Coloring composition, optical filter, infrared camera, and infrared sensor

Abstract

To provide a coloring composition which is excellent in light-shielding property in a region at a wavelength of 400-800 nm, and exhibits excellent characteristics such as a low foreign matter generation rate, high storage stability, filterability, and coating uniformity of a coated film, an optical filter using the same, and an infrared camera and an infrared sensor having the optical filter.SOLUTION: A coloring composition contains a near infrared absorptive coloring material (A) having maximum absorption at 700-1,300 nm, a chromatic coloring material (B) having maximum absorption at 400-700 nm, a resin type dispersion agent (C), a binder resin (D) and a solvent (E), and contains 67-90 mass% of the near infrared absorptive coloring material (A) in 100 mass% of the total of the near infrared absorptive coloring material (A) and the chromatic coloring material (B).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a coloring composition using a near-infrared absorbing coloring material and a chromatic coloring material, an optical filter, an infrared camera, and an infrared sensor. [Background technology]

[0002] In recent years, the development of optical sensors that use infrared rays with wavelengths of 900 nm or more as light sources has been studied. Because infrared rays have a longer wavelength than visible light, they are less likely to scatter, making them suitable for use in proximity sensors and motion sensors. Furthermore, because they are invisible to the human and animal eye, they can be used in cameras for night photography, without the subject noticing the infrared radiation. As such, optical sensors that detect infrared rays (infrared sensors) can be used in a variety of applications, and there is a need for the development of optical filters that can be used in infrared sensors.

[0003] Optical filters used in infrared sensors are required to have the ability to block visible light and infrared light in a specific range and selectively transmit some infrared light depending on the application. Coloring compositions for optical filters that combine multiple near-infrared absorbing colorants and chromatic colorants are known (Patent Documents 1 and 2). However, previously known coloring compositions sometimes have problems with the generation of foreign matter due to the mixing of multiple colorants, as well as problems with storage stability and filterability. Furthermore, the coating uniformity of the coating film required for producing optical filters has not been sufficient. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] WO2015 / 061129 Brochure [Patent Document 2] WO2016 / 190162 Brochure Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a coloring composition that exhibits excellent light-shielding properties in the wavelength region of 400 to 800 nm, produces little aggregated foreign matter, and exhibits excellent properties such as high storage stability, filterability, and coating uniformity of a coating film; an optical filter using the same; and an infrared camera and an infrared sensor that are equipped with the optical filter. [Means for solving the problem]

[0006] As a result of extensive research into solving the above-mentioned problems, the present inventors have found that a coloring composition comprising a near-infrared absorbing colorant (A) having an absorption maximum in the range of 700 to 1300 nm, a chromatic colorant (B) having an absorption maximum in the range of 400 to 700 nm, a resin-type dispersant (C), a binder resin (D), and a solvent (E), wherein the coloring composition contains 67 to 90 mass% of the near-infrared absorbing colorant (A) relative to a total of 100 mass% of the near-infrared absorbing colorant (A) and the chromatic colorant (B), exhibits excellent properties, and have completed the present invention based on this finding.

[0007] That is, the present invention relates to a coloring composition comprising a near-infrared absorbing colorant (A) having an absorption maximum in the range of 700 to 1300 nm, a chromatic colorant (B) having an absorption maximum in the range of 400 to 700 nm, a resin-type dispersant (C), a binder resin (D), and a solvent (E), wherein the coloring composition contains 67 to 90 mass% of the near-infrared absorbing colorant (A) relative to a total of 100 mass% of the near-infrared absorbing colorant (A) and the chromatic colorant (B).

[0008] The present invention also relates to the coloring composition, wherein the near-infrared absorbing colorant (A) contains a near-infrared absorbing colorant (A1) that satisfies the following conditions (1) and (2): (1) Average primary particle size is 5 to 150 nm. (2) When a film having a thickness of 1.0 μm is formed, the maximum value S of the light transmittance in the thickness direction of the film in the range of 400 to 900 nm and the minimum value T in the range of 700 to 1300 nm satisfy the following formula: S / T=5~150

[0009] The present invention also relates to the colored composition, wherein the resin-type dispersant (C) contains an acidic resin-type dispersant having an acid value of 30 to 80 mgKOH / g.

[0010] The present invention also relates to the colored composition, wherein the acidic resin-type dispersant comprises a resin-type dispersant that is a reaction product obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product between a polymer having a hydroxyl group at at least one terminal and a tricarboxylic acid anhydride or a tetracarboxylic acid dianhydride and / or a reaction product between a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride or a tetracarboxylic acid dianhydride.

[0011] The present invention also relates to the above coloring composition, wherein the solvent (E) contains methoxypropyl acetate.

[0012] The present invention also relates to the colored composition, wherein the water content in the colored composition is 0.1 to 2.0% by mass relative to 100% by mass of the colored composition.

[0013] The present invention also relates to the coloring composition, which contains a metal component containing a metal atom selected from Li, Na, K, Cs, Mg, Ca, Fe, and Zr, and the total amount of the metal atoms contained in the metal component is 1 to 1000 ppm by mass relative to 100% by mass of the coloring composition.

[0014] The present invention also relates to the coloring composition, which further contains a photopolymerizable monomer and / or a photopolymerization initiator.

[0015] The present invention also relates to an optical filter having a coating formed on a substrate from the coloring composition.

[0016] The present invention also relates to an infrared camera equipped with the optical filter.

[0017] The present invention also relates to an infrared sensor comprising the optical filter. [Effects of the Invention]

[0018] The present invention can provide a coloring composition that exhibits excellent light-shielding properties in the wavelength region of 400 to 800 nm, produces little aggregated foreign matter, and exhibits excellent properties such as high storage stability, filterability, and coating uniformity of a coating film; an optical filter using the coloring composition; and an infrared camera and an infrared sensor that are equipped with the optical filter. DETAILED DESCRIPTION OF THE INVENTION

[0019] The constituent features of the present invention will be described in detail below. In this application, unless otherwise specified, the terms "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", or "(meth)acrylate" refer to "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", or "acrylate and / or methacrylate", respectively. Furthermore, "CI" in this specification means , stands for color index (CI).

[0020] <Coloring composition> The coloring composition of the present invention is a coloring composition containing a near-infrared absorbing colorant (A) having an absorption maximum in the range of 700 to 1300 nm, a chromatic colorant (B) having an absorption maximum in the range of 400 to 700 nm, a resin-type dispersant (C), a binder resin (D), and a solvent (E), and contains 67 to 90 mass% of the near-infrared absorbing colorant (A) relative to a total of 100 mass% of the near-infrared absorbing colorant (A) and the chromatic colorant (B). This allows the coloring composition to exhibit excellent effects in terms of light-shielding properties in the wavelength range of 400 to 800 nm, reduction of foreign matter, storage stability, filterability, and coating uniformity of the coating film.

[0021] The coloring material preferably contains 70 to 85 mass % of the near-infrared absorbing coloring material (A) and 15 to 30 mass % of the chromatic coloring material (B). By satisfying these requirements, a coloring composition excellent in storage stability, reduced foreign matter, and light-shielding properties can be obtained.

[0022] <Colorant> The coloring material means a near-infrared absorbing coloring material (A) having a maximum absorption in the range of 700 to 1300 nm, and a chromatic coloring material (B) having a maximum absorption in the range of 400 to 700 nm.

[0023] <Near-infrared absorbing colorant (A)> The near-infrared absorbing colorant (A) is a colorant having an absorption maximum in the wavelength range of 700 to 1300 nm. The near-infrared absorbing colorant (A) in the present invention may be either a pigment or a dye. Examples of the near-infrared absorbing colorant (A) include indigo compounds, anthraquinone compounds, dipyrromethene compounds, pyrrolopyrrole compounds, phthalocyanine compounds, naphthalocyanine compounds, perylene compounds, cyanine compounds, dithiol metal complex compounds, naphthoquinone compounds, iminium compounds, azo compounds, quinoline compounds, and squarylium compounds. Examples of indigo compounds that may be used include compounds disclosed in JP-A-2012-224593 and JP-A-2013-87233. Examples of dipyrromethene compounds that may be used include compounds disclosed in JP-A-2018-123093 and WO2017 / 159610. Examples of the pyrrolopyrrole compound that can be used include compounds disclosed in JP 2009-263614 A and WO 2018 / 043218 A. Examples of the quinoline compound that can be used include compounds disclosed in JP 2012-131862 A. [Near-infrared absorbing colorant (A1)] The near-infrared absorbing colorant (A) in the present invention preferably contains a near-infrared absorbing colorant (A1) that satisfies the following conditions (1) and (2). (1) Average primary particle size is 5 to 150 nm. (2) When a film having a thickness of 1.0 μm is formed, the maximum value S of the light transmittance in the thickness direction of the film in the range of 400 to 900 nm and the minimum value T in the range of 700 to 1300 nm satisfy the following formula: S / T=5~150

[0024] The transmittance of the near-infrared absorbing colorant (A1) is a value measured by the method described in the examples below.

[0025] The near-infrared absorbing colorant (A) that satisfies (1) can be obtained by pulverization. The pulverization method is not particularly limited, and examples thereof include wet grinding, dry grinding, and solution precipitation. Among these, salt milling treatment using a kneader method, which is a type of wet grinding, is preferred. The average primary particle size of the near-infrared absorbing colorant (A) that satisfies (1) as determined by TEM (transmission electron microscope) is preferably 5 to 150 nm, more preferably 10 to 100 nm. Having an appropriate particle size improves storage stability and filterability.

[0026] Salt milling is a process in which a mixture of near-infrared absorbing colorant (A), a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded under heating using a batch or continuous mixer such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, or planetary mixer, and then the water-soluble inorganic salt and water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the near-infrared absorbing colorant (A) is crushed during salt milling by utilizing the high hardness of the inorganic salt. By optimizing the conditions for salt milling the near-infrared absorbing colorant (A), a near-infrared absorbing colorant (A) with an extremely fine primary particle size and a narrow, sharp particle size distribution can be obtained.

[0027] Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate. Among these, inexpensive sodium chloride (table salt) is preferred. From the viewpoints of both processing efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000 mass%, more preferably 300 to 1000 mass%, relative to 100 mass% of the near-infrared absorbing colorant (A).

[0028] The water-soluble organic solvent functions to moisten the near-infrared absorbing colorant (A) and the water-soluble inorganic salt. It is not particularly limited as long as it dissolves (is miscible with) water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent becomes prone to evaporation, a high-boiling solvent with a boiling point of 120°C or higher is preferred for safety reasons. Examples of water-soluble organic solvents that can be used 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 water-soluble organic solvent is preferably used in an amount of 5 to 1000% by mass, more preferably 50 to 500% by mass, relative to 100% by mass of the near-infrared absorbing colorant (A).

[0029] When the near-infrared absorbing colorant (A) is subjected to salt milling, a resin may be added as needed. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc. can be used. The resin used is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in the above organic solvents. The amount of resin used is preferably 5 to 200% by mass relative to 100% by mass of the near-infrared absorbing colorant (A).

[0030] Examples of near-infrared absorbing colorants (A) that satisfy (2) include indigo compounds, anthraquinone compounds, dipyrromethene compounds, phthalocyanine compounds, naphthalocyanine compounds, perylene compounds, cyanine compounds, dithiol metal complex compounds, and quinoline compounds. Indigo compounds and naphthalocyanine compounds are more preferred as near-infrared absorbing colorants (A) that satisfy (2). Examples of commercially available products include SDO-C33 (manufactured by Arimoto Chemical Industry Co., Ltd.), 5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine copper(II), IR-813-p-toluenesulfonate, indocyanine green, bis[4,4'-dimethoxy(dithiobenzyl)]nickel(II), and tetrabutylammonium bis(3,6-dichloro-1,2-benzenedithiolato)nickelate (all manufactured by Tokyo Chemical Industry Co., Ltd.).

[0031] By using a near-infrared absorbing colorant (A) that satisfies (2) in the coloring composition, the light-blocking properties are improved. An excellent coloring composition can be obtained.

[0032] By micronizing the near-infrared absorbing colorant (A) that satisfies the above-mentioned (2), a near-infrared absorbing colorant (A1) that satisfies both (1) and (2) can be obtained.

[0033] <Chromatic color material (B)> The chromatic colorant (B) is a colorant having an absorption maximum in the wavelength range of 400 to 700 nm. A colorant having an absorption maximum in the wavelength range of 400 nm or more and less than 700 nm is preferred. The chromatic colorant (B) may be a pigment or a dye, but a pigment is preferred because it is easier to obtain a colored composition that can form a film with excellent heat resistance. As the pigment, organic or inorganic pigments can be used alone or in combination of two or more types. As the pigment, a pigment with high color development and high heat resistance, particularly a pigment with high resistance to thermal decomposition, is preferred, and organic pigments are usually used. Specific examples of chromatic colorants (B) that can be used in the colored composition are shown below by color index number.

[0034] Examples of red colorants include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 13 3:1, 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, 288, 289, 290, 300, 301, 302, 303, 304, 305, 306, 307, 308, 309, 310, 311, 312, 313, 314, 315, 316, 317, 318, 319, 320, 321, 322, 323, 324, 325, 326, 327, 328, 329, 63, 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, or 296, the pigments described in JP-A-2014-134712, and the pigments described in Japanese Patent No. 6368844 can be used.

[0035] As the orange colorant, orange pigments such as CI Pigment Orange 34, 36, 38, 43, 51, 55, 59, 61, 62, 64, 71, or 73 can be used.

[0036] Yellow colorants include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, Yellow pigments such as 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221, 231, 233, or 234 can be used.

[0037] Green pigments include, for example, CI Pigment Green 7, 10, 36, 37, 58, Green pigments such as Nos. 59, 62, and 63 can be used. Aluminum phthalocyanine pigments are also preferably used, and aluminum phthalocyanine pigments such as those described in JP-A No. 2004-333817 and Japanese Patent No. 4893859 can also be used.

[0038] Examples of blue pigments that can be used include CI Pigment Blue 1, 1:2, 1:3, 2, 2:1, 2:2, 3, 8, 9, 10, 10:1, 11, 12, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 18, 19, 22, 24, 24:1, 53, 56, 56:1, 57, 58, 59, 60, 61, 62, and 64. Examples of purple pigments that can be used in combination include CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50.

[0039] Inorganic pigments include titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (iron (III) red), cadmium red, ultramarine, iron blue, chromium oxide green, and cobalt. Examples of inorganic pigments include green, amber, synthetic iron black, etc. Inorganic pigments are used in combination with organic pigments to ensure good coating properties, sensitivity, developability, etc. while maintaining a balance between saturation and brightness.

[0040] In the present invention, dyes can also be used. Examples include anthraquinone dyes, monoazo dyes, disazo dyes, oxazine dyes, aminoketone dyes, xanthene dyes, quinoline dyes, and triphenylmethane dyes. When using dyes, it is effective to incorporate the polar groups of anionic or cationic dyes into the resin to impart solubility in solvents.

[0041] Specific examples of usable anionic dyes are shown below by color index number.

[0042] Red dyes include CI Acid Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 25:1, 26, 26:1, 26:2, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 44, 45, 47, 50, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 3, 54, 55, 56, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76:1, 80, 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 107, 108, 110, 111, 113, 114, 115, 116, 120, 123, 125, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 186, 187, 18 28, 131, 132, 133, 134, 135, 137, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161, 163, 164, 167, 170, 171, 172, 173, 175, 176, 177, 181, 229, 231, 237, 239, 240, 241, 242, 243 9, 252, 253, 255, 257, 260, 263, 264, 266, 267, 274, 276, 280, 286, 289, 299, 306, 309, 311, 323, 333, 324, 325, 326, 334, 335, 336, 337, 340, 343, 344, 347, 348, 350, 351, 353, 354, 356, 388, etc.

[0043] Also, CI Direct Red 1, 2, 2:1, 4, 5, 6, 7, 8, 10, 10:1, 13, 14, 15, 16, 17, 18, 21, 22, 23, 24, 26, 26:1, 28, 29, 31, 33, 33:1, 34, 35, 36, 37, 39, 42, 43, 43:1, 44, 46, 49, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 110, 111, 112, 113, 114, 115, 116, 117, 118, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131 5, 56, 57, 58, 59, 60, 61, 62, 67, 67:1, 68, 72, 72:1, 73, 74, 75, 77, 78, 79, 81, 81:1, 85, 86, 88, 89, 90, 97, 100, 101, 101:1, 107, 108, 110, 114, 116, 117, 120, 121, 122, 123 :1, 124, 125, 127, 127:1, 127:2, 128, 129, 130, 132, 134, 135, 136, 137, 138, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, 169, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 186, 189, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237, 238, etc. can also be used.

[0044] Yellow dyes include CI Acid Yellow 2, 3, 4, 5, 6, 7, 8, 9, 9:1, 10, 11, 11:1, 12, 13, 14, 15, 16, 17, 17:1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40:1, 41, 42, 42:1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, and 66. , 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199, etc.

[0045] Also usable are CI Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44:1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134, and the like.

[0046] Examples of orange dyes include CI Acid Orange 1, 1:1, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 17, 18, 19, 20, 20:1, 22, 23, 24, 24:1, 25, 27, 28, 28:1, 30, 31, 33, 35, 36, 37, 38, 41, 45, 49, 50, 51, 54, 55, 56, 59, 79, 83, 94, 95, 102, 106, 116, 117, 119, 128, 131, 132, 134, 136, and 138. CI Direct Orange 1, 2, 3, 4, 5, 6, 7, 8, 10, 13, 17, 19, 20, 21, 24, 25, 26, 29, 29:1, 30, 31, 32, 33, 43, 49, 51, 56, 59, 69, 72, 73, 74, 75, 76, 79, 80, 83, 84, 85, 87, 88, 90, 91, 92, 95, 96, 97, 98, 101, 102, 102:1, 104, 108, 112, 114, etc. can also be used.

[0047] Blue dyes include CI Acid Blue 1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 13, 14, 15, 17, 19, 21, 22, 23, 24, 25, 26, 27, 29, 34, 35, 37, 40, 41, 41:1, 43, 44, 45, 46, 47, 48, 49, 50, 51, and 52. , 53, 54, 55, 56, 57, 58, 62, 62:1, 63, 64, 65, 68, 69, 70, 73, 75, 78, 79, 80, 81, 83, 8485, 86, 88, 89, 90, 90:1, 91, 92, 93, 95, 96, 99, 100, 103, 104, 108, 109, 11 0, 111, 112, 113, 114, 116, 117, 118, 119, 120, 123, 124, 127, 127:1, 128, 129, 135, 137, 138, 143, 145, 147, 150, 155, 159, 169, 174, 175, 176, 183, 198, 203 , 204, 205, 206, 208, 213, 227, 230, 231, 232, 233, 235, 239, 245, 247, 253, 257, 258, 260, 261, 262, 264, 266, 269, 271, 272, 273, 274, 277, 278, 280, etc.

[0048] Also, CI Direct Blue 1, 2, 3, 4, 6, 7, 8, 8:1, 9, 10, 12 , 14, 15, 16, 19, 20, 21, 21:1, 22, 23, 25, 27, 29, 31, 35, 36, 37, 40, 42, 45, 48, 49, 50, 53, 54, 55, 58, 60, 61, 64, 65, 67, 79, 96, 97, 98:1, 101, 106, 107, 108, 109, 111, 116, 122, 123, 124, 128, 129130, 130:1, 132, 136, 138, 1 40, 145, 146, 149, 152, 153, 154, 156, 158, 158:1, 164, 165, 166, 167, 168, 169, 170, 174, 177, 181, 184, 185, 188, 190, 192, 193, 206, 207, 209, 213, 215, 225, 226, 229, 230, 231, 242, 243, 244, 253, 254, 260, 263, etc. can also be used.

[0049] Examples of purple dyes include CI Acid Violet 1, 2, 3, 4, 5, 5:1, 6, 7, 7:1, 9, 11, 12, 13, 14, 15, 16, 17, 19, 20, 21, 23, 24, 25, 27, 29, 30, 31, 33, 34, 36, 38, 39, 41, 42, 43, 47, 49, 51, 63, 67, 72, 76, 96, 97, 102, 103, and 109.

[0050] You can also use CI Direct Violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64, 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93, 97, etc.

[0051] Examples of green dyes include CI Acid Green 2, 3, 5, 6, 7, 8, 9, 10, 11, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 25:1, 27, 34, 36, 37, 38, 40, 41, 42, 44, 54, 55, 59, 66, 69, 70, 71, 81, 84, 94, and 95. CI Direct Green 11, 13, 14, 24, 30, 34, 38, 42, 49, 55, 56, 57, 60, 78, 79, 80, etc. can also be used.

[0052] Specific examples of usable cationic dyes are shown below by color index number.

[0053] As a triphenylmethane cationic dye, CI Basic Violet 1 ( Methyl Violet), 3 (Crystal Violet), 14 (Magenta), CI Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 26 (Victoria Blue B conc.), CI Basic Green 1 (Brilliant Green GX), CI Basic Green 4 (Malachite Green), etc.

[0054] Xanthene cationic dyes include CI Basic Red 1 (Rhodamine 6G , 6GCP), 3, 8 (Rhodamine G), etc. It is preferable to use Cred 1.

[0055] Cyanine cationic dyes include CI Basic Yellow 11, 21, and 2. 8, etc.

[0056] Anthraquinone cationic dyes include CI Basic Blue 72 and flavin dyes. Cationic dyes include CI Basic Yellow 1 and Auramine-based cationic dyes. The dyes used are CI Basic Yellow 2, 3, and safranine cationic dyes. As for the cationic dyes of the acridine series, CI Basic Red 2 is used, as for the cationic dyes of the oxazine series, CI Basic Yellow 5 is used, as for the cationic dyes of the oxazine series, CI Basic Blue Thiazine cationic dyes include CI Basic Blue 24, methylene As a blue cationic dye, CI Basic Blue 9 (Methylene Blue FZ , Methylene Blue B), 25 (Basic Blue GO), 24 (New Methylene Blue NX), etc. Among them, CI Basic Yellow 1, CI Basic Blue 9, CI Basic Blue 2 It is preferable to use 4 and 25.

[0057] Examples of squarylium-based cationic dyes include (SQ-1K) described in JP-A-2017-114956.

[0058] A preferred embodiment of the chromatic colorant (B) is one containing two or more colorants selected from the group consisting of red, yellow, blue, green, and violet colorants, and more preferably one containing a yellow, blue, and violet colorant. A preferred specific example is one containing CI Pigment Yellow 139 as a yellow pigment, CI Pigment Blue 15:3 as a blue pigment, and CI Pigment Violet 23 as a violet pigment.

[0059] When the chromatic colorant (B) is a pigment, it is preferably micronized before use from the viewpoint of the storage stability and filterability of the coloring composition. The micronization method is the same as the method for the near-infrared absorbing colorant (A) that satisfies (1), except that the near-infrared absorbing colorant (A) is replaced with the chromatic colorant (B).

[0060] When the chromatic colorant (B) contained in the coloring composition is a combination of a yellow colorant, a blue colorant, and a purple colorant, it is preferable that the yellow colorant accounts for 10 to 50 mass% relative to 100 mass% of the total chromatic colorants (B), the blue colorant accounts for 20 to 60 mass% relative to 100 mass% of the total chromatic colorants (B), and the purple colorant accounts for 20 to 50 mass% relative to 100 mass% of the total chromatic colorants (B).

[0061] <Dye derivatives> The coloring composition of the present invention may contain a dye derivative having a structure in which a part of the dye skeleton is substituted with an acidic group, a basic group, or a phthalimidomethyl group. From the viewpoint of reducing foreign matter, it is preferable that the coloring composition contains one type of dye derivative. As the dye derivative, from the viewpoint of dispersibility and storage stability, a dye derivative having an acidic group or a basic group is preferred. Examples of the acidic group possessed by the dye derivative include sulfonic acid, carboxylic acid, and quaternary ammonium salts thereof. The basic group contained in the dye derivative is preferably an amino group, and more preferably a tertiary amino group.

[0062] <Resin-type dispersant (C)> The colored composition of the present invention contains a resin-type dispersant (C). The resin-type dispersant (C) may be any dispersant that has a colorant-affinity moiety that has the property of adsorbing to the colorant and a moiety that is compatible with the colorant carrier, and that functions to adsorb to the colorant and stabilize its dispersion in the colorant carrier.Specific examples include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphate salts, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof, oil-based dispersants such as amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups and their salts, 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 compounds, modified polyacrylate-based compounds, ethylene oxide / propylene oxide adducts, and phosphate ester-based compounds, and these may be used alone or in combination of two or more.

[0063] Examples of basic resin-type dispersants having a basic functional group include nitrogen-atom-containing graft copolymers, and nitrogen-atom-containing acrylic block copolymers and urethane-based resin-type dispersants having functional groups containing tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc. in the side chains.

[0064] Examples of acidic resin-type dispersants having an acidic functional group include those having a carboxyl group, a sulfonic acid group, a phosphate group, etc. in the resin, but from the viewpoints of storage stability and heat resistance, acidic resin-type dispersants having a carboxyl group are preferred.

[0065] [Acidic resin type dispersant] The resin-type dispersant (C) in the present invention preferably contains an acidic resin-type dispersant having an acid value of 30 to 80 mgKOH / g, thereby making it possible to obtain a colored composition having low viscosity and high storage stability.

[0066] The acidic resin-type dispersant preferably contains a resin-type dispersant (S1) which is a reaction product of a hydroxyl group of a polymer having at least one hydroxyl group at its terminal with a tricarboxylic acid anhydride or a tetracarboxylic acid dianhydride, and / or an acidic resin-type dispersant (S2) which is a reaction product of polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a hydroxyl group-containing compound with an acid anhydride group of a tricarboxylic acid anhydride or a tetracarboxylic acid dianhydride. This provides an excellent effect in reducing foreign matter.

[0067] The resin-type dispersant (S1) can be produced by known methods such as those described in WO2008 / 007776, JP2008-029901A, and JP2009-155406A. The polymer (p) having a hydroxyl group is preferably a polymer having a terminal hydroxyl group, and can be obtained, for example, as a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) in the presence of a compound (q) having a hydroxyl group. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Since it is preferable that the compound has multiple terminal hydroxyl groups, a compound (q1) having two hydroxyl groups and one thiol group in the molecule is particularly preferred.

[0068] That is, a more preferred example of a polymer having two hydroxyl groups at one end can be obtained as a polymer (p1) by polymerizing an ethylenically unsaturated monomer (r) containing a monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. The hydroxyl groups of the polymer (p) having hydroxyl groups react with the acid anhydride groups of a tricarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride to form an ester bond, while the anhydride ring opens to generate a carboxylic acid.

[0069] The resin-type dispersant (S2) can be produced by known methods such as those described in JP 2009-155406 A, JP 2010-185934 A, and JP 2011-157416 A, for example, by polymerizing an ethylenically unsaturated monomer (r) in the presence of a reaction product between the hydroxyl group of a hydroxyl-containing compound (q) and the acid anhydride group of a tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride. Among these, a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) containing a monomer (r1) in the presence of a reaction product between the hydroxyl group of a compound (q1) having two hydroxyl groups and one thiol group in the molecule and the acid anhydride group of a tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride is preferred.

[0070] The difference between (S1) and (S2) is whether the polymer moiety obtained by polymerizing the ethylenically unsaturated monomer (r) is introduced first or later. The molecular weight may differ slightly depending on various conditions, but in theory, the same product can be produced if the raw materials and reaction conditions are the same.

[0071] The resin-type dispersants (S1) and (S2) described above each have a carboxyl group-containing polyester moiety and a vinyl polymer moiety. However, it is impossible or practical to specify and describe how these are bonded, so they are described in terms of their manufacturing methods.

[0072] The content of the resin-type dispersant (C) is preferably 5 to 200% by mass relative to 100% by mass of the total colorant, and more preferably 10 to 100% by mass from the viewpoint of film-forming properties.

[0073] <Binder resin (D)> The coloring composition of the present invention contains a binder resin (D). The binder resin (D) is a compound necessary for film formation. Examples of the binder resin (D) include a thermoplastic resin, a thermosetting resin, and an active energy ray-curable resin having an ethylenically unsaturated double bond. It is also preferable that the active energy ray-curable resin has thermosetting properties. From the viewpoint of developability, the binder resin (D) is preferably an alkali-soluble resin.

[0074] 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, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

[0075] Examples of thermosetting resins include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenolic resins.

[0076] The binder resin (D) is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more over the entire wavelength range of 400 to 700 nm in the visible light region.

[0077] The alkali-soluble resin is a resin having an acidic group such as a carboxyl group or a sulfonic group. Examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / maleic acid (anhydride) copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth)acrylic acid copolymer, or an isobutylene / maleic acid (anhydride) copolymer. Among these, an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, which further improve heat resistance and transparency, are preferred, and an acrylic resin having an acidic group is more preferred.

[0078] It is preferable to use an active energy ray-curable resin having an ethylenically unsaturated active double bond to impart photoreactivity to the alkali-soluble resin, which improves the solvent resistance of the cured coating.

[0079] Examples of active energy ray-curable resins having an ethylenically unsaturated double bond include resins into which an unsaturated ethylenically double bond has been introduced by the following methods (a) to (c).

[0080] [Method (a)] In the method (a), for example, an unsaturated ethylenic monomer having an epoxy group and another One method involves subjecting the carboxyl group of an unsaturated monobasic acid having an unsaturated ethylenic double bond to an addition reaction with the side-chain epoxy group of the copolymer obtained by copolymerizing the above-mentioned monomers, and then reacting the resulting hydroxyl group with a polybasic acid anhydride to introduce the unsaturated ethylenic double bond and the carboxyl group.

[0081] Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate, which may be used alone or in combination of two or more. Glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with the unsaturated monobasic acid in the next step.

[0082] Examples of unsaturated monobasic acids include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position, and these may be used alone or in combination of two or more.

[0083] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These may be used alone or in combination of two or more. If necessary, for example, to increase the number of carboxyl groups, a tricarboxylic acid anhydride such as trimellitic anhydride or a tetracarboxylic acid dianhydride such as pyromellitic dianhydride may be used to hydrolyze the remaining anhydride groups. Furthermore, using tetrahydrophthalic anhydride or maleic anhydride, which have unsaturated ethylenic double bonds, as the polybasic acid anhydride can further increase the number of unsaturated ethylenic double bonds.

[0084] [Method (b)] As a method similar to method (a), for example, there is a method in which an unsaturated ethylenic monomer having an epoxy group is subjected to an addition reaction with a part of the side chain carboxyl groups of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group with one or more other monomers, thereby introducing an unsaturated ethylenic double bond and a carboxyl group. In this method, a larger amount of hydroxyl groups derived from the unsaturated ethylenic monomer having an epoxy group is produced than in method (a).When the resin having a cationic group in the side chain used to obtain the salt-forming compound of the present invention contains an oxetanyl group or a t-butyl group as a thermally crosslinkable functional group, it is preferable to use the resin obtained by method (b) as the binder resin (D) because it exhibits higher heat resistance.

[0085] [Method (c)] Method (c) is a method in which an unsaturated ethylenic monomer having a hydroxyl group is used and copolymerized with another unsaturated monobasic acid monomer having a carboxyl group or another monomer, and the side chain hydroxyl group of the copolymer is reacted with the isocyanate group of an unsaturated ethylenic monomer having an isocyanate group.

[0086] Examples of the unsaturated ethylenic monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3-, or 4-hydroxybutyl (meth)acrylate, and glycerol (meth)acrylate. Examples of the hydroxyalkyl (meth)acrylate include hydroxyalkyl (meth)acrylates such as cyclohexanedimethanol mono(meth)acrylate, and these may be used alone or in combination of two or more. In addition, a polyester obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth)acrylate may be used. Ester mono(meth)acrylates and (poly)ester mono(meth)acrylates with (poly)γ-valerolactone, (poly)ε-caprolactone, and / or (poly)12-hydroxystearic acid added thereto can also be used. From the viewpoint of suppressing foreign matter in the coating, 2-hydroxyethyl (meth)acrylate or glycerol (meth)acrylate is preferred.

[0087] Examples of unsaturated ethylenic monomers having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis[(meth)acryloyloxy]ethyl isocyanate, but are not limited to these and two or more types can also be used in combination.

[0088] From the viewpoint of film-forming properties and coating film resistance, the weight average molecular weight (Mw) of the binder resin (D) is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

[0089] When the binder resin (D) is used as a photosensitive composition, it is preferable to use a resin with an acid value of 20 to 300 mgKOH / g from the viewpoints of dispersibility, penetration, developability, and heat resistance of the pigment and salt-forming compound. If the acid value is less than 20 mgKOH / g, the solubility in the developer is poor, making it difficult to form a fine pattern. If the acid value exceeds 300 mgKOH / g, the fine pattern may not remain.

[0090] The binder resin (D) is preferably used in an amount of 30% by mass or more relative to 100% by mass of the total colorant, since it has good film-forming properties and various resistances, and is preferably used in an amount of 500% by mass or less, since it has a high colorant concentration and can express good color properties. <Solvent (E)> The solvent (E) is used to assist the dispersion of the colorant and to appropriately adjust the viscosity of the coloring composition. The solvent (E) used in the coloring composition of the present invention preferably contains methoxypropyl acetate. By using the above solvent, it is possible to form a coating film that is excellent in the dispersibility and penetration of the colorant and excellent in coating uniformity.

[0091] The solvents can be used alone or in combination of two or more.

[0092] Other solvents include, for example, ethyl lactate, benzyl alcohol, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3- Methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-diethylbenzene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether diethylene glycol acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, Examples of the alkyl esters include triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, cyclopentanone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

[0093] The solvent (E) is preferably used in an amount of 500 to 4,000% by mass relative to 100% by mass of the total of the coloring materials, since it adjusts the viscosity of the coloring composition to an appropriate level and enables the formation of a colored film with the desired uniform thickness.

[0094] <Photopolymerizable monomer> The coloring composition of the present invention can be used as a photosensitive coloring composition by further adding a photopolymerizable monomer and / or a photopolymerization initiator. The photopolymerizable monomer that may be added to the coloring composition of the present invention includes a monomer or oligomer that is cured by ultraviolet light, heat, or the like to form a transparent resin.

[0095] Examples of monomers and oligomers that harden when exposed to ultraviolet light or heat to form a transparent resin include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, and bisphenol A diglycidyl. Examples of the acrylic acid esters and methacrylic acid esters include, but are not limited to, ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, ester acrylate, (meth)acrylic acid ester of methylolated melamine, epoxy (meth)acrylate, and urethane acrylate; (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.

[0096] The photopolymerizable compounds can be used alone or in combination of two or more.

[0097] The content of the photopolymerizable monomer is preferably 5 to 400% by mass, and more preferably 10 to 300% by mass, relative to 100% by mass of the total colorant. When an appropriate amount is added, photocurability and developability are further improved.

[0098] <Photopolymerization initiator> The coloring composition of the present invention may contain a photopolymerization initiator. This facilitates photocuring when forming filter segments by photolithography. The amount of the photopolymerization initiator is preferably 5 to 200% by mass, more preferably 10 to 150% by mass, relative to 100% by mass of the total coloring materials. When an appropriate amount is added, photocurability and developability are further improved.

[0099] Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[ 4-(4-morpholinyl)phenyl]-1-butanone, or 2-benzyl-2-dimethyl acetophenone compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzil dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylpermethyl)benzoate benzophenone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, triazine compounds such as 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-chloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; 1-(N-4-benzoylphenyl-carbazol-3-yl)-butane-1,2-dione-2-oxime-O-acetate, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-( 2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxy) Examples of the usable organic solvent include oxime ester compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxy-naphthyl)ethylidene)hydroxylamine; phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds.

[0100] The photopolymerization initiators can be used alone or in combination of two or more.

[0101] <Sensitizer> The colored composition of the present invention can use a photopolymerization initiator and a sensitizer in combination. Examples of the sensitizer include chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzil and camphorquinone, polymethine dyes such as benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triphenylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazinoporphyrazine derivatives. compounds, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4′-diethylisophthalophenone, 3,3′ or 4,4′-tetra(t-butylperoxycarbonyl)benzophenone, 4,4′-diethylaminobenzophenone, and the like.

[0102] Other examples include sensitizers described in "Dye Handbook" edited by Makoto Okawara et al. (1986, Kodansha), "Chemistry of Functional Dyes" edited by Makoto Okawara et al. (1981, CMC), and "Special Functional Materials" edited by Chuzaburo Ikemori et al. (1986, CMC).

[0103] The sensitizers can be used alone or in combination of two or more.

[0104] The amount of the sensitizer used is preferably 3 to 60% by mass, more preferably 5 to 50% by mass, relative to 100% by mass of the photopolymerization initiator. When an appropriate amount is used, photocurability and developability are further improved.

[0105] <Amine compounds> The coloring composition of the present invention may contain an amine compound, which is capable of reducing dissolved oxygen.

[0106] Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and N,N-dimethyl-p-toluidine.

[0107] <Leveling agent> The colored composition of the present invention may contain a leveling agent, which further improves the coatability and coating uniformity of the coating film. Examples of the leveling agent include dimethylsiloxane, as well as various surfactants such as silicon-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants. The dimethylsiloxane is preferably a dimethylsiloxane having a polyether structure and / or polyester structure in the main chain. Commercially available dimethylsiloxanes having a polyether structure in the main chain include FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, and FZ-2207 manufactured by Toray Dow Corning Co., Ltd., and BYK-333 manufactured by BYK-Chemie. Commercially available dimethylsiloxanes having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie.

[0108] Examples of anionic surfactants include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonates, sodium alkyldiphenyletherdisulfonates, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphates.

[0109] Examples of cationic surfactants include alkyl quaternary ammonium salts and their ethylene oxide adducts. Examples of nonionic surfactants that can be added to the leveling agent as an auxiliary include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; alkyl betaines such as alkyl dimethylaminoacetic acid betaine; amphoteric surfactants such as alkyl imidazolines; and fluorine-based and silicone-based surfactants.

[0110] The leveling agents can be used alone or in combination of two or more kinds.

[0111] The content of the leveling agent is preferably 0.003 to 0.5% by mass in 100% by mass of the colored composition.

[0112] <Epoxy compounds> The coloring composition of the present invention can contain an epoxy compound.

[0113] Examples of epoxy compounds include phenol novolac type epoxy resins, cresol novolac type epoxy resins, trishydroxyphenylmethane type epoxy resins, dicyclopentadiene phenol type epoxy resins, bisphenol-A type epoxy resins, bisphenol-F type epoxy resins, biphenol type epoxy resins, bisphenol-A novolac type epoxy resins, naphthalene skeleton-containing epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins.

[0114] Commercially available phenol novolac epoxy resins include, for example, Epiclon N-740, Epiclon N-770, and Epiclon N-775 manufactured by DIC Corporation, DEN438 manufactured by Dow Chemical Company, RE-306 manufactured by Nippon Kayaku Co., Ltd., and jER152 and jER154 manufactured by Mitsubishi Chemical Corporation.

[0115] Commercially available cresol novolac epoxy resins include Epicron N-660, Epicron N-665, Epicron N-670, Epicron N-673, Epicron N-680, Epicron N-695, Epicron N-665-EXP, and Epicron N-672-EXP manufactured by DIC Corporation, EOCN-102S, EOCN-103S, and EOCN-104S manufactured by Nippon Kayaku Co., Ltd., UVR-6650 manufactured by Union Carbide Corporation, and ESCN-195 manufactured by Sumitomo Chemical Co., Ltd.

[0116] Commercially available trishydroxyphenylmethane epoxy resins include EPPN-503, EPPN-502H, and EPPN-501H manufactured by Nippon Kayaku Co., Ltd., TACTIX-742 manufactured by Dow Chemical Company, and jERE1032H60 manufactured by Mitsubishi Chemical Corporation.

[0117] The commercially available dicyclopentadiene phenol type epoxy resin is Epicron E manufactured by DIC. XA-7200, and TACTIX-556 manufactured by Dow Chemical Company.

[0118] Commercially available bisphenol-type epoxy resins include bisphenol-A type epoxy resins such as jER828 and jER1001 manufactured by Mitsubishi Chemical Corporation, UVR-6410 manufactured by Union Carbide, DER-331 manufactured by Dow Chemical Company, and YD-8125 manufactured by Shin-Nippon Epoxy Manufacturing Co., Ltd., and bisphenol-F type epoxy resins such as UVR-6490 manufactured by Union Carbide and YDF-8170 manufactured by Shin-Nippon Epoxy Manufacturing Co., Ltd.

[0119] Commercially available biphenol-type epoxy resins include biphenol-type epoxy resins such as NC-3000 and NC-3000H manufactured by Nippon Kayaku Co., Ltd., and jER YX-4000 and jE Examples of suitable epoxy resins include bixylenol type epoxy resins such as ® YL-6121.

[0120] Commercially available bisphenol A novolac epoxy resins include Epiclon N-880 manufactured by DIC Corporation and jER E157S75 manufactured by Mitsubishi Chemical Corporation.

[0121] Commercially available naphthalene skeleton-containing epoxy resins include NC-7000 and NC-7300 manufactured by Nippon Kayaku Co., Ltd., and EXA-4750 manufactured by DIC Corporation.

[0122] Commercially available alicyclic epoxy resins include Seikicide 2021P, 2081, 2000, Epolead PB3600, PB4700, GT401, EHPE-3150, and Cyclomer M100 manufactured by Daicel Corporation.

[0123] Commercially available heterocyclic epoxy resins include TEPIC-L, TEPIC-H, and TEPIC-S manufactured by Nissan Chemical Industries, Ltd.

[0124] The epoxy compounds can be used alone or in combination of two or more.

[0125] The content of the epoxy compound is preferably 0.5 to 50 mass %, more preferably 1 to 40 mass %, based on 100 mass % of the nonvolatile content of the colored composition. When an appropriate amount is contained, heat resistance is further improved.

[0126] <Oxetane compounds> The coloring composition of the present invention may contain an oxetane compound. Examples of the oxetane compound include monofunctional, difunctional, and trifunctional or higher functional compounds having an oxetane group.

[0127] Examples of the compound having one functional oxetane group include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, and 3-ethyl 3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane, etc. Commercially available products include OXE-10 and OXE-30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101 and 212 manufactured by Toagosei Co., Ltd.

[0128] Examples of compounds having two functional oxetane groups include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether-3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl] ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycose bis(3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene Examples of suitable bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether include ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, ethylene oxide (EO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, propylene oxide (PO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl)ether. Commercially available bisphenol A bis(3-ethyl-3-oxetanylmethyl)ethers include OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

[0129] Examples of compounds having three or more functional oxetane groups include pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, and caprolactone-modified dipentaerythritol. Examples of such polymers include dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (for example, the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the above-mentioned OXE-30.

[0130] The oxetane compounds can be used alone or in combination of two or more.

[0131] The content of the oxetane compound is preferably from 0.5 to 50% by mass, and more preferably from 1 to 40% by mass, relative to 100% by mass of the nonvolatile content of the colored composition. When an appropriate amount is contained, heat resistance is further improved.

[0132] <UV absorber> The coloring composition of the present invention may contain an ultraviolet absorber. Examples of the ultraviolet absorber include benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds.

[0133] The content of the ultraviolet absorber is preferably 5 to 70% by mass, based on 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. This allows for a high degree of compatibility between photosensitivity and resolution. When the coloring composition contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

[0134] The total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass relative to 100% by mass of the nonvolatile content of the coloring composition. If the total content of the photopolymerization initiator and the ultraviolet absorber is less than the above range, adhesion may be weakened, causing pixel peeling, while if it is more than the above range, sensitivity may be too high, resulting in poor resolution.

[0135] Benzotriazole organic compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, benzotriazole, a mixture of octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-[2-hydroxy -3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 5% of 2-methan Examples include 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side chain and straight chain alkyl esters.

[0136] Commercially available products include BASF's "TINUVIN P," "TINUVIN PS," "TINUVIN 109," "TINUVIN 234," "TINUVIN 326," and "TINUVIN 327." UVIN 328”, “TINUVIN 329”, “TINUVIN 360”, “TI NUVIN 384-2”, “TINUVIN 900”, “TINUVIN 928”, Examples include "TINUVIN 99-2", "TINUVIN 1130", "ADEKA STAB LA-29" manufactured by ADEKA Corporation, and "RUNA-93" manufactured by Otsuka Chemical Co., Ltd.

[0137] Examples of triazine organic compounds include 2-[4,6-di(2,4-xylyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, a reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl-glycidic acid ester), and 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3-5-triazine.

[0138] Commercially available products include "KEMISORB 102" manufactured by Chemipro Chemicals and "TINUV" manufactured by BASF. IN 400”, “TINUVIN 405”, “TINUVIN 460”, “TINU VIN 477-DW”, “TINUVIN 479”, “TINUVIN 1577”, Examples include "ADEKA STAB LA-46" and "ADEKA STAB LA-F70" manufactured by ADEKA Corporation, and "CYASORB UV-1164" manufactured by Sun Chemical Company.

[0139] Examples of benzophenone-based organic compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3-oxide, 2-hydroxy-4-n-octoxybenzophenone, and 2,2-dihydroxy-4-methoxybenzophenone.

[0140] Commercially available products include KEMISORB 10, KEMISORB 11, KEMISORB 11S, KEMISORB 12, and KEMISORB11 manufactured by Chemipro Chemicals. 1”, Shipro Kasei Co., Ltd.'s “SEESORB 101” and “SEESORB 107”, and ADEKA Corporation's “ADEKA STAB 1413”.

[0141] <Thiol-based chain transfer agents> The coloring composition of the present invention can contain a thiol-based chain transfer agent. When a thiol-based chain transfer agent is used together with a photopolymerization initiator, it acts as a chain transfer agent in the radical polymerization process after light irradiation. This generates thiyl radicals that are less susceptible to polymerization inhibition by oxygen, improving photosensitivity, and thereby improving photocuring from the surface of the coating to its depths.

[0142] Examples of polyfunctional thiols include hexanedithiol and decanedithiol. , 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, and the like are mentioned, and preferably, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate.

[0143] The thiol chain transfer agents can be used alone or in combination of two or more.

[0144] The content of the thiol chain transfer agent is preferably 1 to 10 mass %, more preferably 2 to 8 mass %, based on 100 mass % of the nonvolatile content of the coloring composition. When used in an appropriate amount, photosensitivity is improved and a coating film with a good shape can be obtained.

[0145] <Antioxidants> The coloring composition of the present invention can contain an antioxidant. The antioxidant prevents a coating film formed from the coloring composition from oxidizing and yellowing during a heating process such as thermal curing, thereby maintaining the transmittance of the coating film. This is because, particularly when the colorant concentration of the photosensitive coloring composition is high, the amount of crosslinking component is relatively small, and measures such as using a highly sensitive crosslinking component or increasing the amount of photopolymerization initiator can intensify yellowing during the heating 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.

[0146] The "antioxidant" in the present invention may be any compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function, and specific examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylic acid ester-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, etc. can be used. Furthermore, the antioxidant used in the present invention is preferably one that does not contain a halogen atom.

[0147] Among these antioxidants, from the viewpoint of achieving both transmittance and sensitivity of the coating film, preferred ones include hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.

[0148] Hindered phenol antioxidants include 2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-tris(trimethylsilyl)-2,4-bis ... din, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), 2,2'-thio-bis-(6-t-butyl-4-methylphenol), Examples include 2,5-di-t-amyl-hydroquinone, 2,2'-thiodiethyl bis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), etc. Other oligomer and polymer compounds having a hindered phenol structure can also be used. Commercially available products include ADK STAB AO-20, AO-30, AO-40, AO50, AO60, AO80, and AO320 manufactured by ADEKA Corporation; KEMINOX 101, 179, 76, and 9425 manufactured by Chemipro; IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 manufactured by BASF; and Cyanox CY-1790 and CY-2777 manufactured by Sun Chemical Company.

[0149] Hindered amine antioxidants include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine, and 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino. -N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)(1,2,3,4-butanetetracarboxylate), poly[{6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl)imino}], poly[(6-morpholino-1,3,5-triazine-2,4-diyl){(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethine{(2,2,6,6-tetramethyl-4-piperidyl)imino}], polycondensation product of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, etc. Other oligomeric and polymeric compounds having a hindered amine structure can also be used. Commercially available products include ADK STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, and LA-502XP manufactured by ADEKA Corporation; KAMISTAB 29, 62, 77, 29, and 94 manufactured by Chemipro Chemicals; Tinuvin 249, TINUVIN 111FDL, 123, 144, 292, and 5100 manufactured by BASF; and Cyasorb UV-3346, UV-3529, and UV-3853 manufactured by Sun Chemical Company.

[0150] Phosphorus-based antioxidants include tris(isodecyl)phosphite, tris(tridecyl)phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl)phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris(nonylphenyl)phosphite, 4,4'-isopropylidenediphenol alkyl phosphite, trisnonylphenyl phosphite, tris(dinonylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(biphenyl)phosphite, distearyl pentaerythritol diphosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenyl Examples include bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl) phosphite, sodium 2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, and ethyl bis(2,4-ditert-butyl-6-methylphenyl) phosphite. Other oligomer and polymer compounds having a phosphite structure can also be used. Commercially available products include ADK STAB PEP-36, PEP-8, HP-10, ADK STAB 2112, 1178, 1500, C, 3013, and TPP manufactured by ADEKA Corporation, IRGAFOS168 manufactured by BASF, and HostanoxP-EPQ manufactured by Clariant Chemicals.

[0151] Examples of sulfur-based antioxidants include 2,2-thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, 2,4-bis[(laurylthio)methyl]-o-cresol, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], 2,2-thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], etc. Other oligomeric and polymeric compounds having a thioether structure can also be used. Commercially available products include ADK STAB AO-412S and AO-503 manufactured by ADEKA Corporation, and KEMINOXPLS manufactured by Chemipro Chemicals.

[0152] As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used. Commercially available products include ADK STAB LA-29, LA-31RG, LA-32, LA-36, and -412S manufactured by ADEKA Corporation, KEMISORB71, 73, 74, 79, and 279 manufactured by Chemipro Chemicals, and TINUVIN PS, 99-2, 384-2, 900, 928, and 1130 manufactured by BASF.

[0153] Benzophenone antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc. Oligomeric and polymeric compounds having a benzophenone structure can also be used. Commercially available products include ADK STAB 1413 manufactured by ADEKA Corporation, KEMISORB10, 11, 11S, 12, and 111 manufactured by Chemipro Chemicals, and UV-12 and UV-329 manufactured by Sun Chemical.

[0154] Examples of triazine antioxidants include 2,4-bis(allyl)-6-(2-hydroxyphenyl)1,3,5-triazine, etc. Oligomeric and polymeric compounds having a triazine structure can also be used. Commercially available products include ADEKA's ADK STAB LA-46 and F70, and ChemiPro Chemical's KEMI SORB102, BASF's TINUVIN 400, 405, 460, 477, and 479, and Sun Chemical's Cyasorb UV-1164.

[0155] Examples of salicylate antioxidants include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, etc. Oligomeric and polymeric compounds having a salicylic acid ester structure can also be used.

[0156] These antioxidants can be used alone or in combination of two or more kinds in any ratio as required.

[0157] Furthermore, when the content of the antioxidant is 0.5 to 5.0% by mass relative to 100% by mass of the nonvolatile content of the coloring composition, the spectral characteristics and sensitivity are more favorable.

[0158] <Other additives> The colored composition of the present invention may contain, as other additives, a storage stabilizer for stabilizing the viscosity of the composition over time, and an adhesion improver such as a silane coupling agent for improving adhesion to a transparent substrate.

[0159] Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, phosphites, etc. The amount of storage stabilizer used is preferably 0.1 to 10% by mass relative to 100% by mass of the total colorant.

[0160] Examples of adhesion improvers include vinyl silanes such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth)acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane. Examples of suitable silane coupling agents include epoxy silanes such as N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The amount of the adhesion improver used is preferably 0.01 to 10% by mass, and more preferably 0.05 to 5% by mass, relative to 100% by mass of the total colorant.

[0161] <Method of producing colored composition> The coloring composition of the present invention is preferably produced by finely dispersing a mixture containing a near-infrared absorbing colorant (A), a chromatic colorant (B), a resin-type dispersant (C), a binder resin (D), and a solvent (E) using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. The coloring composition of the present invention can also be produced by dispersing the colorants separately and then mixing them. When the dye or the like has high solubility, specifically, when it is highly soluble in the solvent used and dissolves by stirring, and no foreign matter is detected, the above-mentioned fine dispersion step does not need to be carried out. Furthermore, when the mixture is a pigment, When the compound contains the compound, it is preferable to use a dye derivative or the like in combination.

[0162] In addition, when used as a photosensitive coloring composition, it is preferable to prepare it as a solvent-developable or alkali-developable composition. The photosensitive coloring composition can be prepared by mixing the coloring composition, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other dispersing aids, additives, etc. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

[0163] When dispersing the colorant, a dispersing aid (for example, a surfactant) can be used as appropriate. The dispersing aid is excellent in dispersing the colorant and is highly effective in preventing re-aggregation of the colorant after dispersion, so that high storage stability and excellent effects in reducing foreign matter can be obtained.

[0164] <Dispersion aid> (surfactant) Examples of surfactants include anionic surfactants such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphate esters; nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine, and amphoteric surfactants such as alkylimidazolines. These may be used alone or in combination of two or more, but are not necessarily limited to these.

[0165] The dispersing aids can be used alone or in combination of two or more kinds.

[0166] The amount of the dispersing aid used is preferably 0.1 to 55% by mass, and more preferably 0.1 to 45% by mass, relative to 100% by mass of the total coloring materials. When an appropriate amount is used, dispersibility is further improved.

[0167] <Removal of large particles> The coloring composition of the present invention is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably coarse particles of 0.5 μm or more, and contaminated dust by means of centrifugation, filtration with a sintered filter or membrane filter, etc. In this way, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more, and more preferably 0.3 μm or less.

[0168] <Water content> The colored composition of the present invention preferably has a water content of 0.1 to 2.0% by mass relative to 100% by mass of the colored composition.

[0169] The water content of the colored composition is preferably 0.15 to 1.80% by mass, more preferably 0.15 to 1.60% by mass. Within the above range, a colored composition having excellent storage stability and filterability can be obtained.

[0170] The method for controlling the water content is not particularly limited, and known methods can be used. For example, a method of producing a colored composition while blowing in dry air, an inert gas, or a mixed gas thereof, a method of dehydrating the produced colored composition by adding a molecular sieve, etc. Among these, the method of producing the colored composition while blowing in dry air or an inert gas is preferred.

[0171] The water content can be measured by a known method such as the Karl Fischer method.

[0172] <Content of specific metal elements> The coloring composition of the present invention may contain small amounts of Li, Na, K, Cs, Mg, Ca, Fe, and Zr (hereinafter also referred to as specific metal elements) in addition to the constituent components of the colorant. If a large amount of metal components containing these specific metal atoms is present, foreign matter may be generated, filterability may be deteriorated, or coating uniformity may be deteriorated. Furthermore, an optical filter produced using a colored composition containing a large amount of metal components containing such specific metal atoms is likely to suffer from reduced transmittance due to the generation of foreign matter. The total content of the specific metal atoms in the metal components contained in the colored composition of the present invention is preferably 1 to 1,000 ppm by mass with respect to the entire colored composition.

[0173] The total amount of specific metal atoms contained in the coloring composition of the present invention is more preferably 300 mass ppm or less, particularly preferably 200 mass ppm or less, based on the entire coloring composition.In addition, the lower limit of the total amount of specific metal atoms is not particularly limited, but is preferably 1 mass ppm or more, more preferably 5 mass ppm or more, based on the entire coloring composition.If it is within the above range, it is possible to obtain a coloring composition that can form an optical filter that can reduce costs, generate little foreign matter, have excellent filterability and coating uniformity, and have little transmittance reduction.

[0174] The content of each specific metal atom contained in the colored composition of the present invention is preferably 100 ppm by mass or less, and more preferably 50 ppm by mass or less, for each of the specific metal atoms relative to the entire colored composition.

[0175] Furthermore, when metal atoms such as Al, Ni, Cu, Pd, Zn, and Co are contained in part of the colorant structure, these metal atoms may also exist that do not constitute part of the compound or organic dye structure. The fewer such metal atoms, the better, and they can be removed in the same way as specific metal atoms by the following method. Furthermore, it is preferable that the concentrations of Mn, Cs, Ti, Si, and other contaminants that are introduced as a result of materials (e.g., catalysts) used in the manufacturing process of various raw materials for the coloring composition are low.

[0176] Methods for removing metal atoms that have been mixed into the various raw materials contained in the coloring composition or that have been mixed in from the equipment during the manufacturing process include methods using water washing as described in JP-A Nos. 2010-83997, 2018-36521, 7-198928, 8-333521, and 2009-7432, and methods such as removing magnetic foreign matter using a magnet as described in JP-A No. 2011-48736, and these methods can be used alone or in combination as appropriate.

[0177] The content of specific metal elements can be measured by inductively coupled plasma emission spectrometry (ICP).

[0178] <Optical filters> Next, the optical filter of the present invention will be described. [Optical filter manufacturing method] The optical filter can be produced by a method of applying the coloring composition of the present invention to various plastic substrates or glass substrates, or by kneading it into a plastic material and molding it. As long as a film that transmits infrared rays is formed, the method can be varied and the optical filter can be produced by various methods. The films produced by these methods can be combined with photodiodes to be used as various sensors such as illuminance sensors, distance sensors, medical sensors, touch sensors for displays, and biometric authentication sensors. Furthermore, by patterning a photodiode using the colored composition of the present invention by photolithography, the film can be used as an optical filter for a solid-state imaging device. The optical filter produced by photolithography will be described in detail below.

[0179] The optical filter segments according to the present invention can be formed by any known method without any particular limitations, but it is preferable to use optical lithography. When an optical filter segment is formed on a corresponding photoelectric conversion element, it is formed using a negative photosensitive coloring composition, and in this case, the thickness of the negative resist layer is set in the range of 0.1 to 3.0 μm.

[0180] The surface of the negative resist layer formed by the negative colored film is exposed to light using a photomask to form a pattern in a number of areas corresponding to a number of photoelectric conversion elements to be formed. Usually, the photomask has a size four to five times larger than the size of the pattern to be actually formed. During the laser exposure, the pattern is reduced to 1 / 4 to 1 / 5.

[0181] A typical photomask is a 4 to 5 times larger reticle, and has a pattern with dimensions 4 to 5 times larger than the dimensions of the pattern exposed on the surface of a negative infrared-transmitting resist layer. Then, using a stepper exposure device (not shown), the pattern of the photomask is reduced to 1 / 4 to 1 / 5 and exposed onto the surface of the negative resist layer.

[0182] Following the exposure step, an alkaline development treatment (development step) is performed to dissolve the uncured portions after exposure into the developer, leaving the photocured portions. This development step allows the formation of a patterned film consisting of optical filter segments.

[0183] The development method may be any of a dip method, shower method, spray method, paddle method, etc., and these may be combined with a swing method, spin method, ultrasonic method, etc. Uneven development can be prevented by wetting the surface to be developed with water or other liquid before contact with the developer. An organic alkaline developer is preferred as the developer, as it does not damage the underlying circuitry. The development temperature is usually 20 to 30°C, and the development time is 20 to 90 seconds.

[0184] Examples of the alkaline agent contained in the developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and the like. Organic alkalis such as ethylammonium hydroxide, choline, pyrrole, and piperidine Examples of suitable organic compounds include inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, and potassium hydrogen carbonate.

[0185] As the developer, an alkaline aqueous solution obtained by diluting these alkaline agents with pure water to a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass, is preferably used. When such a developer consisting of an alkaline aqueous solution is used, after development, the substrate is generally washed with pure water to remove excess developer, and then dried.

[0186] Finally, the filter segments thus formed are subjected to a hardening treatment. In the manufacturing method of the present invention, after the above-mentioned colored layer forming step, exposure step, and development step are performed, a curing step of curing the formed colored pattern by post-heating (post-baking) or post-exposure may be included as necessary. Post-baking is a heat treatment after development to complete the curing, and is usually a thermal curing treatment at 100 to 270°C. In this case, g-ray, h-ray, i-ray, excimer laser such as KrF or ArF, electron beam, X-ray, etc. However, it is preferable to use an existing high-pressure mercury lamp at a low temperature of about 20 to 50°C. The irradiation time is preferably 10 to 180 seconds, and more preferably 30 to 60 seconds. When post-exposure and post-heating are used in combination, it is preferable to carry out post-exposure first.

[0187] An optical filter is produced by the infrared transmission layer forming step, the exposure step, and the development step (and further, the curing step, if necessary) described above.

[0188] <Infrared camera, infrared sensor> The infrared camera and infrared sensor of the present invention have the optical filter of the present invention. Types of infrared cameras include near-infrared cameras, surveillance cameras, vehicle-mounted cameras, medical cameras, and inspection / analysis cameras, while types of infrared sensors include temperature sensors, distance sensors, medical sensors, touch sensors for displays, biometric authentication sensors, and the like. The configuration of the infrared camera and infrared sensor is not particularly limited as long as it has the optical filter of the present invention and functions as an infrared camera or infrared sensor. [Example]

[0189] The present invention will be described below based on examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass."

[0190] (average primary particle size of pigment) The average primary particle size of the pigment was measured by electron microscopy using a TEM (JEOL "JEM-1200EX"). The size of primary particles was measured directly from a micrograph. Specifically, the minor axis and major axis diameter of each pigment primary particle were measured, and the average was taken as the particle size of the pigment primary particle. Next, the volume (mass) of each of 100 or more pigment particles was calculated by approximating it to the cube of the calculated particle size, and the volume-average particle size was taken as the average primary particle size.

[0191] (Mass average molecular weight of resin-type dispersant (C) and binder resin (D)) The mass average molecular weight (Mw) of the resin is the polystyrene-equivalent mass average molecular weight (Mw) measured using a TSKgel column (manufactured by Tosoh Corporation) and a GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector, using THF as the developing solvent.

[0192] (Acid value of resin-type dispersant (C) and binder resin (D)) The resin acid value is the acid value (mgKOH / g) measured in accordance with the potentiometric titration method of JIS K 0070 and converted into nonvolatile content.

[0193] (Water content in coloring composition) The amount of water contained in the colored composition was measured using a Karl Fischer titrator (volumetric titration water meter KF-06 manufactured by Mitsubishi Chemical Corporation).

[0194] (Method for measuring specific metal atoms in coloring composition) The amount of the specific metal atoms in the colored composition was measured by drying the colored composition at 180°C, decomposing the powder with microwaves, and then using an ICP optical emission spectrometer Varian 720-ES manufactured by Agilent Technologies.

[0195] (Maximum absorption wavelength of near-infrared absorbing dye (a)) The maximum absorption wavelength of the near-infrared absorbing dye (a) was measured by preparing a 40 ppm solution of the near-infrared absorbing dye (a) in N-methyl-2-pyrrolidone, and then measuring the wavelength showing the maximum absorbance in the absorption spectrum in the range of 400 to 1300 nm using a UV-visible-near-infrared spectrophotometer U-4150 (manufactured by Hitachi High-Technologies Corporation).

[0196] <Synthesis of near-infrared absorbing dye (a1)> (Near-infrared absorbing dye (a1-1)) As the near-infrared absorbing dye (a1-1), SDO-C33 (manufactured by Arimoto Chemical Industry Co., Ltd.) was used. The maximum absorption wavelength of the near-infrared absorbing dye (a1-1) was 849 nm.

[0197] (Near-infrared absorbing dye (a1-2)) The near-infrared absorbing dye (a1-2) used was 5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine copper(II) (manufactured by Tokyo Chemical Industry Co., Ltd.) The maximum absorption wavelength of the near-infrared absorbing dye (a1-2) was 858 nm.

[0198] (Near-infrared absorbing dye (a1-3)) The near-infrared absorbing dye (a1-3) used was IR-813-p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) The maximum absorption wavelength of the near-infrared absorbing dye (a1-3) was 817 nm.

[0199] (Near-infrared absorbing dyes (a1-4) to (a1-5)) Near-infrared absorbing dyes (a1-4) to (a1-5) represented by the following structural formulas were synthesized in the same manner as described in JP 2012-224593 A. The maximum absorption wavelengths of the near-infrared absorbing dyes (a1-4) and (a1-5) were 1000 nm and 1070 nm, respectively.

[0200] [ka]

[0201] (Near-infrared absorbing dyes (a1-6) to (a1-10)) Near-infrared absorbing dyes (a1-6) to (a1-10) represented by the following structural formulas were synthesized in the same manner as described in JP 2013-87233 A. The maximum absorption wavelengths of the near-infrared absorbing dyes (a1-6) to (a1-10) were 905 nm, 756 nm, 835 nm, 883 nm, and 890 nm, respectively.

[0202] [ka]

[0203] (Near-infrared absorbing dyes (a1-11)) In a reaction vessel, 10.7 parts of aniline, 120 parts of bromobenzene, and 25.7 parts of diazabicyclooctane were added and stirred. Then, 95.2 parts of a 1 mol / L toluene solution of titanium tetrachloride was added dropwise. After the dropwise addition, 10.0 parts of indigo was added and refluxed for 10 hours. After the reaction was completed, methanol was added and the mixture was filtered to obtain a green powder. This was separated with dichloromethane and water, and the organic layer was concentrated to obtain 14.6 parts of compound (1).

[0204] Compound (1) [ka]

[0205] In a reaction vessel, 13.5 parts of compound (1), 8.8 parts of bis(2,4-pentanedionato)nickel(II) hydrate, and 120 parts of tetrahydrofuran were mixed and stirred, and after heating, the mixture was stirred at 40°C for 5 hours. The reaction solution was cooled to 30°C while still stirring, and poured into 500 parts of methanol with stirring to obtain a blue slurry. This slurry was filtered, washed with 500 parts of methanol, and dried to obtain 11.5 parts of near-infrared absorbing dye (a1-11). The maximum absorption wavelength of the near-infrared absorbing dye (a1-11) was 753 nm.

[0206] (a1-11) [ka]

[0207] (Near-infrared absorbing dyes (a1-12)) The same procedure as in the synthesis of the near-infrared absorbing dye (a1-11) was carried out, except that the 8.8 parts of bis(2,4-pentanedionato)nickel(II) hydrate used in the synthesis of the near-infrared absorbing dye (a1-11) was replaced with 9.0 parts of bis(2,4-pentanedionato)zinc(II), to obtain 12.2 parts of the near-infrared absorbing dye (a1-12). As a result, the molecular ion peak in the mass spectrum obtained matched the mass number obtained by calculation, and the compound obtained was identified. The maximum absorption wavelength of the near-infrared absorbing dye (a1-12) was 765 nm.

[0208] (a1-12) [ka]

[0209] (Near-infrared absorbing dye (a1-13)) The same procedure as in the synthesis of near-infrared absorbing dye (a1-11) was carried out, except that 8.8 parts of bis(2,4-pentanedionato)nickel(II) hydrate used in the synthesis of near-infrared absorbing dye (a1-11) was replaced with 12.6 parts of bis(2,4-pentanedionato)cobalt(II), to obtain 12.7 parts of near-infrared absorbing dye (a1-13). The maximum absorption wavelength of the near-infrared absorbing dye (a1-13) was 780 nm.

[0210] (a1-13) [ka]

[0211] (Near-infrared absorbing dye (a1-14)) The same procedure as in the synthesis of near-infrared absorbing dye (a1-11) was carried out, except that 8.8 parts of bis(2,4-pentanedionato)nickel(II) hydrate used in the synthesis of near-infrared absorbing dye (a1-11) was replaced with 17.0 parts of nickel(II) acetate tetrahydrate, to obtain 10.1 parts of near-infrared absorbing dye (a1-14). The maximum absorption wavelength of the near-infrared absorbing dye (a1-14) was 820 nm.

[0212] (a1-14) [ka]

[0213] (Near-infrared absorbing dye (a1-15)) The same procedure as in the synthesis of near-infrared absorbing dye (a1-12) was carried out, except that the 9.0 parts of bis(2,4-pentanedionato)zinc(II) used in the synthesis of near-infrared absorbing dye (a1-12) was changed to 25.0 parts, to obtain 11.7 parts of near-infrared absorbing dye (a1-15). The maximum absorption wavelength of the near-infrared absorbing dye (a1-15) was 830 nm.

[0214] (a1-15) [ka]

[0215] (Near-infrared absorbing dye (a1-16)) In a reaction vessel, 178 parts of 2,3-dicyanonaphthalene and 890 parts of n-amyl alcohol 137 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) and 40 parts of anhydrous aluminum chloride were mixed and stirred, heated, and refluxed at 136°C for 5 hours. The reaction solution was cooled to 30°C while stirring, and poured into a mixed solvent of 5,000 parts of methanol and 10,000 parts of water while stirring, to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2,000 parts of methanol and 4,000 parts of water, and dried to obtain 159 parts of compound (2). Mass spectrometry and elemental analysis by TOF-MS confirmed that the molecular ion peak in the mass spectrum matched the calculated mass number, identifying the compound.

[0216] Next, 10 parts of compound (2) were added to 100 parts of concentrated sulfuric acid in a reaction vessel in an ice bath, and the mixture was stirred for 1 hour. Subsequently, this sulfuric acid solution was poured into 1,000 parts of cold water at 3°C, and the resulting precipitate was filtered, washed with water, washed with a 2.5% aqueous sodium hydroxide solution, and then washed with water. The resulting precipitate was then dried to obtain 125 parts of compound (3). As a result of TOF-MS mass spectrometry and elemental analysis, the molecular ion peak in the mass spectrum obtained matched the calculated mass number, and the resulting compound was identified. The molecular weight was 756.75.

[0217] Compound (3) [ka]

[0218] Next, 5 parts of diphenyl phosphate was added to 200 parts of N-methylpyrrolidone, thoroughly mixed, and then heated to 50°C. 10 parts of compound (3) was gradually added to this solution, and the mixture was stirred at 90°C for 120 minutes. The end point of the reaction was confirmed, for example, by dropping the reaction solution onto filter paper and determining that no bleeding had occurred. Subsequently, this reaction solution was poured into 2000 parts of water, and the resulting precipitate was filtered, washed with water, and dried to obtain 12 parts of near-infrared absorbing dye (a1-16). The maximum absorption wavelength of the near-infrared absorbing dye (a1-16) was 771 nm.

[0219] (a1-16) [ka]

[0220] (Near-infrared absorbing dye (a1-17)) The same procedure as in the synthesis of near-infrared absorbing dye (a1-16) was carried out, except that 64 parts of phthalonitrile and 89 parts of 2,3-dicyanonaphthalene were used instead of 178 parts of 2,3-dicyanonaphthalene used in the synthesis of near-infrared absorbing dye (a1-16), to obtain 12 parts of near-infrared absorbing dye (a1-17). The maximum absorption wavelength of the near-infrared absorbing dye (a1-17) was 770 nm.

[0221] (a1-17) [ka]

[0222] (Near-infrared absorbing dye (a1-18)) In the same manner as in WO2005 / 044782, a compound represented by the following structural formula was synthesized. The near-infrared absorbing dye (a1-18) was synthesized. The maximum absorption wavelength of the near-infrared absorbing dye (a1-18) was 1092 nm.

[0223] (a1-18) [ka]

[0224] (Near-infrared absorbing dye (a1-19)) The near-infrared absorbing dye (a1-19) used was indocyanine green (manufactured by Tokyo Chemical Industry Co., Ltd.) The maximum absorption wavelength of the near-infrared absorbing dye (a1-19) was 793 nm.

[0225] (Near-infrared absorbing dye (a1-20)) A near-infrared absorbing dye (a1-20) represented by the following structural formula was synthesized in the same manner as described in JP 2018-123093 A. The maximum absorption wavelength of the near-infrared absorbing dye (a1-20) was 768 nm.

[0226] (a1-20) [ka]

[0227] (Near-infrared absorbing dye (a1-21)) In the same manner as in WO2017 / 159610, a compound represented by the following structural formula was synthesized. The near-infrared absorbing dye (a1-21) was synthesized. The maximum absorption wavelength of the near-infrared absorbing dye (a1-21) was 915 nm.

[0228] (a1-21) [ka]

[0229] (Near infrared absorbing dye (a1-22) As the near-infrared absorbing dye (a1-22), bis[4,4'-dimethoxy(dithiobenzyl)] [Il] nickel(II) (Tokyo Chemical Industry Co., Ltd.) was used. The maximum absorption wavelength of 2) was 914 nm.

[0230] (Near infrared absorbing dye (a1-23) The near-infrared absorbing dye (a1-23) used was tetrabutylammonium bis(3,6-dichloro-1,2-benzenedithiolato) nickelate (manufactured by Tokyo Chemical Industry Co., Ltd.) The maximum absorption wavelength of the near-infrared absorbing dye (a1-23) was 1052 nm.

[0231] (Near-infrared absorbing dye (a1-24)) 400 parts of toluene were mixed with 40.0 parts of 1,8-diaminonaphthalene, 32.2 parts of 3,5-dimethylcyclohexanone, and 0.087 parts of p-toluenesulfonic acid monohydrate, and the mixture was heated and stirred in a nitrogen gas atmosphere and refluxed for 3 hours. Water produced during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the dark brown solid obtained by distilling the toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, and 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added. The mixture was then refluxed under a nitrogen gas atmosphere for 3 hours. The mixture was heated and stirred under reflux for 8 hours, and the water generated during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the solvent was distilled off, and 200 parts of hexane was added to the resulting reaction mixture while stirring. The resulting black-brown precipitate was filtered off, washed successively with hexane, ethanol, and acetone, and dried under reduced pressure to obtain 72.6 parts of near-infrared absorbing dye (a1-24). The maximum absorption wavelength of the near-infrared absorbing dye (a1-24) was 825 nm.

[0232] (a1-24) [ka]

[0233] (Near-infrared absorbing dye (a1-25)) The same procedure as in the synthesis of near-infrared absorbing dye (a1-24) was carried out, except that 46.0 parts of 9-fluorenone was used instead of 32.2 parts of 3,5-dimethylcyclohexanone used in the synthesis of near-infrared absorbing dye (a1-24), to obtain 84.6 parts of near-infrared absorbing dye (a1-25). The maximum absorption wavelength of the near-infrared absorbing dye (a1-25) was 845 nm.

[0234] (a1-25) [ka]

[0235] (Near-infrared absorbing dye (a1-26)) A near-infrared absorbing dye (a1-26) represented by the following structural formula was synthesized in the same manner as described in JP-A-2009-263614: The maximum absorption wavelength of the near-infrared absorbing dye (a1-26) was 851 nm.

[0236] (a1-26) [ka]

[0237] (Near-infrared absorbing dye (a1-27)) In the same manner as in WO2018 / 043218, a compound represented by the following structural formula was synthesized. The near-infrared absorbing dye (a1-27) was synthesized. The maximum absorption wavelength of the near-infrared absorbing dye (a1-27) was 860 nm.

[0238] (a1-27) [ka]

[0239] <Production of near-infrared absorbing colorant (A1)> (Production of near-infrared absorbing colorant (A1-1)) 200 parts of near-infrared absorbing dye (a1-1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 8 hours at 70°C. Next, this kneaded mixture was poured into warm water and stirred for 1 hour while heating to about 70°C to form a slurry. After repeated filtration and washing with water to remove the sodium chloride and diethylene glycol, the mixture was dried overnight at 80°C to obtain 189 parts of near-infrared absorbing colorant (A1-1). The average primary particle diameter of the obtained near-infrared absorbing colorant (A1-1) was 73.0 nm.

[0240] (Production of near-infrared absorbing colorants (A1-2) to (A1-23), (A1-24-2) to (A1-27-2)) Near-infrared absorbing colorants (A1-2) to (A1-23), (A1-24-2) to (A1-27-2) were obtained in the same manner as for the near-infrared absorbing colorant (A1-1), except that the near-infrared absorbing dye (a1-1) was changed to the near-infrared absorbing dyes (a1-2) to (a1-23), (a1-24) to (a1-27). Near-infrared absorbing colorants (A1-2) to (A1-23), (A1-24-2) to (A1-27-2) were obtained in the same manner as for the near-infrared absorbing colorant (A1-1).

[0241] (Production of near-infrared absorbing colorants (A1-7-2), (A1-11-2), (A1-12-2), (A1-16-2), and (A1-17-2)) (Production of near-infrared absorbing colorants (A1-7-2), (A1-11-2), (A1-12-2), (A1-16-2), and (A1-17-2)) Near-infrared absorbing colorants (A1-7-2), (A1-11-2), (A1-12-2), (A1-16-2), and (A1-17-2) were obtained in the same manner as for the near-infrared absorbing colorant (A1-1), except that the near-infrared absorbing colorant (a1-1) was replaced with near-infrared absorbing colorants (a1-7), (a1-11), (a1-12), (a1-16), and (a1-17), and the kneading temperature was changed to 80°C.

[0242] (Production of near-infrared absorbing colorants (A1-24) to (A1-27)) Near-infrared absorbing colorants (A1-24) to (A1-27) were the same as those of near-infrared absorbing dyes (a1-24) to (a1-27).

[0243] (Average primary particle size of near-infrared absorbing colorants (A1-2) to (A1-23), (A1-7-2), (A1-11-2), (A1-12-2), (A1-16-2), (A1-17-2), (A1-24-2) to (A1-27-2)) The average primary particle sizes of the near-infrared absorbing colorants (A1-2) to (A1-23), (A1-7-2), (A1-11-2), (A1-12-2), (A1-16-2), (A1-17-2), and (A1-24-2) to (A1-27-2) were the values ​​shown in Table 3.

[0244] (Maximum absorption wavelength of finely divided chromatic pigments) The maximum absorption wavelength of the finely divided chromatic pigment was measured using a UV-visible-near-infrared spectrophotometer U-4150 (manufactured by Hitachi High-Technologies Corporation) by preparing a 40 ppm solution of the finely divided chromatic pigment in sulfuric acid and then measuring the wavelength showing the maximum absorbance in the absorption spectrum in the range of 400 to 1300 nm as the maximum absorption wavelength.

[0245] <Production of finely divided chromatic pigments> (Yellow Micronized Pigment (BP-1)) 100 parts of a yellow pigment, CI Pigment Yellow 139 (Clariant's "Novoperm Yellow P-M3R"), 800 parts of ground salt, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (Inoue Manufacturing Co., Ltd.) and kneaded at 70°C for 12 hours. This mixture was added to 3,000 parts of warm water and stirred in a high-speed mixer for approximately 1 hour while heating to approximately 70°C to form a slurry. The salt and solvent were removed by repeated filtration and water washing, and the slurry was then dried at 80°C for 24 hours to obtain 97 parts of a finely divided yellow pigment (BP-1). The average primary particle diameter of the resulting pigment was 41.1 nm. The maximum absorption wavelength of the finely divided yellow pigment (BP-1) was 410 nm.

[0246] (Blue Micronized Pigment (BP-2)) 100 parts of blue organic pigment CI Pigment Blue 15:3 (PB15:3) ("Lionol Blue FG-7351" manufactured by Toyocolor Co., Ltd.), 800 parts of ground salt, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 70°C. This mixture was added to 3000 parts of warm water and stirred in a high-speed mixer for approximately 1 hour while heating to approximately 70°C to form a slurry. The salt and solvent were removed by repeated filtration and water washing, and the slurry was then dried at 80°C for 24 hours to obtain a finely divided blue pigment (BP-2). The average primary particle diameter of the resulting pigment was 30.9 nm. The maximum absorption wavelength of the blue pigment (BP-2) was 586 nm.

[0247] (Purple Micronized Pigment (BP-3)) 100 parts of the purple pigment CI Pigment Violet 23 ("LIONOGEN VIOLET FG-6140" manufactured by Toyocolor Co., Ltd.), 800 parts of ground salt, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 12 hours at 70°C. This mixture was added to 3000 parts of warm water and stirred in a high-speed mixer for approximately 1 hour while heated to approximately 70°C to form a slurry. The salt and solvent were removed by repeated filtration and water washing, and the slurry was dried at 80°C for 24 hours to obtain 95 parts of a purple microfiber pigment (BP-3). The average primary particle diameter of the resulting pigment was 53.7 nm. The maximum absorption wavelength of the purple microfiber pigment (BP-3) was 545 nm.

[0248] <Chromatic color material (B)> (Chromatic color materials (B-1)~(B-4)) The chromatic colorants (B-1) to (B-4) were mixed in the compositions shown in Table 1 and used to produce colored compositions.

[0249] [Table 1]

[0250] <Production of dye derivatives> (dye derivatives) The dye derivatives used were compounds represented by the following structural formulas (G-1) and (G-2).

[0251] (G-1) [ka]

[0252] (G-2) [ka]

[0253] <Production of resin-type dispersants> [Manufacturing Example 1] (Resin-type dispersant (C-1)) A reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer was charged with 3 parts methacrylic acid, 137 parts methyl methacrylate, and 60 parts t-butyl acrylate, and the atmosphere was replaced with nitrogen gas. The reaction vessel was heated to 50°C with stirring, and 4 parts 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution of 0.1 parts 2,2'-azobisisobutyronitrile in 90 parts propylene glycol monomethyl ether acetate was added while the reaction was continued for 7 hours. Solid content measurement confirmed that 95% had reacted. Pyromellitic dianhydride 6 parts, propylene glycol monomethyl ether acetate 31 parts 0.5 parts of the ethanol and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out for 7 hours at 100° C. After confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, the reaction was terminated, and propylene glycol monomethyl ether acetate was added to dilute the mixture to a solids content of 40% by measuring the solids content, yielding a resin-type dispersant (C-1) with an acid value of 22 mgKOH / g and a mass average molecular weight of 20,000.

[0254] [Manufacturing Examples 2 to 9] (Resin-type dispersants (C-2) to (C-9)) Resin-type dispersants (C-2) to (C-9) were prepared in the same manner as (C-1), except that the compositions were changed as shown in Table 2.

[0255] [Table 2]

[0256] (Resin-type dispersant (C-10)) DISPER BYK-110 (non-volatile content: 51%, amine value: 0, acid value: 53) manufactured by BYK Chemie Co., Ltd. was diluted in the same manner as the resin-type dispersant (C-1) to obtain a resin-type dispersant (C-10) with a non-volatile content of 40%.

[0257] (Resin-type dispersant (C-11)) DISPER BYK-111 (non-volatile content: 95%, amine value: 0, acid value: 129) manufactured by BYK Chemie Co., Ltd. was diluted in the same manner as the resin-type dispersant (C-1) to obtain a resin-type dispersant (C-11) with a non-volatile content of 40%.

[0258] (Resin-type dispersant (C-12)) BYK-LPN6919 (non-volatile content: 60%, amine value: 73, acid value: 0) manufactured by BYK Chemie Co., Ltd. was diluted in the same manner as for the resin-type dispersant (C-1) to obtain a resin-type dispersant (C-12) with a non-volatile content of 40%.

[0259] <Production of binder resin> (Binder resin (D-1)) A separable four-neck flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer was charged with 370 parts of cyclohexanone, and the temperature was raised to 80°C. The atmosphere in the flask was replaced with nitrogen, and then 18 parts of dicyclopentanyl methacrylate, 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2'-benzophenone were added through the dropping tube. A mixture of 2.0 parts of azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition, the reaction was continued for another 3 hours at 100°C, followed by the addition of a solution of 1.0 parts of azobisisobutyronitrile in 50 parts of cyclohexanone, and the reaction was continued for another hour at 100°C. Next, the atmosphere in the vessel was purged with air, and 9.3 parts of acrylic acid (100% of glycidyl groups), 0.5 parts of trisdimethylaminophenol, and 0.1 parts of hydroquinone were added to the vessel. The reaction was continued for 6 hours at 120°C, and the reaction was terminated when the solids acid value reached 0.5, yielding an acrylic resin solution. Next, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added, and the reaction was continued for 3.5 hours at 120°C, yielding an acrylic resin solution. After cooling to room temperature, approximately 2 g of the resin solution was sampled and dried at 180°C for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether acetate was added to the resin solution synthesized earlier to obtain a nonvolatile content of 20% by mass, yielding binder resin (D-1). The mass-average molecular weight (Mw) was 19,000.

[0260] <Production of near-infrared absorbing composition> [Manufacturing Example 10] (Production of near-infrared absorbing composition (IR-1)) The following mixture was stirred and mixed to become uniform, and then dispersed for 5 hours in an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) using zirconia beads with a diameter of 0.5 mm. The mixture was then filtered through a 5.0 μm filter to obtain a near-infrared absorbing composition (IR-1) with a non-volatile component content of 20 parts by mass. Near-infrared absorbing colorant (A1-1): 8.0 parts Pigment derivative (G-1): 2.0 parts Resin-type dispersant (C-5): 10.0 parts Binder resin (D-1): 30.0 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.0 parts

[0261] [Manufacturing Examples 11 to 45] (Production of Near-Infrared Absorbing Compositions (IR-2) to (IR-36)) Near-infrared absorbing compositions (IR-2) to (IR-36) were obtained in the same manner as in Production Example 1, except that the compositions were changed to those shown in Table 3.

[0262] (Spectral characteristics of near-infrared absorbing composition) The obtained near-infrared absorbing composition was applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater, and baked in an oven at 230°C for 20 minutes to prepare a coated substrate so that the coating film would have a thickness of 1.0 μm after heat treatment. The film thickness was measured using a DEKTAK, and spectroscopy was performed using a UV-Vis-Infrared Spectrophotometer. The substrate having the colored layer was measured using a UV-Vis-Infrared Spectrophotometer U-4150 (manufactured by Hitachi High-Technologies Corporation) (ref. glass substrate) for light transmittance in the wavelength range of 300 to 1300 nm, maximum transmittance S in the wavelength range of 400 to 900 nm, and minimum transmittance T in the wavelength range of 700 to 1300 nm. was measured. [Table 3]

[0263] [Example 1] (Preparation of Coloring Composition (PP-1)) The following mixture was stirred and mixed until uniform, and then dispersed for 5 hours using zirconia beads with a diameter of 0.5 mm in an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.), and then filtered through a 5.0 μm filter to obtain a colored composition having a non-volatile component of 20 parts by mass. (PP-1) was obtained. Near-infrared absorbing colorant (A1-24): 6.0 parts Chromatic color material (B-1): 2.0 parts Pigment derivative (G-1): 2.0 parts Resin-type dispersant (C-11): 10.0 parts Binder resin (D-1): 30.0 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.0 parts The colored composition (PP-1) had a water content of 0.6 mass % and a total amount of metal atoms of 1106 mass ppm relative to 100 mass % of the colored composition.

[0264] [Examples 2 to 38] (Preparation of Colored Compositions (PP-2) to (PP-38)) Hereinafter, colored compositions (PP-2) to (PP-38) were prepared in the same manner as for the colored composition (PP-1), except that the compositions and amounts were changed as shown in Table 4-1.

[0265] [Table 4-1]

[0266] [Example 39] (Preparation of Coloring Composition (PP-39)) The same procedure as in Example 1 was carried out except that the near-infrared absorbing colorant (A1-24) and the resin-type dispersant (C-1) were changed to the near-infrared absorbing colorant (A1-7) and the resin-type dispersant (C-5). Thus, a colored composition (PP-39) was obtained. The colored composition (PP-39) had a water content of 0.7 mass% and a total amount of specific metal atoms of 1050 mass ppm relative to 100 mass% of the colored composition.

[0267] [Examples 40 to 71] (Preparation of Colored Compositions (PP-40) to (PP-71)) Colored compositions (PP-40) to (PP-71) were prepared in the same manner as for colored composition (PP-39), except that the compositions and amounts were changed as shown in Table 4-2.

[0268] [Table 4-2]

[0269] [Example 72] (Preparation of Coloring Composition (PP-72)) Water was added to the colored composition (PP-39) so that the water content became 2.5% by mass, and the mixture was stirred for 5 minutes to obtain a colored composition (PP-72). The colored composition (PP-72) had a water content of 2.5 mass % and a total amount of specific metal atoms of 1061 mass ppm relative to 100 mass % of the colored composition.

[0270] [Examples 73 to 76] (Preparation of Colored Compositions (PP-73) to (PP-76)) Colored compositions (PP-73) to (PP-76) were prepared in the same manner as for colored composition (PP-72), except that the compositions and amounts were changed as shown in Table 4-3.

[0271] [Table 4-3]

[0272] <Purification of near-infrared absorbing colorant (A1-7)> 15.0 parts of near-infrared absorbing colorant (A1-7) were placed in a beaker and heated to 60°C. The mixture was heated and stirred at room temperature for 1 hour, filtered, washed with 2000 parts of ion-exchanged water, and dried.

[0273] <Purification of near-infrared absorbing colorants (A1-1) to (A1-6) and (A1-8) to (A1-23)> The same operations as in the purification of the near-infrared absorbing colorant (A1-7) were carried out, except that the near-infrared absorbing colorant (A1-7) was changed to the near-infrared absorbing colorants (A1-1) to (A1-6) and (A1-8) to (A1-23), respectively.

[0274] [Example 77] (Preparation of Coloring Composition (PP-77)) A colored composition (PP-77) was obtained in the same manner as in the colored composition (PP-39), except that the near-infrared absorbing colorant (A1-7) was changed to a colorant obtained by purifying the near-infrared absorbing colorant (A1-7). The coloring composition (PP-77) has a water content of 0.5% by mass relative to 100% by mass of the coloring composition. The total amount of specific metal atoms was 45 ppm by mass.

[0275] [Examples 78 to 151, Comparative Examples 1 to 6] (Preparation of Colored Compositions (PP-78) to (PP-157)) Colored compositions (PP-78) to (PP-157) were prepared in the same manner as colored composition (PP-77), except that the compositions and amounts were changed to those shown in Tables 4-4, 4-5, and 6-1.

[0276] [Table 4-4]

[0277] [Table 4-5]

[0278] [Table 6-1]

[0279] <Evaluation of Coloring Composition> The obtained colored compositions were evaluated for spectral characteristics, storage stability, agglomerated foreign matter, coating uniformity, and filterability as described below.

[0280] (Evaluation of light blocking properties at 400 to 800 nm) The obtained colored composition was applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater, and baked in an oven at 230 ° C for 20 minutes to prepare a coated substrate so that the thickness of the coating film after heat treatment would be 1.0 μm. The film thickness was measured using a DEKTAK. The maximum transmittance of the prepared substrate from 400 to 800 nm was measured to evaluate the light-shielding ability in the visible region. ◎ indicates a very good level, ○ indicates a good level, △ indicates a level that can be used in practice, and × indicates a level that is not suitable for practical use. ◎: Maximum transmittance is less than 3.0% 〇: Maximum transmittance is 3.0% or more and less than 5.0% △: Maximum transmittance is 5.0% or more and less than 7.0% ×: Maximum transmittance is 7.0% or more

[0281] (Evaluation of storage stability) The viscosity of the obtained colored composition was measured immediately after preparation and after storage at 10°C for one month using an E-type viscometer. The ratio of (viscosity after storage for one month) / (viscosity immediately after preparation) was calculated and evaluated according to the following criteria. ⊚ indicates a very good level, ○ indicates a good level, △ indicates a level that can be used in practice, and × indicates a level that is not suitable for practical use. ◎: Viscosity ratio is 1.00 or more and less than 1.02 Good: Viscosity ratio is 1.02 or more and less than 1.05 △: Viscosity ratio is 1.05 or more and less than 1.10 ×: Viscosity ratio is 1.10 or more

[0282] (Evaluation of agglomerated foreign matter) The resulting colored composition was applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater and baked in an oven at 230°C for 20 minutes to prepare a coated substrate so that the coating film would have a thickness of 1.0 μm after heat treatment. The film thickness was measured using a DEKTAK. The resulting substrate was then heated at 250°C for 1 hour and the surface was observed. Evaluation was performed using an Olympus Systems BX60 metallurgical microscope. The magnification was 500x, and the number of particles observable in any five fields of view was counted in transmission to evaluate. ◎ indicates a very good level, ○ indicates a good level, △ indicates a practically acceptable level, and × indicates a level not suitable for practical use. ◎: The number of foreign objects is less than 5 ◎○: Number of foreign objects is 5 or more but less than 10 ○: The number of foreign objects is 10 or more but less than 20 △: Number of foreign objects is 20 or more but less than 60 ×: 60 or more foreign objects

[0283] (Evaluation of filterability) 15 g of the obtained colored composition was passed through a filter (φ0.2 μm, manufactured by ADVANTEC, model number: 39115221) under nitrogen pressure (0.3 MPa), the amount of the colored composition that passed through the filter was measured, and the result was evaluated according to the following criteria: ◎ indicates a very good level, ○ indicates a good level, △ indicates a practically acceptable level, and × indicates a level that is not suitable for practical use. ◎: Filtration volume is 8.0g or more 〇: Filtration volume is 5.0g or more but less than 8.0g △: Filtration volume is 3.0g or more but less than 5.0g ×: Filtration volume is 3.0g or less

[0284] (Evaluation of coating uniformity) The obtained coloring composition was spin-coated onto a 360 mm × 465 mm substrate having a thickness of 0.7 mm so that the film thickness (referred to as A) at the center was 2.0 μm, and then dried at 70° C. for 30 minutes. After that, the average value of the film thickness at the center and the film thickness at four points 200 mm from the center on the diagonal line (referred to as B) was measured. The coating uniformity of the film thickness was evaluated using the following formula. (A+B)×100 / {(A+B) / 2} [%] ◎: Less than 1% ○: 1% or more and less than 2% △: 2% or more and less than 5% ×: 5% or more

[0285] The results of the evaluation by the above methods are shown in Tables 5-1 to 5-5 and 6-2.

[0286] [Table 5-1]

[0287] [Table 5-2]

[0288] [Table 5-3]

[0289] [Table 5-4]

[0290] [Table 5-5]

[0291] [Table 6-2]

[0292] As shown in Examples 1 to 151, by containing 67 to 90 mass% of near-infrared absorbing colorant (A) and 10 to 33 mass% of chromatic colorant (B) out of a total of 100 mass% of the near-infrared absorbing colorant (A) and the chromatic colorant (B), excellent properties were exhibited in all evaluation items.

[0293] In the comparative examples, results that satisfied all the items were not obtained, proving the effectiveness of the present invention.

[0294] <Production of Photosensitive Coloring Composition> [Example 152] (Photosensitive coloring composition (PR-1)) The following mixture was mixed and stirred until uniform, then filtered through a 1.0 μm filter. A photosensitive coloring composition (PR-1) was prepared. Coloring composition (PP-78): 60.0 parts Binder resin (D-1): 11.0 parts Photopolymerizable monomer 1: 3.6 parts Dipentaerythritol penta- and hexaacrylate ("Aronix M402" manufactured by Toagosei Co., Ltd.) Photopolymerizable monomer 2: 1.0 part Trimethylolpropane PO modified triacrylate ("Aronix M310" manufactured by Toagosei Co., Ltd.) Photopolymerization initiator 1: 0.6 parts Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) (BASF Japan "Irgacure OXE02") Photopolymerization initiator 2: 0.6 parts 1-(N-4-Benzoylphenyl-carbazol-3-yl)-butane-1,2-dione-2-oxime-O-acetate Cyclohexanone (Anone): 5.2 parts Propylene glycol monomethyl ether acetate (PGMAc): 18.0 parts

[0295] [Examples 153 to 187, Comparative Examples 7 to 10] (Photosensitive coloring composition (PR-2)~(PR-40)) Photosensitive coloring compositions (PR-2) to (PR-40) were prepared in the same manner as in Example 147, except that the coloring compositions were changed to the coloring compositions shown in Tables 7-1 and 8-1.

[0296] [Table 7-1]

[0297] [Table 8-1]

[0298] <Evaluation of Photosensitive Coloring Composition> The obtained photosensitive coloring composition was evaluated in the same manner as the coloring composition.

[0299] (Light blocking properties at 400 to 800 nm) The obtained photosensitive coloring composition was spin-coated onto a 1.1 mm thick glass substrate using a spin coater, dried at 60°C for 5 minutes, and then irradiated with 100 mJ / cm 2 using an ultra-high pressure mercury lamp. 2 The coated substrate was prepared by irradiating the substrate with ultraviolet light, spray-developing with an alkaline developer consisting of a 0.2% by mass aqueous solution of sodium carbonate, and then baking at 230°C for 20 minutes so that the coating film had a thickness of 1.0 μm after heat treatment. The film thickness was measured using a DEKTAK. The spectrum of the obtained substrate was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation) to measure the maximum transmittance of the substrate from 400 to 800 nm, thereby evaluating its light-blocking ability in the visible region. ◎ indicates a very good level, ○ indicates a good level, △ indicates a practically acceptable level, and × indicates a level not suitable for practical use. ◎: Maximum transmittance is less than 3.0% 〇: Maximum transmittance is 3.0% or more and less than 5.0% △: Maximum transmittance is 5.0% or more and less than 7.0% ×: Maximum transmittance is 7.0% or more

[0300] (Evaluation of storage stability) The viscosity of the obtained photosensitive coloring composition was measured immediately after preparation and after storage at 10°C for one month using an E-type viscometer. The ratio of (viscosity after storage for one month) / (viscosity immediately after preparation) was calculated and evaluated according to the following criteria. ⊚ indicates a very good level, ○ indicates a good level, △ indicates a practically acceptable level, and × indicates a level not suitable for practical use. ◎: Viscosity ratio is 1.00 or more and less than 1.02 Good: Viscosity ratio is 1.02 or more and less than 1.05 △: Viscosity ratio is 1.05 or more and less than 1.10 ×: Viscosity ratio is 1.10 or more

[0301] (Evaluation of agglomerated foreign matter) The obtained photosensitive coloring composition was spin-coated onto a 1.1 mm thick glass substrate using a spin coater, dried at 60°C for 5 minutes, and then irradiated with 100 mJ / cm 2 using an ultra-high pressure mercury lamp. 2 The coated substrate was irradiated with ultraviolet light of 1000 kJ / cm², spray-developed with an alkaline developer consisting of a 0.2% by mass aqueous solution of sodium carbonate, and then baked at 230°C for 20 minutes to produce a coated substrate with a coating thickness of 1.0 μm after heat treatment. The film thickness was measured using a DEKTAK. The resulting substrate was then heated at 250°C for 1 hour and the surface was observed. Evaluation was performed using an Olympus Systems BX60 metallurgical microscope. Magnification was set to 500x, and the number of particles observable in any five fields of view was counted in transmission to evaluate. ◎ indicates an excellent level, ◎ ○ indicates a very good level, ○ indicates a good level, △ indicates a practical level, and × indicates a level not suitable for practical use. ◎: The number of foreign objects is less than 5 ◎○: Number of foreign objects is 5 or more but less than 10 ○: The number of foreign objects is 10 or more but less than 20 △: Number of foreign objects is 20 or more but less than 60 ×: 60 or more foreign objects

[0302] (Evaluation of coating uniformity) The obtained photosensitive coloring composition was spin-coated onto a 360 mm x 465 mm substrate with a thickness of 0.7 mm so that the film thickness (referred to as A) at the center was 2.0 μm, and dried at 70°C for 30 minutes. After drying, the film thickness at the center and the average film thickness (referred to as B) at four points diagonally 200 mm from the center were measured, and the coating uniformity of the film thickness was evaluated using the following formula. (A+B)×100 / {(A+B) / 2} [%] ◎: Less than 1% ○: 1% or more and less than 2% △: 2% or more and less than 5% ×: 5% or more

[0303] (Evaluation of filterability) 10 g of the obtained photosensitive coloring composition was passed through a filter (φ0.2 μm, manufactured by ADVANTEC, model number: 39115221) under nitrogen pressure (0.3 MPa), the amount of the filtered composition was measured, and the result was evaluated according to the following criteria: ◎ is a very good level, ○ is a good level, △ is a practically acceptable level, and × is a level not suitable for practical use. ◎: Filtration volume is 8.0g or more 〇: Filtration volume is 5.0g or more but less than 8.0g △: Filtration volume is 3.0g or more but less than 5.0g ×: Filtration volume is 3.0g or less

[0304] The results of the evaluation using the above methods are shown in Tables 7-2 and 8-2.

[0305] [Table 7-2]

[0306] [Table 8-2]

[0307] In the photosensitive coloring compositions, the same results as those of the coloring compositions shown in Examples 78 to 84, 89 to 90, 92 to 93, 96 to 99, 101 to 104, 106 to 109, 113 to 126 and Comparative Examples 1 to 6 were obtained.

[0308] <Film production for various purposes> From the above results, it is expected that the optical films using the colored compositions prepared in the examples can be suitably used in near-infrared cameras, surveillance cameras, in-vehicle cameras, medical cameras, inspection and analysis cameras, temperature sensors, distance sensors, medical sensors, touch sensors for displays, biometric authentication sensors, etc., due to their excellent properties.

Claims

1. A coloring composition comprising a near-infrared absorbing colorant (A) having an absorption maximum in the range of 700 to 1300 nm, a chromatic colorant (B) having an absorption maximum in the range of 400 to 700 nm, a resin-type dispersant (C), a binder resin (D), a solvent (E), and a metal component containing a metal atom selected from Li, Na, K, Cs, Mg, Ca, Fe, and Zr, wherein the near-infrared absorbing colorant (A) accounts for 67 to 90% by mass of a total of 100% by mass of the near-infrared absorbing colorant (A) and the chromatic colorant (B), A coloring composition, wherein the total amount of the metal atoms contained in the metal component is 1 to 1000 ppm by mass relative to 100% by mass of the coloring composition.

2. The colored composition according to claim 1 , wherein the near-infrared absorbing colorant (A) comprises a near-infrared absorbing colorant (A1) that satisfies the following conditions (1) and (2): (1) The average primary particle size is 5 to 150 nm. (2) When a film having a thickness of 1.0 μm is formed, the maximum value S of the light transmittance in the thickness direction of the film in the range of 400 to 900 nm and the minimum value T in the range of 700 to 1300 nm satisfy the following formula: S / T = 5 to 150

3. 3. The colored composition according to claim 1, wherein the resin-type dispersant (C) comprises an acidic resin-type dispersant having an acid value of 30 to 80 mgKOH / g.

4. 4. The colored composition according to claim 3, wherein the acidic resin-type dispersant comprises a resin-type dispersant which is a reaction product obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product between a polymer having a hydroxyl group at at least one terminal and a tricarboxylic acid anhydride or a tetracarboxylic acid dianhydride and / or a reaction product between a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride or a tetracarboxylic acid dianhydride.

5. The coloring composition according to any one of claims 1 to 4, wherein the solvent (E) comprises methoxypropyl acetate.

6. The colored composition according to any one of claims 1 to 5, wherein the water content in the colored composition is 0.1 to 2.0% by mass relative to 100% by mass of the colored composition.

7. The colored composition according to any one of claims 1 to 6, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

8. An optical filter having a coating formed on a substrate using the coloring composition according to any one of claims 1 to 7.

9. An infrared camera comprising the optical filter according to claim 8.

10. An infrared sensor comprising the optical filter according to claim 8.

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