by mass.

[0013] Furthermore, the mixture may contain 0 to 35 parts by mass of any blue pigment selected from CI Pigment Blue 15:1, 15:2, 15:3, 15:4, or 15:6, per 100 parts by mass of the total pigment.

[0014] When a film with a thickness of 0.7 μm is formed, the average transmittance of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 650 nm is 2.5% or less, and the average transmittance of the light transmittance in the thickness direction of the film in the wavelength range of 800 to 1000 nm is 90% or more. By doing so, unnecessary light in the visible light region is reduced, and the transmittance in the near-infrared region becomes high, so that a high-quality near-infrared transmission film can be produced.

[0015] The average transmittance in the wavelength range of 400 to 650 nm is the average of the values for each 1 nm from 400 to 650 nm, and the average transmittance in the wavelength range of 800 to 1000 nm is the average of the values for each 1 nm from 800 to 1000 nm.

[0016] Other blue pigments and other color pigments can be used within the range that satisfies the optical properties of the present invention. Specific examples are shown below.

[0017] Examples of the yellow pigment include C.I. 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, 8, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, a152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, a185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233. Preferably, they are C.I. Pigment Yellow 138, 139, 150, 185, 231, 233.

[0018] Examples of blue pigments other than C.I. Pigment Blue 15:1, 15:2, 15:3, 15:4 or 15:6 include, for example, C.I. 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, 79, etc.

[0019] Examples of red pigments include, for example, C.I. 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, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296.

[0020] 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, 39, 42, 44, 47, 49, and 50.

[0021] Examples of green pigments include 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, and 63.

[0022] In addition, examples of 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 oxide green, cobalt green, amber, and synthetic iron black.

[0023] <Pigment miniaturization> When using organic pigments as colorants, it is preferable to mix them with other raw materials after micronization. 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 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] During the salt milling process, a resin may be added as needed. Examples of resins include natural resins, 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.

[0028] <Metal Removal> If specific metal elements are present in large quantities as impurities other than the pigment components in the colored composition, it can impair the dispersion stability over time, and may also reduce heat resistance or sensitivity. Furthermore, color filters made using such compositions may develop foreign matter, which can easily lead to a decrease in brightness. It is preferable that the total content of Li, Na, K, Mg, Ca, Fe, Al, and Cr (hereinafter also referred to as specific metal elements) in the colored composition is 500 ppm by mass or less.

[0029] The total amount of specific metal elements contained in the coloring composition is more preferably 300 ppm by mass or less, and particularly preferably 200 ppm by mass or less. The lower limit of the total amount of specific metal elements is not particularly limited, but is preferably 1 ppm by mass or more, and more preferably 5 ppm by mass or more. Within the above range, a coloring composition can be obtained that suppresses costs, has excellent storage stability, and forms a color filter with minimal generation of foreign matter and reduction in brightness.

[0030] The amount of each specific metal element contained in the coloring composition is preferably 100 ppm by mass or less, and more preferably 50 ppm by mass or less.

[0031] Furthermore, it is preferable that the metals that make up the pigment, such as Ni, Zn, Cu, Al, Fe, Fe, Co, and Co, contain fewer impurities that do not function effectively, and these can be removed in the same way as specific metal elements by the following method. In addition, it is preferable that the concentrations of Mn, Cs, Ti, Co, Si, Pd, etc., that have been introduced due to materials used in the manufacturing process of the various raw materials of the coloring composition (for example, catalysts) be low.

[0032] Methods for removing colorants (A) or metals introduced from equipment 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 for removing magnetic foreign matter using a magnet as described in Japanese Patent Publication No. 2011-48736, and one or more of these methods may be used as appropriate.

[0033] The content of specific metal elements can be measured by inductively coupled plasma atomic emission spectroscopy (ICP).

[0034] <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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] <Dye derivatives> Dye derivatives may be used in the colored composition as needed. Dye derivatives are compounds having acidic groups, basic groups, neutral groups, etc., in organic dye residues. Examples of dye derivatives include compounds having acidic substituents such as sulfo groups, carboxyl groups, or phosphate groups, 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 phenyl groups or phthalimidoalkyl groups. 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.

[0039] 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; phthalocyanine dye derivatives are described in Japanese Patent Publication No. 2007-226161, WO2016 / 163351, Japanese Patent Publication No. 2017-165820, and Japanese Patent No. 5753266; and anthraquinone dye derivatives are described in Japanese Patent Publication No. 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, Brochure WO2009 / 025325, Quinacridone-based dye derivatives are Japanese Patent Publication No. 48-54128, Japanese Patent Publication No. 03-9961, Japanese Patent Publication No. 2000-273383, Dioxazine-based dye derivatives are Japanese Patent Publication No. 2011-162662, Thiazine-indigo-based dye derivatives are Japanese Patent Publication No. 2007-3147 Japanese Patent Publication No. 85, Triazine-based dye derivatives are described in Japanese Patent Publication No. 61-246261, Japanese Patent Publication No. 11-199796, 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, Japanese Patent Publication No. 2008-31281, Japanese Patent Publication No. 2 Examples of dye derivatives include those described in Japanese Patent Publication No. 012-226110, those described in Japanese Patent Publication Nos. 2012-208329 and 2014-5439 for naphthol-based dye derivatives, those described in Japanese Patent Publication Nos. 2001-172520 and 2012-172092 for azo-based dye derivatives, those described in Japanese Patent Publication Nos. 2004-307854 for acidic substituents, and those described in Japanese Patent Publication Nos. 2002-201377, 2003-171594, 2005-181383 and 2005-213404 for basic substituents. 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.

[0040] These dye derivatives can be used individually or in combination of two or more types.

[0041] The dye derivative is preferably added in an amount of 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, and even more preferably 5 to 50 parts by mass, per 100 parts by mass of pigment.

[0042] By adding a pigment derivative to a pigment and performing pigmentation treatments such as acid basting, acid slurry, dry milling, salt milling, or solvent-salt milling, the pigment derivative is adsorbed onto the pigment surface, making the primary particles of the pigment finer compared to when no pigment derivative is added.

[0043] By adding a dye derivative to the pigment and performing dispersion treatments such as wet dispersion using two-roll, three-roll, or bead-based processes, the dye derivative is adsorbed onto the pigment surface, giving the pigment surface polarity and promoting the adsorption of resin-type dispersants. This improves compatibility with the pigment, dye derivative, resin-type dispersant, solvent, and other additives, resulting in improved dispersion stability and viscosity stability over time when used in colored compositions and colored curable compositions. Furthermore, the improved compatibility leads to excellent film stability over time when colored curable compositions are coated onto glass substrates, etc., resulting in good stability and property dependence of pattern shape, etc., on 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 good line width sensitivity stability. In addition, the adsorption and coating of the pigment surface with the dye derivative and resin-type dispersant suppresses pigment aggregation and crystal precipitation due to sublimation when the coating film is heated and fired. Furthermore, variations in development time and development residue are also suppressed.

[0044] <Resin-type dispersant (B)> The colored composition of the present invention can use known resin-type dispersants. 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, and variations thereof. Oily dispersants such as amides and their salts formed by the reaction of poly(lower alkyleneimines) with polyesters having free carboxyl groups, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide adduct compounds, and phosphate ester-based compounds can be used, and these can be used individually or in combination of two or more.

[0045] A preferred example of a resin-type dispersant having an acidic functional group is a resin-type dispersant (B1) having an aromatic carboxylic acid structure, which can be manufactured by known methods such as those described in WO2008 / 007776, JP 2008-029901, JP 2009-155406, JP 2010-185934, JP 2011-157416, JP 2009-251481, JP 2007-23195, and JP 1996-143651.

[0046] Particularly preferred examples of resin-type dispersants having acidic functional groups include those having a main chain containing an aromatic carboxylic acid ester moiety having an ester bond, obtained by esterifying an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups, and a side chain containing a vinyl polymer moiety. The ratio of acid anhydride groups to 1 mole of hydroxyl groups is 0.9 to 1.5 moles, preferably 1.0 to 1.3 moles. Furthermore, the main chain containing the aromatic carboxylic acid ester moiety has a structure having a encapsulation site derived from a monoalcohol, which will be described later. That is, the acid anhydride group remaining in the main chain is ring-opened with a monoalcohol, resulting in the presence of an alcohol ester group and a carboxyl group. By using such a resin-type dispersant (B), the filterability of the colored composition is improved, the generation of foreign matter in the coating film formed by coating the colored composition is suppressed, and furthermore, when coating the colored composition, the resolubility of the solidified material derived from the colored composition formed in the coating apparatus in propylene glycol monomethyl ether acetate is improved, thus improving productivity. In this invention, the side chains based on the vinyl polymer moiety are formed by polymerization of ethylenically unsaturated monomers. The total monomer units constituting the vinyl polymer moiety refer to the substructures derived from each ethylenically unsaturated monomer after vinyl polymerization.

[0047] (Aromatic compounds having two or more acid anhydride groups) Aromatic compounds having two or more acid anhydride groups include, for example, pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and 2,3,6,7-naphthalene Tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether Examples include dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, or 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic acid dianhydride.

[0048] (Compounds having two or more hydroxyl groups) As described above, compounds having two or more hydroxyl groups are preferably compounds having a hydroxyl group and a thiol group in the molecule, and more preferably compounds having two hydroxyl groups and one thiol group in the molecule.

[0049] Examples of compounds having two hydroxyl groups and one thiol group in their molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, or 2-mercaptoethyl-2-ethyl-1,3-propanediol.

[0050] (Monoalcohol) Monoalcohols include, for example, methanol, ethanol, 1-butanol, 2-butanol, isobutanol, t-butanol, 1-pentanol, isopentyl alcohol, tert-pentyl alcohol, cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, isononyl alcohol, 1-nonyl alcohol, amyl alcohol, lauryl alcohol, n-butyl alcohol, isobutyl alcohol, cyclohexanol, benzyl alcohol, methylcyclohexanol, and other monoalcohols. Monoalcohols having an ether group, such as 3-methoxy-3-methyl-1-butanol, 3-methoxybutanol, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, etc. Examples include monoalcohols having a carbonyl group, such as methyl lactate, ethyl lactate, and diacetone alcohol. These can be used individually or in combination of two or more.

[0051] The monoalcohol is preferably a compound having an ether group or a carbonyl group. The dispersant may have an ether group or a carbonyl group at the end of its main chain, improving the resolubility of the dispersant in PGMAc. Among these, 3-methoxybutanol, propylene glycol monomethyl ether, and diacetone alcohol are preferred.

[0052] The main chain, which is an aromatic carboxylic acid ester moiety, may have encapsulation sites derived from monoalcohols, as well as encapsulation sites formed by reaction with water.

[0053] Regarding the synthesis of the encapsulation site, the amount of monoalcohol used relative to the acid anhydride group is preferably 1 to 30 molar equivalents, and more preferably 1.5 to 20 molar equivalents, per equivalent of acid anhydride group remaining in the main chain. If the amount is 1 molar equivalent or more, no acid anhydride group remains, resulting in good storage stability. If the amount is 30 molar equivalents or less, transesterification reactions due to ester bonding between the monoalcohol and the dispersant are less likely to occur, and a decrease in molecular weight is less likely to occur.

[0054] (Side chains, which are vinyl polymer components) The side chains of the resin-type dispersant are obtained by polymerizing a vinyl polymerizable compound in the presence of a compound having a thiol group. When a compound having two hydroxyl groups and one thiol group in its molecule is used as the compound having the thiol group, the main chain is formed after the side chain is formed. Furthermore, if the compound having the thiol group is the main chain after the esterification reaction (which has multiple thiol groups derived from a compound having two hydroxyl groups and one thiol group in its molecule), then side chains are formed after the main chain is formed.

[0055] Preferred 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.

[0056] 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).

[0057] The resin-type dispersant (B) is preferably used in an amount of 3 to 200% by mass relative to the total amount of colorant, and more preferably in an amount of 5 to 100% by mass from the viewpoint of film formation.

[0058] <Binder resin (C)> The colored compositions of this specification may include a binder resin (C). The binder resin (C) is a resin with a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm. Preferably, the transmittance in the entire wavelength range of 400 to 700 nm is 95% or more. In terms of curability, examples of binder resin (C) include thermoplastic resins, thermosetting resins, and active energy ray curable resins. The active energy ray curable resin may be a thermoplastic resin or a thermosetting resin having an active energy ray reactive functional group. In terms of physical properties, the binder resin (C) is preferably an alkali-soluble resin from the viewpoint of developability. Alkali solubility is necessary to provide developability in the alkali development process when manufacturing color filters, and an acidic group is required.

[0059] Binder resin (C) can be used alone or in combination of two or more types.

[0060] The binder resin (C) content is preferably 20 to 400 parts by mass, and more preferably 50 to 250 parts by mass, per 100 parts by mass of colorant. Including an appropriate amount allows for easy film formation and facilitates obtaining good color characteristics.

[0061] <Thermoplastic resin> Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclic rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. Examples of alkali-soluble thermoplastic resins include resins having acidic groups such as carboxyl groups and sulfone groups. Examples of alkali-soluble thermoplastic resins include acrylic resins having acidic groups, α-olefin / (anhydride) maleic acid copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, or isobutylene / (anhydride) maleic acid copolymers. Among these, acrylic resins having acidic groups and styrene / styrene sulfonic acid copolymers are preferred in terms of improved developability, heat resistance, and transparency.

[0062] <Activated energy ray curable resin> Active energy ray curable resins preferably have ethylenically unsaturated double bonds. Ethyleneenly unsaturated double bonds can be introduced, for example, by the method shown in (i) or (ii) below. Curing with active energy rays causes the resin to undergo three-dimensional crosslinking, increasing the crosslinking density and improving chemical resistance.

[0063] [Method (i)] Method (i) involves, for example, adding a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond to the side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with another monomer. Then, the resulting hydroxyl group is reacted with a polybasic acid anhydride to introduce an ethylenically unsaturated double bond and a carboxyl group.

[0064] Examples of ethylenically unsaturated 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. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with unsaturated monobasic acids.

[0065] 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.

[0066] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. Furthermore, if necessary, such as increasing the number of carboxyl groups, tricarboxylic acid anhydrides such as trimellitic anhydride or tetracarboxylic dianhydrides such as pyromellitic dianhydride may be used to hydrolyze the remaining anhydride groups.

[0067] Other monomers include the following: For example, (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate. Alternatively, examples include (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or styrenes such as acryloylmorpholine, or styrenes such as α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, and vinyl fatty acid compounds such as vinyl acetate or vinyl propionate.

[0068] Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide Examples include imidobenzoates, N-succinimidyl-3-maleimidepropionate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimidehexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimideacridine, and other N-substituted maleimides; EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

[0069] A method similar to method (i) is, for example, a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with another monomer, to which an ethylenically unsaturated monomer having an epoxy group is added to some of the side chain carboxyl groups of the copolymer, thereby introducing an ethylenically unsaturated double bond and a carboxyl group.

[0070] [Method (ii)] Method (ii) involves reacting the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group with the isocyanate group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another monomer.

[0071] Examples of ethylenically unsaturated monomers having hydroxyl groups include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate. Also included are polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to hydroxyalkyl (meth)acrylates, and polyester mono(meth)acrylates obtained by adding polyγ-valerolactone, polyε-caprolactone, and / or poly12-hydroxystearic acid. From the viewpoint of suppressing foreign matter in the coating film, 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferred, and from the viewpoint of sensitivity, it is preferable to use a material having 2 to 6 hydroxyl groups, with glycerol mono(meth)acrylate being even more preferred.

[0072] Examples of ethylenically unsaturated monomers having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0073] Other monomers that can constitute alkali-soluble resins include, in addition to the other ethylenically unsaturated monomers already described, N-substituted maleimides, alkylene oxy group-containing monomers, phosphate ester group-containing ethylenically unsaturated monomers, carboxyl group-containing ethylenically unsaturated monomers, and the like. N-substituted maleimides include, for example, cyclohexyl maleimide, phenyl maleimide, methyl maleimide, ethyl maleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-( Examples include 2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzoimidazolyl)phenyl]maleimide, and 9-maleimidacridine. Examples of alkylene oxy group-containing monomers include EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

[0074] For carboxyl group-containing ethylenically unsaturated monomers, the monomers already described can be used.

[0075] Phosphate ester group-containing ethylenically unsaturated monomers are, for example, compounds obtained by reacting the hydroxyl group of the above-mentioned hydroxyl group-containing ethylenically unsaturated monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphate.

[0076] <Alkali-soluble resin without ethylenically unsaturated double bonds> The coloring compositions of this specification may contain alkali-soluble resins that do not have ethylenically unsaturated double bonds in order to adjust the degree of curing of the coating.

[0077] In this invention, the weight-average molecular weight (Mw) of the alkali-soluble resin is 2,000 to 40,000, preferably 3,000 to 30,000, and more preferably 4,000 to 20,000, in order to impart alkali-developable solubility. Furthermore, the Mw / Mn value is preferably 10 or less. If the weight-average molecular weight (Mw) is less than 2,000, adhesion to the substrate decreases, and the exposure pattern becomes difficult to retain. If it exceeds 40,000, alkali-developable solubility decreases, residue is generated, and the linearity of the pattern deteriorates. In this invention, the acid value of the alkali-soluble resin is 50 to 200 (KOH mg / g) to impart alkali-developable solubility, preferably in the range of 70 to 180, and more preferably in the range of 90 to 170. If the acid value is less than 50, alkali-developable solubility decreases, residue is generated, and the linearity of the pattern deteriorates. If it exceeds 200, adhesion to the substrate decreases, and the exposure pattern becomes difficult to retain.

[0078] Each raw material used in the synthesis of the binder resin (C) can be used individually or in combination of two or more types.

[0079] <Thermosetting compound (CE)> In the present invention, the binder resin (C) can be used in combination with a thermoplastic resin and may also contain a thermosetting compound (CE). When producing a color filter using the coloring composition for color filters of the present invention, the inclusion of the thermosetting compound (CE) 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.

[0080] The thermosetting compound (CE) may be a low-molecular-weight compound or a high-molecular-weight compound such as a resin. Examples of thermosetting compounds (CE) 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 present invention, epoxy compounds and oxetane compounds are preferably used.

[0081] <Polymerizable compound (D)> Polymerizable compound (D) is a monomer or oligomer containing a polymerizable unsaturated group. Examples of polymerizable compound (D) include hydroxyl group-containing monomers, acid group-containing monomers, urethane bond-containing monomers, and other monomers. Examples of polymerizable unsaturated groups include vinyl groups, (meth)acryloyl groups, and (meth)allyl groups. Oligomers are compounds with a molecular weight of 1000 or more.

[0082] (Hydroxyl group-containing monomer) The hydroxyl group-containing monomer is preferably compound (D1) represented by general formula (1). A film containing the compound represented by general formula (1) has increased solubility in alkaline developers due to the action of the hydroxyl group, which suppresses development residue. Furthermore, the presence of the hydroxyl group results in the film having highly polar hydrophilic sites, making it difficult for nonpolar oxygen molecules to coexist. This reduces polymerization inhibition by oxygen during exposure, making it easier to create highly rectangular patterns. General formula (1) [ka]

[0083] However, in general formula (1), X is a substructure shown in general formula (2), general formula (3), or general formula (4) below. 1 , R 2 represents a hydrogen atom or a methyl group. [ka]

[0084] In general formula (2), n represents an integer from 1 to 4, and R 3 represents a hydrogen atom or a methyl group. In general formula (3), n represents an integer from 1 to 4. In general formula (4), n represents an integer from 1 to 4.

[0085] Examples of compounds represented by general formula (1) (D1) include ethylene glycol diglycidyl ether diacrylate, diethylene glycol diglycidyl ether diacrylate, triethylene glycol diglycidyl ether diacrylate, tetraethylene glycol diglycidyl ether diacrylate, propylene glycol diglycidyl ether diacrylate, dipropylene glycol diglycidyl ether diacrylate, tripropylene glycol diglycidyl ether diacrylate, tetrapropylene glycol diglycidyl ether diacrylate, 1,3-propanediol diglycidyl ether diacrylate, butylene glycol diglycidyl ether diacrylate, glycerin diglycidyl ether diacrylate, diglycerin diglycidyl ether diacrylate, triglycerin diglycidyl ether diacrylate, and tetraglycerin diglycidyl ether diacrylate. Among these, propylene glycol diglycidyl diacrylate is more preferred in terms of polymerizable unsaturated group equivalent and inter-polymerizable unsaturated group distance, and glycerin diglycidyl ether diacrylate is more preferred in terms of hydroxyl group equivalent. Both contribute to improved curability, making it easier to create highly rectangular patterns.

[0086] The content of the compound represented by general formula (1) is preferably 1 to 50% by mass, and more preferably 2 to 40% by mass, based on 100% by mass of the nonvolatile content of the colored composition.

[0087] (Acid group-containing monomer) Examples of acidic groups in acidic monomers include sulfonic acid groups, carboxyl groups, and phosphate groups.

[0088] Examples of acid group-containing monomers include esters of polyhydric alcohols and (meth)acrylic acid-containing poly(meth)acrylates with free hydroxyl groups and dicarboxylic acids; and esters of polyhydric acids and 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.

[0089] (Urethane bond-containing monomer) Examples of urethane bond-containing 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.

[0090] Examples of hydroxyl group-containing (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, dipentaerythritol caprolactone-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 polyacrylates.

[0091] Examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanates.

[0092] (Other monomers) Other monomers 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, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanurate EO-modified di(meth)acrylate, isocyanurate EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pe Examples include tetraerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, various acrylic acid esters and methacrylic acid esters such as methylolated melamine (meth)acrylate, epoxy(meth)acrylate, and urethane acrylate, as well as (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, and acrylonitrile.

[0093] Polymerizable compound (D) can be used alone or in combination of two or more types.

[0094] The amount of polymerizable compound (D) 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. Adding an appropriate amount further improves curability and developability.

[0095] <Photopolymerization initiator (E)> Various photopolymerization initiators can be used as the photopolymerization initiator (E), but in this specification, oxime ester-based photopolymerization initiators are preferred. Oxime ester-based photopolymerization initiators undergo cleavage of the NO bond in the oxime upon absorption of ultraviolet light, generating iminyl radicals and alkyloxy radicals. These radicals further decompose to generate highly reactive radicals, resulting in improved photocurability as patterns can be formed with less exposure compared to using other photopolymerization initiators.

[0096] Examples of oxime ester-based photopolymerization initiators include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. Commercially available oxime compounds include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (all manufactured by BASF Japan), TR-PBG-304, TR-PBG-305, TR-PBG-3057, TR-PBG-345, TR-PBG-358 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Optomer N-1919, ADEKA Arclus NCI-730, NCI-831, and NCI-930 (manufactured by ADEKA).

[0097] Oxime ester-based photopolymerization initiators include monooxime-based initiators having one oxime ester group and a carbazole, fluorene, or diphenyl skeleton in the molecule, and dioxime-based initiators having two oxime ester groups. Furthermore, preferred specific structures of oxime ester-based photopolymerization initiators include, for example, hydroxyl groups, nitro groups, carbonyl groups, fluorocarbon groups, and benzofurans.

[0098] (Oxime ester photopolymerization initiator with a carbazole skeleton) [ka] JPEG2026057784000005.jpg121170

[0099] (Oxime ester photopolymerization initiator having a fluorene skeleton) [ka]

[0100] (Oxime ester-based photopolymerization initiators having a diphenyl skeleton) [ka]

[0101] (Photopolymerization initiator having two oxime ester groups) Examples of photopolymerization initiators include those having two oxime ester groups on either side of a carbazole skeleton or a phenothiazine skeleton, as shown below. [ka]

[0102] The photopolymerization initiator (E) preferably contains one or more oxime ester compounds selected from the group consisting of (E1), (E2), and (E3) below, among the oxime ester photopolymerization initiators described above. Using these oxime ester compounds further improves rectangularity and adhesion. (E1) Compounds having two oxime ester groups and a carbazole skeleton. A compound having two (E2) oxime ester groups and a phenothiazine skeleton. (E3) Compounds represented by the following general formula (5) General formula (5) [ka]

[0103] In general formula (5), R 2 R represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. 3 R represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. 4 R represents a branched alkyl group or cyclic organic group having 6 or more carbon atoms. 5 represents a monovalent substituent (excluding oxime ester groups). n represents an integer from 0 to 3.

[0104] (E1) The following are examples of compounds having two oxime ester groups and a carbazole skeleton. [ka]

[0105] The following are examples of compounds having two (E2) oxime ester groups and a phenothiazine skeleton. [ka]

[0106] Examples of compounds represented by general formula (5) are given below. [ka] JPEG2026057784000013.jpg126170

[0107] For the photopolymerization initiator (E), other polymerization initiators other than oxime ester-based photopolymerization initiators can be used. Other photopolymerization initiators include, 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 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; and titanocene compounds.

[0108] The amount of photopolymerization initiator (E) is preferably 0.1 to 20 parts by mass, and more preferably 0.2 to 10 parts by mass, per 100 parts by mass of the nonvolatile content of the colored composition. When an appropriate amount is added, the photocurability and developer resistance are improved, and the surface condition of the coating tends to become smoother.

[0109] <Sensitizer> Furthermore, the coloring composition 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, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiaidine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyradinoporphyrazine derivatives. Examples include phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxaliloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrillium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospilopyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxyesters, acylphosphine oxides, methylphenylglyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like.

[0110] Among the sensitizers mentioned above, thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives are particularly suitable for sensitizing. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N-ethylcarbazole, etc., can be used.

[0111] 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.

[0112] Sensitizers can be used alone or in combination of two or more types.

[0113] The sensitizer content is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass, per 100 parts by mass of the photopolymerization initiator. Including an appropriate amount further improves curability and developability.

[0114] <Thiol-based chain transfer agents> The colored composition of the present invention preferably contains a thiol-based chain transfer agent. By using thiols together with a photopolymerization initiator, thiyl radicals are generated in the radical polymerization process after light irradiation that act as chain transfer agents and are less susceptible to polymerization inhibition by oxygen, resulting in a highly sensitive colored composition.

[0115] Furthermore, the thiol-based chain transfer agent is preferably a polyfunctional aliphatic thiol, which has two or more thiol groups bonded to aliphatic groups such as methylene or ethylene groups. More preferably, it is a polyfunctional aliphatic thiol with four or more thiol groups. Increasing the number of functional groups improves the polymerization initiation function, allowing curing from the surface of the pattern to near the substrate.

[0116] Examples of polyfunctional thiols include hexanedithiol and decanedithiol. Examples include 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. Preferably, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate are used.

[0117] Thiol-based chain transfer agents can be used alone or in combination of two or more types.

[0118] The content of thiol-based chain transfer agents is preferably 0.1 to 10% by mass, and more preferably 0.1 to 3% by mass, based on 100% by mass of the non-volatile content of the colored composition. When an appropriate amount is included, the light sensitivity and tapered shape are improved, and wrinkles are less likely to occur on the surface of the coating.

[0119] <Polymerization inhibitor> The coloring composition may contain a polymerization inhibitor. This suppresses photosensitivity due to diffracted light on the mask during photolithography exposure, making it easier to obtain patterns of the desired shape.

[0120] Examples of polymerization inhibitors include alkylcatechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n- Examples include alkylresorcinol compounds such as butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, and 4-tert-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tripenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphine and trisnonylphenylphosphine; pyrogallol and phloroglucin.

[0121] The polymerization inhibitor content is preferably 0.01 to 0.4% by mass of 100% by mass of the non-volatile content of the colored composition. Within this range, the effect of the polymerization inhibitor is enhanced, resulting in improved linearity of the taper, reduced wrinkles in the coating film, and better pattern resolution.

[0122] <UV absorber> The colored composition of the invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function, and examples include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, and salicylate compounds.

[0123] The UV absorber content is preferably 5 to 70% by mass of the total 100% by mass of the photopolymerization initiator and UV absorber. Including an appropriate amount further improves resolution after development.

[0124] Furthermore, the total content of the photopolymerization initiator and ultraviolet absorber is preferably 1 to 20% by mass of the nonvolatile content of the colored composition. Including an appropriate amount further improves the adhesion between the substrate and the coating, resulting in good resolution.

[0125] Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, and 2-[2-hydroxy-3,5-bis(α, α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, a mixture of 3-(2H-benzotriazole2-yl)-(1,1-dimethylethyl)-4-hydroxy,C7-9 side chain and linear alkyl ester, 2-(2H-benzotriazole2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazole2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl Reaction product of 3-(3-(2H-benzotriazole2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300, 2-(2H-benzotriazole2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazole2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazole2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazole2-yl)-6-t-butyl Examples include 4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole2-yl)phenyl]propionate.

[0126] Examples of triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction between 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester. Examples of the resulting compounds include 2,4-bis"2-hydroxy-4-butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine. Other oligomeric and polymer-type compounds having a triazine structure can also be used.

[0127] Examples of benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. Other oligomeric and polymeric compounds having a benzophenone structure can also be used.

[0128] Examples of salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Other oligomeric and polymeric compounds having a salicylic acid ester structure can also be used.

[0129] <Antioxidant> The colored composition of the present invention may contain an antioxidant. The antioxidant prevents the photopolymerization initiator and thermosetting compound contained in the colored composition from oxidizing and yellowing due to the heat process during thermosetting and ITO annealing, thereby improving the transmittance of the coating film. In particular, when the colorant concentration of the colored composition is high, the amount of coating film crosslinking component decreases, so countermeasures such as using a highly sensitive crosslinking component or increasing the amount of photopolymerization initiator are taken, which can lead to a phenomenon intensifying yellowing during the heat process. 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.

[0130] Examples of antioxidants include hindered phenol, hindered amine, phosphorus, sulfur, and hydroxylamine compounds. In this specification, antioxidants that do not contain halogen atoms are preferred.

[0131] Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred from the viewpoint of achieving both the transmittance and sensitivity of the coating film.

[0132] Antioxidants can be used alone or in combination of two or more types.

[0133] Furthermore, an antioxidant content of 0.5 to 5.0% by mass, relative to 100% by mass of the non-volatile content of the colored composition, is more preferable because it results in good transmittance, spectral characteristics, and sensitivity.

[0134] <Leveling agent> In order to improve the coatability of the composition on a transparent substrate and the drying properties of the colored film, it is preferable to add a leveling agent to the colored composition of the present invention. Various surfactants such as silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants can be used as leveling agents.

[0135] Examples of silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0136] More specifically, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345 / 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 from BIC Chemie, and FZ-7002, 2110 from Toray Dow Corning Co., Ltd. Examples include 2122, 2123, 2191, 5609, and Shin-Etsu Chemical Co., Ltd.'s X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341, etc.

[0137] Examples of fluorine-based surfactants include surfactants or leveling agents having fluorocarbon chains.

[0138] More specifically, examples include Surflon S-242, S-243, S-420, S-611, S-651, S-386 from AGC Seimi Chemical Co., Ltd., Megafac F-253, F-477, F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, DS-21 from DIC Corporation, FC-4430, FC-4432 from Sumitomo 3M Limited, EF-PP31N09, EF-PP33G1, EF-PP32C1 from Mitsubishi Materials Electronic Chemicals Co., Ltd., and Futergent 602A from Neos Co., Ltd.

[0139] Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristelle ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tripenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and sorbitan tristearate. Examples include sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkylimidazoline, etc.

[0140] More specifically, Kao Corporation's Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, L S-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD450, Leodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L1 06, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amito 102, 105, Examples include 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Pluronic® L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R manufactured by ADEKA Corporation, and (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0141] Cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and their ethylene oxide adducts.

[0142] More specifically, examples include Acetamine 24, Cotamin 24P, 60W, and 86P Concentrate manufactured by Kao Corporation.

[0143] Examples of anionic surfactants 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.

[0144] More specifically, examples include Neos Co., Ltd.'s Futergent 100 and 150, and ADEKA Corporation's Adeka Hope YES-25, Adeka Call TS-230E, PS-440E, EC-8600, etc.

[0145] Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.

[0146] More specifically, examples include Anchitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N manufactured by Kao Corporation.

[0147] When the colored composition of the present invention contains a surfactant, the amount of surfactant added is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, based on 100% by mass of the non-volatile content of the colored composition of the present invention. Within this range, a good balance is achieved between the applicability, pattern adhesion, and transmittance of the colored composition. The colored composition of the present invention may contain only one type of surfactant, or it may contain two or more types. If it contains two or more types, it is preferable that the total amount thereof is within the above range.

[0148] <Storage stabilizer> The colored composition of the present invention may contain a storage stabilizer to stabilize the viscosity of the composition over time. Examples of storage stabilizers include benzyl trimethyl chloride, quaternary ammonium chlorides such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butyl pyrocatechol, tetraethylphosphine, and tetraphenylphosphine, and phosphates. The storage stabilizer can be used in an amount of 0.1 to 10% by mass relative to 100% by mass of the total amount of the coloring agent.

[0149] <Adhesion enhancer> The colored composition of the present invention may contain adhesion-enhancing agents such as silane coupling agents to improve adhesion to the substrate. Improved adhesion due to the adhesion-enhancing agents results in better reproduction of fine lines and improved resolution.

[0150] Adhesion enhancers include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane, epoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, and N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3- Examples of silane coupling agents include aminosilanes such as aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and hydrochloride salts of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureidos such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatetopropyltriethoxysilane. 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. Within this range, the effect is greater, and the balance between adhesion, resolution, and sensitivity is good, making it more preferable.

[0151] <Solvent> The colored composition of the present invention contains a solvent 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 solvent is selected considering not only good coatability of the colored composition, but also the solubility of each component of the colored composition, as well as safety.

[0152] As the solvent, solvents commonly used in the field can be used, and their properties such as boiling point, SP value, evaporation rate, and viscosity are taken into consideration, and they are used individually or in mixtures as appropriate according to the application conditions (speed, drying conditions, etc.).

[0153] Examples of solvents that can be used include ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), ether ester solvents (solvents containing both -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (solvents containing OH in the molecule but not -O-, -CO-, and -COO- in the molecule), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

[0154] Of the above solvents, it is preferable to include an organic solvent whose boiling point at 1 atm is 120°C or higher and 180°C or lower, from the viewpoint of applicability and drying properties. Among these, propylene glycol monomethyl ether acetate (hereinafter also referred to as PGMAc), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc. are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are more preferred.

[0155] <Method for producing colored composition> The colored compositions included in the present invention can be manufactured by finely dispersing a colorant (A) in a colorant carrier such as a resin-type dispersant (B) and a binder resin (C), and / or a solvent, preferably together with a dispersion aid (pigment derivative or surfactant), 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 has high solubility, such as a dye, 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.

[0156] Furthermore, when used as a colored composition (resist material) for color filters, it can be prepared as a solvent-developable or alkali-developable colored composition. The solvent-developable or alkali-developable colored composition can be prepared by mixing the colorant dispersion with a photopolymerizable monomer and / or a photopolymerization initiator, and optionally with a solvent, other dispersion aids, and additives. The photopolymerization initiator may be added during the preparation of the colored composition, or it may be added to the prepared colored composition afterward.

[0157] <Removal of coarse particles> The colored composition of the present invention is preferably subjected to the removal of coarse particles of 5 μm or larger, preferably 1 μm or larger, and more preferably 0.5 μm or larger, and any mixed dust by means of centrifugal separation at a gravitational acceleration of 3000 to 25000 G, filtration using a sintered filter or a membrane filter, etc. Thus, it is preferable that the colored composition substantially does not contain particles of 0.5 μm or larger. More preferably, it is preferable that the particles are 0.3 μm or smaller.

[0158] <Moisture content in colored composition> In the present invention, it is preferable that the water content in the colored composition is 2% by mass or less relative to 100% by mass of the colored composition.

[0159] If the water content of the coloring composition is within the above range, it exhibits excellent dispersion stability and sensitivity even after storage over time.

[0160] The water content in the colored composition is preferably 1.8% by mass or less, and more preferably 1.6% by mass or less, based on 100% by mass of the colored composition. If the water content is sufficiently low within this range, problems with dispersion stability and sensitivity are unlikely to occur even after storage over time.

[0161] 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.

[0162] The water content can be measured by known methods such as the Karl Fischer method.

[0163] <Amount of toluene in the colored composition> The coloring composition 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 preferably 0.2 ppm by mass or more, more preferably 0.3 ppm by mass or more, and even more preferably 0.4 ppm by mass or more.

[0164] <Cured film> The cured film of the present invention is formed using the resin composition described above. The cured film may be used in a laminated state on a substrate, or the cured film may be peeled off from the substrate. The cured film may be a flat film or a film with a pattern, but a film with a pattern is preferred.

[0165] [Method for manufacturing hardened film] The method for producing the cured film is not particularly limited, and known methods can be used. For example, it can be produced by a process of coating the resin composition of the present invention onto a substrate.

[0166] Examples of substrates include those made of materials such as glass, resin, or silicon. An organic light-emitting layer may be formed on these substrates. An image sensor such as a CCD or CMOS may also be formed on the substrate. Furthermore, a primer layer may be provided on the substrate as needed to improve adhesion with the upper layer, prevent diffusion of materials, and flatten the substrate surface.

[0167] A known coating method can be used. Examples include the drop method, slit coating method, spray method, roll coating method, rotary coating method, casting coating method, inkjet method, flexographic printing, screen printing, gravure printing, and offset printing.

[0168] The film thickness can be adjusted as appropriate depending on the purpose. A film thickness of 0.05 to 20.0 μm is preferred, and 0.3 to 10.0 μm is more preferred.

[0169] Next, a pattern is formed. Methods for forming the pattern include photolithography and dry etching. Note that when used as a flat film, the pattern formation step is unnecessary; the coating is simply dried as needed.

[0170] The following describes in detail how to form the patterns.

[0171] (When forming a pattern using photolithography) When forming a pattern using photolithography, the resin composition of the present invention is coated onto a substrate to form a layer, which is then dried (pre-baked) as needed, exposed in a patterned manner through a mask (exposure step), the unexposed areas are removed by alkaline development (development step), and the pattern is then heat-treated as needed (post-baking step).

[0172] [Exposure process] The exposure process involves exposing a layer formed by coating to a specific pattern via a mask using an exposure device such as a stepper. This allows the exposed area to harden. Examples of active energy rays used for exposure include ultraviolet rays such as g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm). Light with a wavelength of 300 nm or less can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm). Furthermore, exposure may be performed by continuously irradiating with light, or by repeatedly irradiating and pausing with light in short cycles (for example, at the millisecond level or less) (pulsed exposure).

[0173] [Development process] Next, by performing an alkaline development treatment, the unexposed layers dissolve in the alkaline aqueous solution, leaving only the hardened parts and obtaining a patterned film. Examples of alkaline developers include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The concentration of the alkaline developer is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, and more preferably 11.5 to 12.5. Using an appropriate pH suppresses pattern roughness and peeling, and improves the residual film rate after development. Development methods include, for example, the dip method, spray method, and paddle method. The development temperature is preferably 15 to 40°C. After alkaline development, it is preferable to wash with pure water.

[0174] [Post-baking process] After development, heat treatment (post-baking) can be performed as needed. Post-baking improves the durability of the film. The temperature is preferably between 80 and 300°C. The duration is preferably between 2 minutes and 1 hour. When a material with low heat resistance is used as the substrate, or when an organic electroluminescent element is used as the light source, the temperature is preferably 150°C or lower, and more preferably 130°C or lower.

[0175] (When forming a pattern using the dry etching method) When forming a pattern by dry etching, for example, a layer formed by coating a substrate with the resin composition of the present invention is heated and cured. Next, a patterned photoresist layer is formed on the cured film, and then dry etching is performed on the cured film using an etching gas, with the patterned photoresist layer as a mask. For pattern formation by dry etching, the method described in Japanese Patent Application Publication No. 2013-064993 can be referenced.

[0176] <Optical filters> The cured film of the present invention can be used in optical filters. The optical filter can be used, for example, as an input means for various image display devices that incorporate a display panel such as a liquid crystal display panel, such as ticket vending machines and ATM devices. This can be used as a color filter, an infrared cut filter, an infrared transmission filter, or other component of touch panels, solid-state image sensors, organic EL display devices, etc.

[0177] <Image display device> As an example of an image display device equipped with the color filter of the present invention, a liquid crystal display device 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.

[0178] Liquid crystal (LC) is oriented according to the driving mode, such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), and OCB (Optically Compensated Birefringence). A TFT (Thin Film Transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed on top of it. An alignment 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.

[0179] 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).

[0180] 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.

[0181] 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.

[0182] 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. They have a wavelength (λ3) in which the emission intensity is maximum in the range of 430nm to 485nm, a wavelength (λ4) in which the emission intensity is maximum in the range of 530nm to 580nm, and a wavelength (λ5) in which 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. Preferably, a white LED light source (LED1) has spectral characteristics in which the ratio of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 (I5 / I3) is 0.1 or more and 1.3 or less, or a white LED light source (LED2) has spectral characteristics in which the wavelength (λ1) at which the emission intensity is maximum is in the range of 430 nm to 485 nm, the peak wavelength (λ2) of the second emission intensity is in the range of 530 nm to 580 nm, and the ratio of the emission intensity I1 at wavelength λ1 to the emission intensity I2 at wavelength λ2 (I2 / I1) is 0.2 or more and 0.7 or less.

[0183] Examples of LED1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation) and NSSW304D-HG-V1 (manufactured by Nichia Corporation).

[0184] Examples of LED2 include the NSSW440 (manufactured by Nichia Corporation) and the NSSW304D (manufactured by Nichia Corporation).

[0185] <Solid-state image sensor> The film of the present invention can be used in solid-state image sensors. The form in which it is used in solid-state image sensors is not particularly limited, but for example, a substrate has a plurality of photodiodes and transfer electrodes made of polysilicon or the like that constitute the light-receiving area of ​​a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.), a light-shielding film has openings only for the light-receiving portion of the photodiodes on the photodiodes and transfer electrodes, a device protection 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 light-receiving portion of the photodiodes, and a filter has been placed on the device protection film. Furthermore, there may be a configuration in which a light-collecting means (e.g., a microlens, etc.; the same applies hereinafter) is placed on the device protection film below the filter (closer to the substrate), or a configuration in which the light-collecting means is placed on the filter. In addition, the filter may have a structure in which a hardened film that forms each colored pixel is embedded in a space partitioned, for example, in a grid pattern by partitions. In this case, it is preferable that the partitions have a low refractive index with respect to each colored pixel. The imaging device equipped with the solid-state image sensor of the present invention can be used in a variety of applications, such as digital cameras, electronic devices with imaging functions (smartphones, tablet terminals, etc.), in-vehicle cameras, surveillance cameras, and optical sensors.

[0186] <Infrared sensor> The film of the present invention can be used in infrared sensors. The form in which it is used in infrared sensors is not particularly limited. Figure 2 is a schematic cross-sectional view showing an example of the configuration of an infrared sensor equipped with the film of the present invention. The infrared sensor shown in Figure 2 comprises a 100 and a solid-state image sensor 110.

[0187] The imaging area on the solid-state image sensor 110 is formed by combining an infrared cut filter 111 and a color filter 112.

[0188] The infrared cut filter 111 can be formed using the resin composition of the present invention, and transmits light in the visible light region (for example, light with a wavelength of 400 to 700 nm) and blocks light in the infrared region.

[0189] The color filter 112 is a color filter in which pixels that transmit and absorb light of specific wavelengths in the visible light region are formed. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed is used.

[0190] Between the infrared transmission filter 113 and the solid-state image sensor 110, a resin film 114 is arranged that can transmit light of wavelengths that have passed through the infrared transmission filter 113. The infrared transmission filter 113 is a filter that blocks light in the visible light region and transmits infrared light of a specific wavelength, and can be formed using the resin composition of the present invention.

[0191] A microlens 115 is positioned on the incident light h side of the color filter 112 and the infrared transmission filter 113. A planarization film 116 is formed to cover the microlens 115.

[0192] In the configuration shown in Figure 2, a resin film 114 is arranged, but an infrared transmission filter 113 may be formed instead of the resin film 114.

[0193] This infrared sensor can simultaneously capture image information, enabling motion sensing and other applications that recognize moving objects. Furthermore, because it can acquire distance information, it can capture images containing 3D data. In addition, this infrared sensor can also be used as a biometric authentication sensor. [Examples]

[0194] The present invention will be described below with reference to examples. In the examples, "parts" and "%" refer to "parts by mass" and "mass%", respectively. Also, propylene-free monomethyl acetate may be represented as PGMAc.

[0195] Prior to the examples, the methods for calculating the average molecular weight of the resin and the acid value of the resin will be explained.

[0196] (Average molecular weight of resin) The number-average molecular weight (Mn) and mass-average molecular weight (Mw) of the resin were measured using 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 1 wt% solution of the above eluent and injected in 20 microliters. All molecular weights are polystyrene equivalents.

[0197] (Acid value of resin) 0.5 to 1 g of resin solution was mixed with 80 ml of acetone and 10 ml of water and stirred to dissolve uniformly. A 0.1 mol / L aqueous KOH 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 (mgKOH / g) of the resin solution. The acid value per unit solid content of the resin was then calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

[0198] <Method for manufacturing finely milled pigments> (Manufacturing of micronized pigment (V37)) CI Pigment Violet 37 (DIC Corporation's "Chromophthal Violet D5700") was charged with 250 parts of sodium chloride and 25 parts of diethylene glycol in a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 100°C for 6 hours. 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 with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight and then pulverized to obtain fine pigment (V37).

[0199] (Manufacturing of micronized pigment (V23)) Micronized pigment (V23) was obtained in the same manner as the production of micronized pigment (V37), except that CI Pigment Violet 37 (DIC Corporation's "Chromophthal Violet D5700") was replaced with CI Pigment Violet 23 (Toyo Color Corporation's "Lionogen Violet RL").

[0200] (Finely milled pigment (Y139)) Micronized pigment (Y139) was obtained in the same manner as the production of micronized pigment (V37), except that CI Pigment Violet 37 (DIC Corporation's "Chromophthal Violet D5700") was replaced with CI Pigment Yellow 139 (BASF Japan Corporation's "Irgaphor Yellow 2R-CF").

[0201] (Finely milled pigment (Y185)) Micronized pigment (Y185) was obtained in the same manner as the production of micronized pigment (V37), except that CI Pigment Violet 37 (DIC Corporation's "Chromophthal Violet D5700") was replaced with CI Pigment Yellow 185 (BASF Japan's "Paliotol Yellow L 1155").

[0202] (Finely milled pigment (B15:3)) Micronized pigment (B15:3) was obtained in the same manner as the production of micronized pigment (V37), except that CI Pigment Violet 37 (DIC Corporation's "Chromophthal Violet D5700") was replaced with CI Pigment Blue 15:3 (PB15:3, Toyo Color Co., Ltd.'s "LIONOL BLUE FG-7351").

[0203] (Finely milled pigment (B15:4)) Micronized pigment (B15:4) was obtained in the same manner as the production of micronized pigment (V37), except that CI Pigment Violet 37 (DIC Corporation's "Chromophthal Violet D5700") was replaced with CI Pigment Blue 15:4 (PB15:3, Toyo Color Co., Ltd.'s "LIONOL BLUE FG-7400G").

[0204] (Finely milled pigment (B15:6)) Micronized pigment (B15:6) was obtained in the same manner as the production of micronized pigment (V37), except that CI Pigment Violet 37 (DIC Corporation's "Chromophthal Violet D5700") was replaced with CI Pigment Blue 15:6 (Toyo Color Corporation's "Lionol Blue ES").

[0205] <Dye derivative (a)> The following basic pigment derivatives were used. Dye derivative (a-1) [ka] Dye derivative (a-2) [ka] Dye derivative (a-3) [ka] Dye derivative (a-4) [ka] Dye derivative (a-5) [ka]

[0206] (Manufacturing of resin-type dispersants) (Example of preparation of a resin-type dispersant (B1-R-1) solution having an aromatic carboxylic acid structure) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 50.0 parts of t-butyl acrylate, 45.0 parts of methyl methacrylate, and 5.0 parts of methacrylic acid were charged, and the vessel was purged with nitrogen gas. The reaction vessel was heated to 80°C, and a solution of 6.0 parts of 3-mercapto-1,2-propanediol and 0.1 parts of 2,2'-azobisisobutyronitrile dissolved in 70.7 parts of propylene glycol monomethyl ether acetate was added, and the reaction was allowed to proceed for 10 hours. Non-volatile content measurement confirmed that more than 95% of the monomers had reacted. Next, 14.5 parts of pyromellitic dianhydride, 38.0 parts of propylene glycol monomethyl ether acetate, and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 120°C for 5 hours. By measuring the amount of remaining acid anhydride, it was confirmed that 80% of the acid anhydride had reacted. Subsequently, 12.1 parts of 3-methoxybutanol were added, and the mixture was reacted at 120°C for 3 hours to form end-encapsulation sites. The acid value was measured to confirm that more than 98% of the acid anhydride had reacted, and the reaction was terminated. Then, propylene glycol monomethyl ether acetate was added to prepare a solution with an acid value of 110 mg KOH / g and a weight-average molecular weight of 9000, obtained as a dispersant (B1-R-1).

[0207] (Example of preparation of a resin-type dispersant (B1-R-2) solution having an aromatic carboxylic acid structure) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 20.0 parts of t-butyl acrylate, 45.0 parts of methyl methacrylate, 30.0 parts of ethyl acrylate, and 5.0 parts of methacrylic acid were charged and the mixture was purged with nitrogen gas. The reaction vessel was heated to 80°C, and a solution of 6.0 parts of 3-mercapto-1,2-propanediol and 0.1 parts of 2,2'-azobisisobutyronitrile dissolved in 70.7 parts of propylene glycol monomethyl ether acetate was added, and the mixture was reacted for 10 hours. Non-volatile content measurement confirmed that more than 95% of the monomers had reacted. Next, 14.5 parts of pyromellitic dianhydride, 38.0 parts of propylene glycol monomethyl ether acetate, and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 120°C for 5 hours. By measuring the amount of remaining acid anhydride, it was confirmed that 80% of the acid anhydride had reacted. Subsequently, 12.1 g of 3-methoxybutanol was added, and the mixture was reacted at 120°C for 3 hours to form end-encapsulation sites. The acid value was measured to confirm that more than 98% of the acid anhydride had reacted, and the reaction was terminated. Then, propylene glycol monomethyl ether acetate was added to prepare a solution with an acid value of 105 mg KOH / g and a weight-average molecular weight of 9400, obtained as a dispersant (B1-R-2).

[0208] (Example of preparation of a resin-type dispersant (B1-R-3) solution having an aromatic carboxylic acid structure) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 6 parts of 3-mercapto-1,2-propanediol, 14.5 parts of pyromellitic dianhydride, and 70.8 parts of propylene glycol monomethyl ether acetate were charged, and the vessel was purged with nitrogen gas. The reaction vessel was heated to 100°C and reacted for 5 hours. By measuring the amount of residual acid anhydride, it was confirmed that 80% of the acid anhydride had reacted. Subsequently, 12.1 g of 3-methoxybutanol was added, and the mixture was reacted at 120°C for 3 hours to form a terminal encapsulation site. After confirming that more than 98% of the acid anhydride had reacted by measuring the acid value, the temperature of the reaction system was cooled to 70°C, and 50.0 parts of t-butyl acrylate and 50.0 parts of methyl methacrylate were charged. 38.0 parts of propylene glycol monomethyl ether acetate in which 0.1 parts of 2,2'-azobisisobutyronitrile was dissolved was added, and the mixture was reacted for 10 hours. The reaction was terminated after confirming that more than 95% of the monomers had reacted by measuring the non-volatile content. After the reaction was complete, propylene glycol monomethyl ether acetate was added to adjust the non-volatile content to 20% by mass, and a solution of dispersant (B1-R-3) with an acid value of 93 mg KOH / g and a weight-average molecular weight of 10800 was obtained.

[0209] (Preparation of a resin-type dispersant solution (B1-1: comb-type) having an aromatic carboxylic acid structure) In a reaction vessel equipped with a gas inlet tube, temperature control, condenser, and stirrer, 10 parts methacrylic acid, 100 parts methyl methacrylate, 70 parts iso-butyl methacrylate, 20 parts benzyl methacrylate, and 50 parts propylene glycol monomethyl ether acetate (PGMAc) were charged and purged with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts 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 2,2'-azobisisobutyronitrile added to 90 parts PGMAc. Non-volatile content measurement confirmed that more than 95% of the monomers had reacted. 19 parts pyromellitic anhydride, 50 parts PGMAc, 50 parts cyclohexanone, and 0.4 parts 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100°C for 7 hours. After confirming that more than 98% of the acid anhydride groups were half-esterified by measuring the acid value, the reaction was terminated. The solution was then diluted by adding PGMAc to obtain a resin-type dispersant (B1-1) solution with an acid value of 70 mgKOH / g and a weight-average molecular weight of 8500.

[0210] (Preparation of resin-type dispersants (B1-2: comb-type, thermally crosslinked) solutions having aromatic carboxylic acid structures) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 160 parts n-butyl acrylate, 40 parts Karenz MOI-BM (manufactured by Showa Denko: containing a blocked isocyanate group, which is a thermally crosslinkable group), 50 parts propylene glycol monomethyl ether acetate, and 50 parts cyclohexanone were charged and the mixture was purged with nitrogen gas. The reaction vessel was heated to 80°C, and 12 parts 3-mercapto-1,2-propanediol were added and the mixture was reacted for 12 hours. Non-volatile content measurement confirmed that more than 95% of the monomers had reacted. Next, 19 parts pyromellitic dianhydride, 231 parts cyclohexanone, and 0.40 parts 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and the mixture was reacted at 100°C for 7 hours. Acid value measurement confirmed that more than 98% of the acid anhydride had been half-esterified, and the reaction was terminated. The non-volatile content was adjusted to 20% with propylene glycol monomethyl ether acetate to obtain a resin-type dispersant (B1-2) solution containing a blocked isocyanate group, which is a thermally crosslinkable group with an acid value of 42 mg KOH / g and a weight-average molecular weight of 9000.

[0211] (Preparation of resin-type dispersants (B1-3: comb-type, photocrosslinked type) solutions having aromatic carboxylic acid structures) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst were charged, and after purging with nitrogen gas, the mixture was reacted at 120°C for 5 hours (first step). Acid value measurement confirmed that more than 95% of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step (on a non-volatile content basis), 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 acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc 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). Non-volatile content measurement confirmed that more than 95% of the monomers had reacted. Finally, 500 parts of a 50% PGMAc 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 the reaction was carried out by IR until the disappearance of the 2270 cm-1 peak based on the isocyanate group was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled, and the non-volatile content was adjusted with PGMAc to obtain a resin-type dispersant (B1-3) solution containing a photocrosslinking group (meth)acryloyl group with a non-volatile content of 20%. The acid value of the obtained dispersant was 68 mg KOH / g, the double bond equivalent was 1593, and the weight-average molecular weight was 13000.

[0212] (Preparation of resin-type dispersants (B1-4: linear type) containing aromatic carboxylic acid structures) In a reaction vessel equipped with a gas inlet tube, condenser, stirring blade, and thermometer, 80 parts methyl methacrylate, 120 parts ethyl acrylate, and 40 parts methoxypropyl acetate were charged and the mixture was purged with nitrogen gas. The reaction vessel was heated to 80°C, and 4.4 parts 3-mercapto-1,2-propanediol were added. Then, 0.2 parts 2,2'-azobisisobutyronitrile were added in 20 portions every 30 minutes, and the reaction was carried out at 80°C for 12 hours. Non-volatile content measurement confirmed that more than 95% of the monomers had reacted. Next, 12 parts trimellitic anhydride, 190 parts methoxypropyl acetate, and 0.40 parts 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 120°C for 2 hours and then at 80°C for 5 hours. Titration confirmed that more than 90% of the acid anhydride was half-esterified, yielding a resin-type dispersant (B1-4) with an acid value of 44 mg KOH / g per non-volatile content. Furthermore, by adjusting the non-volatile content with PGMAc, a dispersant (B1-4) solution with 20% non-volatile content was obtained.

[0213] (Preparation of resin-type dispersants (B1-5: linear type, thermosetting type) containing aromatic carboxylic acid structures) In a reaction vessel equipped with a gas inlet tube, condenser, stirring blade, and thermometer, 3 parts trimellitic anhydride, 1 part 3-mercapto-1,2-propanediol, 50 parts PGMAc, and 0.1 parts dimethylbenzylamine were charged. After purging with nitrogen gas, the reaction vessel was heated to 120°C and reacted for 4 hours, then reacted at 80°C for 2 hours. Next, 30 parts tert-butyl acrylate, 20 parts ETERNACOLL OXMA (methyl methacrylate (3-ethyloxetane-3-yl), manufactured by Ube Industries, Ltd.), 5 parts methacrylic acid, 40 parts ethyl acrylate, and 10 parts PGMAc were charged. While maintaining the reaction vessel at 80°C, 0.2 parts 2,2'-azobisisobutyronitrile were added in 15 portions every 30 minutes. One hour after the final addition, the non-volatile content was measured and it was confirmed that more than 95% of the monomers had reacted. The solution was diluted by adding PGMAc to achieve a non-volatile content of 20% as measured by non-volatile content measurement, yielding a resin-type dispersant (B1-5) solution containing tert-butyl groups and oxetane groups, which are thermosetting groups with an acid value of 51 mgKOH / g per non-volatile content and a weight-average molecular weight (Mw) of 24,000.

[0214] (Preparation of resin-type dispersant (B2) solution) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin(IV) oxide as a catalyst were charged. After purging with nitrogen gas, the mixture was heated and stirred at 120°C for 4 hours. After confirming that more than 98% of the monomers had reacted by measuring the non-volatile content, 73.3 parts of pyromellitic anhydride were added and the mixture was reacted at 120°C for 2 hours. The reaction was terminated after confirming that more than 98% of the acid anhydride had been half-esterified by measuring the acid value. A dispersant (B2) solution with 20% non-volatile content was obtained by adjusting the non-volatile content with PGMAc. The obtained dispersant was a white solid at room temperature and had an acid value of 49 mgKOH / g.

[0215] (Manufacturing of other acidic resin-type dispersant (B3) solutions) A thermometer, condenser, nitrogen gas inlet tube, and stirrer were attached to a separable four-neck flask, and 1500 parts of cyclohexanone were charged. The temperature was raised to 80°C, and the reaction vessel was purged with nitrogen. A mixed solution of 120 parts methyl methacrylate, 210 parts n-butyl methacrylate, 90 parts 2-hydroxyethyl methacrylate, 60 parts methacrylic acid, 120 parts paracumylphenol ethylene oxide modified acrylate (Toagosei Co., Ltd. "Aronics M-110"), 6 parts acid phosphooxyethyl methacrylate, and 30 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 an acidic resin-type dispersant (B3) solution with a non-volatile content of 20% and a weight-average molecular weight of 24000.

[0216] <Example of binder resin (C) manufacturing> (Preparation of binder resin (C-1) solution) A reaction vessel was prepared by fitting a thermometer, condenser, nitrogen gas inlet, dropping tube, and stirrer into a separable four-neck flask. 196 parts of cyclohexanone were charged into this vessel, and the temperature was raised to 80°C. After purging the reaction vessel with nitrogen, a mixture of 37.2 parts n-butyl methacrylate, 12.9 parts 2-hydroxyethyl methacrylate, 12.0 parts methacrylic acid, 20.7 parts paracumylphenol ethylene oxide modified acrylate (Toagosei Co., Ltd. "Aronics M110"), and 1.1 parts 2,2'-azobisisobutyronitrile was added dropwise over 2 hours via the dropping tube. After the addition was complete, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution were sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. PGMAc was added to the previously synthesized resin solution to achieve a non-volatile content of 20% to prepare the binder resin (C-1) solution. The weight-average molecular weight (Mw) was 26,000.

[0217] (Preparation of binder resin (C-2) solution) 370 parts of cyclohexanone were placed in a separable four-necked flask equipped with a thermometer, condenser, nitrogen gas inlet tube, dropping tube, and stirrer. The temperature was raised to 80°C, and the flask was purged with nitrogen. A mixture of 18 parts of paracumylphenol ethylene oxide-modified acrylate (Aronics M110, manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours via the dropping tube. After the dropwise addition, the mixture was reacted at 100°C for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was continued at 100°C for another hour. Next, the container was replaced with an air-purging system, and 9.3 parts of acrylic acid (equivalent to 100 mol% of glycidyl groups), 0.5 parts of trisdimethylaminophenol, and 0.1 parts of hydroquinone were added to the container. The reaction was continued at 120°C for 6 hours until the non-volatile acid value reached 0.5, at which point the reaction was terminated to obtain an acrylic resin solution. Subsequently, 19.5 parts of tetrahydrophthalic anhydride (equivalent to 100 mol% of the generated hydroxyl groups) and 0.5 parts of 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. The non-volatile content was measured, and PGMAc was added to the previously synthesized resin solution to prepare a binder resin (C-2) solution with a non-volatile content of 20% by mass. The weight-average molecular weight (Mw) was 19000.

[0218] (Preparation of binder resin (C-3) solution) A reaction vessel was prepared by fitting a thermometer, condenser, nitrogen gas inlet, dropping tube, and stirrer into a separable four-neck flask. 207 parts of cyclohexanone were charged into this vessel, and the temperature was raised to 80°C. After purging the reaction vessel with nitrogen, a mixture of 20 parts methacrylic acid, 20 parts paracumylphenol ethylene oxide-modified acrylate (Aronics M110, manufactured by Toagosei Co., Ltd.), 45 parts methyl methacrylate, 8.5 parts 2-hydroxyethyl methacrylate, and 1.33 parts 2,2'-azobisisobutyronitrile was added dropwise over 2 hours via the dropping tube. After the dropwise addition was complete, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the entire copolymer solution was stirred while injecting dry air for 1 hour after stopping the nitrogen gas supply, and then cooled to room temperature. A mixture of 6.5 parts 2-methacryloyloxyethyl isocyanate (Kalenz MOI, Showa Denko Co., Ltd.), 0.08 parts dibutyltin laurate, and 26 parts cyclohexanone was added dropwise at 70°C for 3 hours. After the dropwise addition was complete, the reaction was continued for another hour to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution were sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Cyclohexanone was then added to the previously synthesized resin solution to prepare a binder resin (C-3) with a non-volatile content of 20%. The weight-average molecular weight (Mw) was 18000.

[0219] (Preparation of binder resin (C-4) solution) A separable flask with a condenser was prepared as the reaction vessel, and a monomer dropping vessel was prepared by thoroughly stirring and mixing 40 parts of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 40 parts of methacrylic acid, 120 parts of methyl methacrylate, 4 parts of t-butyl peroxy-2-ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.), and 40 parts of PGMAc. A chain transfer agent dropping vessel was prepared by thoroughly stirring and mixing 8 parts of n-dodecanethiol and 32 parts of PGMAc. 395 parts of PGMAc were charged into a reaction vessel, which was then purged with nitrogen. After that, while stirring, it was heated with an oil bath to raise the temperature of the reaction vessel to 90°C. After the temperature of the reaction vessel stabilized at 90°C, dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was carried out over 135 minutes each while maintaining the temperature at 90°C. Sixty minutes after the dropping was completed, heating was started to raise the temperature of the reaction vessel to 110°C. After maintaining at 110°C for 3 hours, a gas introduction tube was attached to a separable flask, and bubbling of an oxygen / nitrogen = 5 / 95 (volume ratio) mixed gas was started. Next, 70 parts of glycidyl methacrylate, 0.4 part of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 part of triethylamine were charged into the reaction vessel, and the reaction was carried out at 110°C for 12 hours as it was. Then, 150 parts of PGMAc were added and cooled to room temperature. About 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content. PGMAc was added to the previously synthesized resin solution so that the non-volatile content became 20% by mass to obtain a binder resin (C-4) solution. The weight average molecular weight of the resin was 18,000, and the acid value per non-volatile content was 2 mgKOH / g.

[0220] <Method for producing colored composition> [Example 1] (Preparation of colored paste (P-1)) The following mixture was stirred and mixed uniformly, and then dispersed with zirconia beads having a diameter of 0.5 mm using an Eiger mill (Model "Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) for 3 hours, and then filtered through a filter with a pore diameter of 5.0 μm to prepare a colored paste (P-1) having a non-volatile component of 25% by mass. (P-1) Fine pigment (PV37): 20.0 parts Resin type dispersant (B) solution (B1-R-1, non-volatile content 20% solution): 20.0 parts Binder resin (C) solution (C-1, non-volatile content 20% solution): 5.0 parts Solvent (PGMAc): 55.0 parts ​​​​As shown in Table 1, the colored pastes (P-2 to P-26) were prepared in the same manner as the colored paste (P-1) described above, except that the type and quantity of each material were changed.

[0222] [Table 1]

[0223] Next, the following raw materials were mixed and stirred, and filtered through a 1.0 μm pore size filter to obtain a colored composition (R-1). Colored paste (P-1: 25% non-volatile content): 35.0 parts Colored paste (P-2: 25% non-volatile content): 22.4 parts Colored paste (P-3: 25% non-volatile content): 12.6 parts Binder resin (C) liquid (C-2, non-volatile content 20%): 10.0 parts Polymerizable compound (D) (D-1): 3.0 parts Photopolymerization initiator (E)(E1-1): 1.8 parts Thermosetting compound (CE) (CE-1): 1.0 part Thermosetting compound (CE) (CE-2): 1.0 part Sensitizer (H): 0.2 parts Thiol chain transfer agent (I): 0.4 parts Polymerization inhibitor (J): 0.1 part UV absorber (K): 0.1 part Antioxidant (L): 0.1 part Leveling agent (M: 3% non-volatile content): 1.0 part Storage stabilizer (N): 0.1 part Silane coupling agent (O): 0.2 parts Solvent (Q): 11.0 parts

[0224] [Examples 2-23, Comparative Examples 1-7] (Preparation of colored compositions (R-2 to R-30)) The coloring compositions (R-2 to 30) were prepared in the same manner as in Example 1, except that the type and amount of the coloring paste were changed so that the pigment ratio was as described in Tables 2 and 3 when the total amount of the pigments was 100 parts by mass.

[0225] <Measurement and Evaluation of Light Transmittance of Coloring Composition> When a coating film was formed under the condition that the film thickness of the obtained coloring composition was 0.7 μm, the light transmittance was evaluated as follows.

[0226] [Production of Coating Film] Each of the coloring compositions (R-1 to 30) was applied onto a glass substrate of 100 mm × 100 mm and 0.7 mm thick using a spin coater, then dried in an oven at 70 °C for 20 minutes, and ultraviolet exposure was performed using an ultra-high pressure mercury lamp with an integrated exposure amount of 150 mJ / cm 2 Then, development was carried out with an alkaline developer at 23 °C and washed with ion-exchanged water. Subsequently, heating was performed at 220 °C for 30 minutes and then allowed to cool, obtaining a coating film substrate with a film thickness of 0.7 μm. [Measurement of Light Transmittance] For the obtained coating film substrates, the transmittance in the thickness direction was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.), and the average transmittance at wavelengths of 400 to 650 nm and the average transmittance at wavelengths of 800 to 1000 nm were determined. The results are shown in Tables 2, Table 3-1, and Table 3-2.

[0227] [Table 2]

[0228] [Table 3-1]

[0229] [[ID=3x7]] [Table 3-2]

[0230] In Tables 2, 3-1, and 3-2, Ave.(400-650nm) represents the average transmittance in the wavelength range of 400-650nm, calculated by averaging the values ​​for every 1nm from 400-650nm. Similarly, Ave.(800-1000nm) represents the average transmittance in the wavelength range of 800-1000nm, calculated by averaging the values ​​for every 1nm from 800-1000nm. Note that the transmittances shown for 400, 450, 500, 550, 600, and 650 nm represent the transmittance at those specific wavelengths.

[0231] [Examples 24-42] Colored compositions (R-31 to R-48) were prepared in the same manner as in Example 1, except that the types of binder resin (C), polymerizable compound (D), and photopolymerization initiator (E) were changed as shown in Tables 4-1 and 4-2 below. Furthermore, the coloring composition (R-49) was prepared in the same manner as in Example 1, except for the following formulation. Colored paste (P-1: 25% non-volatile content): 35.0 parts Colored paste (P-2: 25% non-volatile content): 22.4 parts Colored paste (P-3: 25% non-volatile content): 12.6 parts Binder resin (C) liquid (C-2, non-volatile content 20%): 10.0 parts Polymerizable compound (D) (D-1): 5.0 parts Photopolymerization initiator (E)(E1-1): 4.0 parts Solvent (Q): 11.0 parts Since the transmittances of each colored composition (R-31~49) are the same as those of colored composition (R-1), their information has been omitted from Tables 4-1 and 4-2.

[0232] [Table 4-1]

[0233] [Table 4-2]

[0234] The ingredients are as follows: <Polymerizable compound (D)> (D-1) Tripropylene glycol diglycidyl ether acrylate adduct [Epoxy ester 200PA (manufactured by Kyoeisha Chemical Co., Ltd.)] (D-2) Glycerin diglycidyl ether acrylate adduct [Epoxy ester 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.)] (D-3) Ethylene glycol diglycidyl ether diacrylate (D-4) Butylene glycol diglycidyl ether diacrylate [Sartomer CN132 (manufactured by Arkema): (D-5) Dipentaerythritol penta and hexaacrylate [Aronix M-402 (manufactured by Toagosei Co., Ltd.)] (D-6) Ethylene oxide 12 molar modified dipentaerythritol hexaacrylate [KAYARAD DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.)]

[0235] <Photopolymerization initiator (E)> Compounds (E1-1), (E1-2), (E2-1), and (E3-1) to (E3-7) were those already exemplified. (E4-1) Ethane-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl], 1-(O-acetyloxime) [Irgacure OXE02 (manufactured by BASF Japan)] (E5-M) and (E5-1) to (E5-7) were mixed in equal amounts to form the photopolymerization initiator (E5-M). (E5-1)2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one [Omnirad907 (manufactured by IGM RESINS BV)] (E5-2)2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [Omnirad379 (manufactured by IGM RESINS BV)] (E5-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [Lucilin TPO (manufactured by IGM Resins)] (E5-4)2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole [Biimidazole (manufactured by Kurogane Kasei Co., Ltd.)] (E5-5)p-dimethylaminoacetophenone [DMA (manufactured by Daikifine Co., Ltd.)] (E5-6)1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one [Omnirad2959 (manufactured by IGM RESINS BV)] (E5-7) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide [Omnirad819 (manufactured by IGM RESINS BV)]

[0236] <Thermosetting compound (CE)> • Epoxy compound (CE-1) (CE-1-1) 1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2,2'-bis(hydroxymethyl)-1-butanol [EHPE-3150 (manufactured by Daicel Corporation)] (CE-1-2) Glycidyl etherified epoxy compound of sorbitol [Denacol EX611 (manufactured by Nagase ChemteX)] (CE-1-3) Triglycidyl Isocyanurate Equal amounts of (CE-1-1) to (CE-1-3) were mixed to form epoxy compound (CE-1). • Oxetane compound (CE-2): 3-Ethyl-3-[(3-ethyloxetane-3-yl)methoxymethyl]oxetane [Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

[0237] <Sensitizer (H)> (H-1)2,4-Diethylthioxanthone [KayaCure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)] (H-2)4,4'-bis(diethylamino)benzophenone [CHEMARK DEABP (manufactured by Chemark Chemical)] As described above, (H-1) and (H-2) were mixed in equal amounts to form the sensitizer (H).

[0238] <Thiol-based chain transfer agent (I)> (I-1) Trimethylolethantris(3-mercaptobutyrate) [TEMB (manufactured by Showa Denko)] (I-2) Trimethylolpropanetris(3-mercaptobutyrate) [TPMB (manufactured by Showa Denko)] (I-3) Pentaerythritol tetrakis(3-mercaptopropionate) [PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)] (I-4) Trimethylolpropanetris (3-mercaptopropionate) [TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)] (I-5) Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate [TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)] The above (I-1) to (I-5) were mixed in equal amounts to form thiol chain transfer agent (I).

[0239] <Polymerization inhibitor (J)> (J-1)3-methylcatechol (J-2) Methylhydroquinone (J-3) tert-butylhydroquinone The above (J-1) to (J-3) were mixed in equal amounts to form polymerization inhibitor (J).

[0240] <UV absorber (K)> (K-1)2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine [TINUVIN400 (manufactured by BASF Japan)] (K-2)2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol [TINUVIN900 (manufactured by BASF Japan)] As described above, (K-1) and (K-2) were mixed in equal amounts to form the ultraviolet absorber (K).

[0241] <Antioxidant (L)> (L-1) Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (L-2)3,3'-Dioctadecyl Thiodipropanoate (L-3) Tris[2,4-di-(tert)-butylphenyl]phosphine (L-4) Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (L-5) p-octylphenyl salicylate The above (L-1) to (L-5) were mixed in equal amounts to form antioxidant (L).

[0242] <Leveling agent (M)> One unit of "BYK-330" manufactured by Big Chemie Co., Ltd. One copy of DIC's "Megafuck F-551". Kao Corporation's "Emulgen 103" (1 unit) The above was dissolved in 97 parts of PGMAc to create a mixed solution which was used as the leveling agent (M).

[0243] <Storage stabilizer (N)> (N-1)2,6-bis(1,1-dimethylethyl)-4-methylphenol (BHT manufactured by Honshu Chemical Industry Co., Ltd.) (N-2)triphenylphosphine (“TPP” manufactured by Hokuko Chemical Industry Co., Ltd.) As described above, (N-1) and (N-2) were mixed in equal amounts to form the storage stabilizer (N).

[0244] <Adhesion enhancer (O)> (O-1)3-Glycidoxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (O-2)3-methacryloxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (O-3)N-2-(aminoethyl)-3-aminopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (O-4)3-mercaptopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)] The above (O-1) to (O-4) were mixed in equal amounts to form the silane coupling agent (O).

[0245] <Solvent (Q)> (Q-1) PGMAc 30 copies (Q-2) Cyclohexanone 30 parts (Q-3) 3-Ethoxypropionate 10 parts (Q-4) Propylene glycol monomethyl ether 10 parts (Q-5) Cyclohexanol acetate 10 parts (Q-6) Dipropylene glycol methyl ether acetate 10 parts The above (Q-1) to (Q-6) were mixed in the above-mentioned parts by mass to obtain solvent (Q).

[0246] <Evaluation of Coloring Composition> (Evaluation of Alkaline Developability) On a 6-inch silicon wafer, a resist solution for a planarizing film (「HL-18s」manufactured by Nippon Steel Chemical Co., Ltd.) was spin-coated, heated on a hot plate at 100°C for 6 minutes, and then heated in an oven at 230°C for 1 hour to cure the coating film and obtain a silicon wafer with a planar film. Next, each of the coloring compositions (R-1, R-31 to 49) was spin-coated on the planarizing film so that the film thickness after drying would be 0.7 μm, pre-baked on a hot plate at 100°C for 1 minute, and exposed through a photomask for forming a 1.0-μm square pixel at a wavelength of 365 nm using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) at an exposure dose of 3000 J / m 2 and pattern exposure was performed. The exposed coating film was paddle-developed with an organic alkaline developer. After paddle development, it was washed with pure water in a spin shower for 20 seconds, the water droplets remaining on the wafer were blown off with high-pressure air, and the substrate was naturally dried to form a square pixel pattern. The surface of the unexposed portion washed away by development was observed with a scanning electron microscope (「S-3000N」manufactured by Hitachi High-Technologies Corporation), and the alkaline developability was determined based on the presence or absence of residues. 3 or more indicates that it can be used without practical problems. 5: No residue at a development time of 1 minute 4: A slight residue is observed at a development time of 1 minute 3: A little residue is observed at a development time of 1 minute 2: A large amount of residue is observed at a development time of 1 minute (not usable) 1: A severe residue is observed at a development time of 1 minute (not usable)

[0247] (Pattern Formability) A test substrate was formed in the same procedure as the above alkaline developability test, and the ratio of pixel defects among 50 pattern pixels of 1.0-μm square diameter was observed with a scanning electron microscope (「S-3000N」manufactured by Hitachi High-Technologies Corporation). If it is 3 or more, it can be used without practical problems. 5: No pixel defects among 50 pattern pixels 4: 1 or more and less than 3 pixel defects among 50 pattern pixels 3: 2: Out of 50 pattern pixels, 6 to 10 pixels are missing (unusable). 1: Out of 50 pattern pixels, 10 or more are missing pixels (unusable). [Explanation of symbols]

[0248] 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 100 Infrared Sensors 110 Photodetector 111 Infrared Absorption Filter 112 Color Filters 113 Infrared Absorption and Transmission Filter 114 Resin film 115 Microlenses 116 Flat membrane

Claims

1. A coloring composition characterized in that, when a film with a thickness of 0.7 μm is formed, the average transmittance of the film in the thickness direction in the wavelength range of 400 to 650 nm is 2.5% or less, and the average transmittance of the film in the thickness direction in the wavelength range of 800 to 1000 nm is 90% or more, the composition containing a coloring agent (A) containing C.I. Pigment Violet 37 and C.I. Pigment Yellow 139, and a resin-type dispersant (B), wherein, with a total pigment of 100 parts by mass, C.I. Pigment Violet 37 is 25 to 75 parts by mass and C.I. Pigment Yellow 139 is 25 to 45 parts by mass.

2. The coloring composition according to claim 1, further comprising 0 to 35 parts by mass of any blue pigment selected from C.I. Pigment Blue 15:1, 15:2, 15:3, 15:4, or 15:6, per 100 parts by mass of the total pigment.

3. The colored composition according to claim 1 or 2, characterized in that the resin-type dispersant (B) contains a resin-type dispersant (B1) having an aromatic carboxyl group.

4. A cured film which is a cured product of the colored composition according to claim 1 or 2.

5. An optical filter having the cured film described in claim 4.

6. An image display device having a cured film as described in claim 4.

7. A solid-state image sensor having the cured film described in claim 4.

8. An infrared sensor having a cured film as described in claim 4.

Images