Infrared-transmitting coloring composition, coating film, and optical semiconductor device

Abstract

To provide an infrared transmission type coloring composition which has good heat resistance and suppresses transmission of visible light, and satisfactorily transmits near-infrared rays of a wavelength of 700 nm or more.SOLUTION: An infrared transmission type coloring composition contains a coloring agent (A) and a dispersion resin (B), wherein the coloring agent (A) contains a violet pigment and a yellow pigment, and when a film with film thickness of 1.0 μm is formed, the following conditions (1) and (2) are satisfied. Condition (1): maximum transmittance of light at a wavelength of 400 to 600 nm is 20% or less. Condition (2): minimum transmittance of light at a wavelength of 700 to 1,000 nm is 75% or more.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an infrared transmitting coloring composition. [Background technology]

[0002] Optical semiconductor devices, infrared sensors, solid-state imaging devices, etc. have been developed that block unnecessary visible light in a specific range and transmit only necessary infrared light in a specific range, sensing it with an optical element (photodiode, etc.). In order to transmit only infrared rays in a specific required range, Patent Document 1 discloses an infrared transmitting coloring composition containing a dye that has an absorption band in the wavelength region of 350 to 650 nm and transmits at least a part of light with a wavelength of 800 to 900 nm. Patent Document 2 discloses a technology that uses a naphthalocyanine coloring material (dye) to transmit wavelengths of 900 nm or more. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2019-131806 A [Patent Document 2] JP 2008-101188 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, the invention of Patent Document 1 has a problem in that heat resistance is insufficient because a dye is used. Furthermore, the invention of Patent Document 2 can transmit wavelengths of 900 nm or more, but cannot transmit wavelengths of 700 to 900 nm well.

[0005] An object of the present invention is to provide an infrared transmitting coloring composition capable of forming a coating film which has good heat resistance, suppresses the transmission of visible light, and has good transmission of near infrared light having a wavelength of 700 nm or more. [Means for solving the problem]

[0006] The present invention provides an infrared transmitting coloring composition comprising a colorant (A) and a dispersing resin (B), The colorant (A) contains a purple pigment and a yellow pigment, This is an infrared transmitting coloring composition that satisfies the following conditions (1) and (2) when a coating having a thickness of 1.0 μm is formed. Condition (1): The maximum transmittance of light at wavelengths of 400 to 600 nm is 20% or less. Condition (2): The minimum transmittance of light at wavelengths of 700 to 1000 nm is 75% or more. Effect of the Invention

[0007] According to the present invention, it is possible to provide an infrared-transmitting coloring composition capable of forming a coating film having good heat resistance, suppressing the transmission of visible light, and having good transmission of near-infrared light having a wavelength of 700 nm or more. In addition, it is possible to provide an optical semiconductor device (such as a liquid crystal display device, an infrared sensor, or a solid-state imaging device). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The terms used in this specification are defined below. When "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" is written, it means "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide", respectively, unless otherwise specified. "CI" in this specification means Color Index (CI). Colorants mean pigments and dyes. Infrared transmission means suppressing light transmission in the visible light region and transmitting light in the wavelength region longer than near infrared. The monomer is an ethylenically unsaturated monomer.

[0009] The infrared transmitting coloring composition of the present invention is an infrared transmitting coloring composition comprising a colorant (A) and a dispersing resin (B), The colorant (A) contains a purple pigment and a yellow pigment, This is an infrared transmitting coloring composition that satisfies the following conditions (1) and (2) when a coating having a thickness of 1.0 μm is formed. Condition (1): The maximum transmittance of light at wavelengths of 400 to 600 nm is 20% or less. Condition (2): The minimum transmittance of light at wavelengths of 700 to 1000 nm is 75% or more. The maximum transmittance of the condition (1) is preferably 15% or less, more preferably 10% or less, and the minimum transmittance of the condition (2) is preferably more than 80%, more preferably more than 85%.

[0010] In this specification, in addition to the above-mentioned "preferable spectral range of the present invention", a composition that satisfies the following condition (3) is more preferable. Condition (3): The difference in wavelength (λ2-λ1) between the maximum wavelength λ1 at which the light transmittance is 30% and the minimum wavelength λ2 at which the light transmittance is 70% is within 60 nm. When condition (3) is satisfied, the wavelength region between the wavelength region sensed and the wavelength region not sensed by the optical semiconductor device becomes narrower, thereby further improving the sensing sensitivity of the optical semiconductor device.

[0011] <Colorant (A)> The colorant (A) includes a purple pigment and a yellow pigment. Examples of purple pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, CI Pigment Violet 23 is preferred. When CI Pigment Violet 23 is contained, the transmittance at wavelengths of 600 nm or less can be further suppressed, and the transmittance at wavelengths of 700 nm or more can be further improved.

[0012] The content of CI Pigment Violet 23 is preferably 50 to 85 mass%, more preferably 55 to 80 mass%, and even more preferably 55 to 70 mass%, in 100 mass% of the colorant (A), which further improves the spectral characteristics of the coating film.

[0013] The yellow pigment suppresses the transmittance of light having a wavelength of 400 to 500 nm, which is transmitted by the violet pigment. Examples of the yellow pigment include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123 , 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, and the pigments described in JP-A-2012-226110. Among these, CI Pigment Yellow 139 and 185 which are isoindoline pigments; CI Pigment Yellow 231 which is a quinophthalone pigment are preferred, isoindoline pigments are more preferred, and CI Pigment Yellow 139 and 185 are even more preferred.

[0014] The content of the yellow pigment is preferably from 15 to 50% by mass, and more preferably from 30 to 45% by mass, in 100% by mass of the colorant (A). When an appropriate amount is contained, the spectral characteristics are further improved.

[0015] In this specification, the colorant (A) may contain other colorants other than those described above as long as the problem can be solved. Examples of the other colorants include organic pigments and dyes.

[0016] The amount of the other colorants is preferably 3% by mass or less, and more preferably 1% by mass or less, based on 100% by mass of the colorant (A).

[0017] <Other colorants> Other colorants are listed below by their color index numbers.

[0018] Red pigments include, for example, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, No. 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, pigments described in JP-A-2014-134712, and pigments described in Japanese Patent No. 6368844.

[0019] Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79.

[0020] Examples of green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, and 63, and pigments described in JP2017-111398A.

[0021] Examples of inorganic pigments include titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, amber, and synthetic iron black.

[0022] <dye> Dyes can be used in combination as long as the problem can be solved. Examples of the dyes include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. In addition, dye derivatives and lake pigments obtained by converting dyes into lakes can also be used.

[0023] In addition, the dye may be an acid dye having an acidic group such as sulfonic acid or carboxylic acid, or in the case of a direct dye, an inorganic salt of an acid dye; a salt-forming compound of an acid dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound; or a salt-forming compound of a resin component having an amino group and an acid dye. A salt-forming compound of an acid dye and a compound having an onium salt group is also preferable because it has excellent fastness. In addition, the compound having an onium salt group is preferably a resin having a cationic group in the side chain.

[0024] Examples of the basic dye include salt-forming compounds with organic acids, perchloric acid, or metal salts thereof. Among the salt-forming compounds, salt-forming compounds of basic dyes are preferred because they have excellent resistance to various types of substances and are compatible with pigments.

[0025] <Minification of pigments> It is preferable that the organic pigment is mixed with other raw materials after being subjected to a micronization treatment. Examples of the method of the micronization treatment include wet grinding, dry grinding, and dissolution precipitation. Among these, a salt milling treatment using a kneader method, which is a type of wet grinding, is preferable. The average primary particle size of the organic pigment after the micronization treatment is preferably 10 to 80 nm, more preferably 15 to 70 nm. A moderate particle size improves dispersibility and the contrast ratio of the coating. The average primary particle size is the average value of about 20 particles arbitrarily selected from an enlarged image of a TEM (transmission electron microscope). When the particle has a vertical axis length and a horizontal axis length, the vertical axis length is used.

[0026] The salt milling process is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded while being heated using a batch or continuous kneader such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, or a planetary mixer, and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed during salt milling by utilizing the high hardness of the inorganic salt. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution.

[0027] Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate. Among these, sodium chloride (table salt) is preferred from the viewpoint of cost. The amount of the water-soluble inorganic salt used is preferably 50 to 2000 parts by mass, and more preferably 300 to 1000 parts by mass, per 100 parts by mass of the pigment, from the viewpoints of both treatment efficiency and production efficiency.

[0028] The water-soluble organic solvent moistens the pigment and the water-soluble inorganic salt. The water-soluble organic solvent is a compound that dissolves (is mixed) in water and does not substantially dissolve the water-soluble inorganic salt. The water-soluble organic solvent is preferably a high-boiling solvent having a boiling point of 120°C or more, in that it is less likely to volatilize due to the temperature rise during salt milling. Examples of the water-soluble organic solvent include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and liquid polypropylene glycol. The amount of the water-soluble organic solvent used is preferably 5 to 1000 parts by mass, more preferably 50 to 500 parts by mass, relative to 100 parts by mass of the pigment.

[0029] During the salt milling treatment, a resin can be added as necessary. Examples of the resin include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. The resin is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in a water-soluble organic solvent. The amount of the resin used is preferably 5 to 200 parts by mass relative to 100 parts by mass of the pigment.

[0030] <Metal Removal> If the coloring composition contains a large amount of specific metal elements as impurities other than the pigment components, it may hinder the dispersion stability over time, and may cause a decrease in heat resistance or a decrease in sensitivity. In addition, an infrared light transmitting film made using this may have foreign matter, which may result in a decrease in transmittance. The total content of Li, Na, K, Mg, Ca, Fe, Al, and Cr (hereinafter also referred to as specific metal elements) contained in the coloring composition is preferably 500 mass ppm or less.

[0031] The total amount of specific metal elements contained in the coloring composition is more preferably 300 mass ppm or less, particularly preferably 200 mass ppm or less.The lower limit of the total amount of specific metal elements is not particularly limited, but is preferably 1 mass ppm or more, more preferably 5 mass ppm or more.Within the above range, it is possible to obtain a coloring composition that can suppress costs, has excellent storage stability, and can form an infrared light transmitting film with little generation of foreign matter and little decrease in transmittance.

[0032] The amount of each specific metal element contained in the coloring composition is preferably 100 ppm by mass or less, and more preferably 50 ppm by mass or less.

[0033] In addition, it is also preferable that the amount of impurities that do not function effectively, such as metals such as Ni, Zn, Cu, Al, Fe, Fe, Co, and Co that constitute the pigment, is small, and these can be removed in the same manner as the specific metal elements by the following method. Furthermore, it is also preferable that Mn, Cs, Ti, Co, Si, Pd, etc., that are mixed in due to materials (e.g., catalysts) used in the manufacturing process of various raw materials of the coloring composition, are low in concentration.

[0034] Methods for removing the colorant (A) or metals that have become mixed in from equipment during the manufacturing process include methods using water washing as described in JP-A-2010-83997, JP-A-2018-36521, JP-A-7-198928, JP-A-8-333521, JP-A-2009-7432, etc., and methods for removing magnetic foreign matter using a magnet as described in JP-A-2011-48736, and the like. One or more of these methods can be used as appropriate.

[0035] The content of specific metal elements can be measured by inductively coupled plasma emission spectrometry (ICP).

[0036] The coloring composition of the present invention contains a dispersing resin (B) for the purposes of preventing aggregation of the finely divided pigment, maintaining dispersion stability in the solvent, and maintaining affinity with other resins. In addition, the addition of a dye derivative is preferable because it can further enhance the effect of the dispersing resin (B). <Dye derivative (a)> The coloring composition can use a dye derivative (a) together with the pigment. The dye derivative is a compound having an acidic group, a basic group, a neutral group, etc. in the organic dye residue. The dye derivative can be, for example, a compound having an acidic substituent such as a sulfo group, a carboxy group, or a phosphoric acid group, as well as the amine salts thereof, a compound having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal, and a compound having a neutral substituent such as a phenyl group or a phthalimidoalkyl group. Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

[0037] These dye derivatives can be used alone or in combination of two or more kinds.

[0038] The amount of the dye derivative used is preferably from 1 to 100 parts by mass, more preferably from 3 to 70 parts by mass, and even more preferably from 5 to 50 parts by mass, relative to 100 parts by mass of the organic pigment.

[0039] By adding a dye derivative to a pigment and carrying out a micronization treatment such as acid pasting, acid slurry, dry milling, salt milling, or solvent salt milling, the dye derivative is adsorbed onto the pigment surface, and the primary particles of the pigment can be made finer than when the dye derivative is not added.

[0040] <Dispersion resin (B)> The infrared transmitting coloring composition of the present invention may contain a dispersing resin (B) (hereinafter, also referred to as a resin-type dispersant). The dispersing resin (B) is a resin having an adsorption site that adsorbs to a colorant and a stress relaxation site that stably disperses colorant particles. Examples of the dispersing resin (B) include urethane-based dispersants such as polyurethane, polycarboxylate esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylate 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 alcohols, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphate esters.

[0041] Examples of the dispersing resin (B) having an acidic functional group include dispersing resins having an aromatic carboxylic acid structure, as described in WO2008 / 007776, JP2008-029901A, JP2009-155406A, JP2010-185934A, JP2011-157416A, JP2009-251481A, JP2007-23195A, and JP1996-143651A.

[0042] The dispersion resin having an aromatic carboxylic acid structure may be, for example, a resin having a main chain containing an aromatic carboxylic acid ester moiety having an ester bond formed by esterification of an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups, and a side chain containing a vinyl polymer moiety. The amount of the acid anhydride group relative to 1 mole of the hydroxyl group is preferably 0.9 to 1.5 moles, more preferably 1.0 to 1.3 moles. The main chain containing the aromatic carboxylate moiety preferably has a structure having a blocking moiety derived from a monoalcohol, which will be described later, whereby the acid anhydride group in the main chain is modified to an alcohol ester group and a carboxyl group. Use of the dispersion resin (B) improves the filterability of the infrared-transmitting coloring composition and suppresses foreign matter in the coating. Furthermore, the solidified material generated when the infrared-transmitting coloring composition is applied with a die coater or the like becomes easily redissolved in propylene glycol monomethyl ether acetate (PGMAc) (resolubility). The side chain based on the vinyl polymer moiety is formed by polymerization of a monomer.

[0043] (Aromatic compounds having two or more acid anhydride groups) Examples of aromatic compounds having two or more acid anhydride groups include pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene Tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride Water, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether tert-butyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, and 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride.

[0044] (Compounds having two or more hydroxyl groups) As described above, the compound having two or more hydroxyl groups is preferably a compound having a hydroxyl group and a thiol group in the molecule, and more preferably a compound having two hydroxyl groups and one thiol group in the molecule.

[0045] Examples of compounds having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and 2-mercaptoethyl-2-ethyl-1,3-propanediol.

[0046] (Monoalcohol) Examples of monoalcohols include monoalcohols such as methanol, ethanol, 1-butanol, 2-butanol, isobutanol, t-butanol, 1-pentanol, isopentyl alcohol, tert-pentyl alcohol, cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, isononyl alcohol, 1-nonyl alcohol, amyl alcohol, lauryl alcohol, n-butyl alcohol, isobutyl alcohol, cyclohexanol, benzyl alcohol, and methylcyclohexanol; monoalcohols having an ether group, such as 3-methoxy-3-methyl-1-butanol, 3-methoxybutanol, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, and propylene glycol monomethyl ether; Examples of the monoalcohol include methyl lactate, ethyl lactate, diacetone alcohol, and other monoalcohols having a carbonyl group.

[0047] The monoalcohol is preferably a compound having an ether group or a carbonyl group, and more preferably 3-methoxybutanol, propylene glycol monomethyl ether, or diacetone alcohol, which generates an ether group or a carbonyl group at the end of the main chain of the dispersion resin, thereby improving the resolubility in PGMAc.

[0048] The main chain which is an aromatic carboxylate moiety may have a blocking moiety which is reacted with water, in addition to a blocking moiety derived from a monoalcohol.

[0049] In the synthesis of the capping portion, the amount of monoalcohol used relative to the acid anhydride group is preferably 1 to 30 molar equivalents relative to 1 equivalent of the acid anhydride group remaining in the main chain, and more preferably 1.5 to 20 molar equivalents. When the amount is 1 molar equivalent or more, no acid anhydride group remains, resulting in good storage stability, and when the amount is 30 molar equivalents or less, ester exchange reaction due to the ester bond between the monoalcohol and the dispersant is unlikely to occur, and a decrease in molecular weight is unlikely to occur.

[0050] (Side chain that is a vinyl polymer moiety) The side chain of the dispersing resin (B) can be synthesized by polymerizing a monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule. The dispersion resin having an aromatic carboxylic acid structure can form a main chain after first forming a side chain, which is a vinyl polymer moiety, or can form a side chain by polymerizing a monomer after forming a main chain through the esterification reaction.

[0051] Examples of dispersion resins having basic functional groups include nitrogen atom-containing graft copolymers, nitrogen atom-containing acrylic block copolymers having functional groups in the side chains including tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc., and urethane-based polymer dispersants.

[0052] As disclosed in JP 2009-185277 A, a preferred example is the combined use of a dispersing resin (B) having an aromatic carboxyl group and a vinyl resin (having the function of dispersing resin (B)) having a tertiary amino group.

[0053] The amount of the dispersing resin (B) used is preferably from 3 to 200% by mass relative to the colorant (A), and from the viewpoint of film-forming properties, more preferably from 5 to 100% by mass.

[0054] <Curable resin (C)> The colored composition of the present invention contains a curable resin (C). The curable resin (C) may be a thermosetting resin or a photocurable resin. (thermosetting resin) Examples of the thermosetting resin include epoxy resin and silicone resin.

[0055] (Epoxy resin) Examples of epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins, alicyclic epoxy resins, those having an isocyanuric ring skeleton, nitrogen-containing ring epoxy resins such as hydantoin epoxy resins, hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol F type epoxy resins, aliphatic epoxy resins, glycidyl ether type epoxy resins, bisphenol S type epoxy resins, biphenyl type epoxy resins which are the mainstream of low water absorption cured body types, dicyclocyclic type epoxy resins, naphthalene type epoxy resins, etc. Among these, bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins, alicyclic epoxy resins, and isocyanuric ring-containing resins are preferred.

[0056] The epoxy resin preferably has an average epoxy equivalent of 90 to 1000, and the softening point of the epoxy resin is preferably 160° C. or lower. When the epoxy equivalent is 90 or higher, the cured product has an appropriate flexibility. When the epoxy equivalent is 1000 or lower, the heat resistance is further improved.

[0057] The epoxy resin can be used in combination with a curing agent. Examples of the curing agent include acid anhydrides and phenol compound-based curing agents. Examples of the acid anhydride include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. Among these, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride are preferred. The molecular weight of the acid anhydride is preferably about 140 to 200.

[0058] Examples of the phenolic compound include resol type phenolic resin, novolac type phenolic resin, novolac type phenol formaldehyde resin, polyhydroxystyrene resin, etc. Examples of the resol type phenolic resin include aniline modified resol resin, melamine modified resol resin, etc. Examples of the novolac type phenolic resin include phenol novolac resin, cresol novolac resin, tert-butylphenol novolac resin, nonylphenol novolac resin, naphthol novolac resin, etc. Examples of the novolac type phenol formaldehyde resin include special phenolic resins such as dicyclopentadiene modified phenolic resin, terpene modified phenolic resin, triphenol methane type resin, phenol aralkyl resin (having a phenylene skeleton, a diphenylene skeleton, etc.), naphthol aralkyl resin, etc. Examples of the polyhydroxystyrene resin include poly(p-hydroxystyrene), etc.

[0059] The mixing ratio of the epoxy resin and the curing agent is preferably 0.5 to 1.5 equivalents of reactive groups (acid anhydride groups or hydroxyl groups) in the curing agent per equivalent of epoxy groups in the epoxy resin, more preferably 0.7 to 1.2 equivalents. By mixing in the appropriate amounts, both the curing speed and the thermosetting properties of the cured product can be achieved at a high level.

[0060] In addition to the acid anhydride and the phenol compound, other curing agents may be used, such as amines and carboxylic acid compounds.

[0061] (Silicone resin) Examples of silicone resins include those described in JP-A-2019-131806 and JP-A-2010-121117.

[0062] (light curing resin) The photocurable resin is a resin having a polymerizable unsaturated group, and examples thereof include the resins described in JP-A-2016-150978 and JP-A-2019-052197. The photocurable resin may be used in combination with a photopolymerization initiator, a sensitizer, and the like.

[0063] (Organic solvent) Examples of the solvent to be used include ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO- or -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

[0064] Of the above solvents, from the viewpoint of coatability and drying property, it is preferable to include an organic solvent having a boiling point at 1 atm of 120° C. or more and 180° C. or less. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc. are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are more preferred.

[0065] (Method for producing infrared transmitting coloring composition) The infrared transmitting coloring composition is prepared, for example, by adding a colorant (A), a dispersing resin (B), a solvent, etc., and carrying out a dispersion treatment. Next, if necessary, a curable resin (C) is added and mixed by stirring. The components to be mixed and the timing of mixing are arbitrary. The dispersion process can also be carried out multiple times.

[0066] Examples of dispersing machines for carrying out the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, and an attritor.

[0067] The coating of the present invention (hereinafter also referred to as infrared-transmitting film) is formed from an infrared-transmitting coloring composition. When the composition contains a curable resin (C), the coating can be cured by heating or the like (in this case, the coating is referred to as a cured film). The coating is formed by applying an infrared-transmitting coloring composition to a base material (also referred to as a substrate) and drying it. Examples of the application include a dropping method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, an inkjet method, flexographic printing, screen printing, gravure printing, offset printing, and the like. Examples of the drying include hot air drying and an infrared heater, and the like.

[0068] The thickness of the coating is preferably from 0.05 μm to 5.0 mm, and more preferably from 0.1 μm to 3.0 mm.

[0069] The curing can be carried out, for example, at a temperature of 100 to 180° C. for 10 minutes to 5 hours.

[0070] The optical semiconductor device of the present invention comprises a coating film formed from an infrared transmitting coloring composition. Examples of optical semiconductor devices include devices that utilize light, such as liquid crystal displays, LEDs, and optical sensors (eg, infrared sensors). In this specification, the infrared-transmitting film can be formed into a thin film and laminated on a liquid crystal display device or a solid-state imaging device. The infrared-transmitting film can also be injected onto an optical semiconductor element during the manufacture of an LED or an optical sensor to seal it. The sealing can be performed by a known molding method such as transfer molding or casting. EXAMPLES

[0071] The present invention will be described below with reference to examples. However, the present invention is not limited to the examples. In the examples, "parts" means "parts by mass" and "%" means "% by mass".

[0072] Prior to the examples, the methods for measuring and calculating the average molecular weight of a resin and the acid value of a resin will be described.

[0073] <Average primary particle size of pigment> The average primary particle size of the pigment was measured by a common method of directly measuring the size of the primary particles from a transmission electron microscope (TEM) photograph. Specifically, the minor axis and major axis diameters of each pigment primary particle were measured, and the average was taken as the particle size of the pigment particle. Next, for 100 or more pigment particles, the volume (weight) of each particle was calculated by approximating it to a rectangular parallelepiped of the calculated particle size, and the volume average particle size was taken as the average primary particle size.

[0074] (Dispersed particle size measurement) Using Nikkiso's Microtrac UPA-EX150 with dynamic light scattering (FFT power spectrum method), particle transmittance was set to absorption mode, particle shape was set to non-spherical, and D50 was set to average diameter. The same solvents used for the dispersion were used as dilution solvents for the measurement, and the samples treated with ultrasonic waves were measured immediately after sample preparation.

[0075] (Average molecular weight of resin) The number average molecular weight (Mn) and mass average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was an HLC-8220GPC (manufactured by Tosoh Corporation), with two separation columns connected in series, and both packings were "TSK-GEL SUPER HZM-N" connected in series. The oven temperature was 40°C, THF solution was used as the eluent, and the flow rate was 0.35 ml / min. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent, and 20 microliters were injected. All molecular weights are polystyrene equivalent values.

[0076] (Acid value of resin) 80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of resin solution, and the solution was stirred to dissolve uniformly. The solution was titrated using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) with a 0.1 mol / L KOH aqueous solution as the titrant, and the acid value (mgKOH / g) of the resin solution was measured. The acid value per unit of non-volatile content of the resin was calculated from the acid value of the resin solution and the concentration of non-volatile content of the resin solution.

[0077] <Method of manufacturing fine pigment> <Fine particle size of colorant (A)> (Colorant (A1)) 300 parts of a dioxazine-based purple pigment, Pigment Violet 23 ("Lionogen Violet RL" manufactured by Toyo Color Co., Ltd.) was added to 3000 parts of 96% sulfuric acid, stirred for 1 hour, and then poured into water at 5°C. After stirring for 1 hour, the mixture was filtered, washed with warm water until the washing liquid became neutral, and dried at 70°C. 120 parts of the obtained acid pasting-treated pigment, 5 parts of the dye derivative (b-2), 1500 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 at 70°C for 20 hours. This mixture was added to 5000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then dried at 80°C for 24 hours to obtain pigment (A1).

[0078] (Colorant (A2-1)) 100 parts of CI Pigment Yellow 139 (BASF Japan "Irgaphor Yellow 2R-CF"), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded for 10 hours at 60° C. Next, this mixture was poured into 3 liters of warm water, heated to about 80° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and the solvent, and then dried at 80° C. for one day and night to obtain colorant (A2-1).

[0079] (Colorant (A2-2)) 500 parts of CI Pigment Yellow 185 (BASF Japan "Paliotol Yellow D1155"), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded for 8 hours at 120° C. Next, this kneaded mixture was poured into 5 liters of warm water, heated to 70° C. and stirred for 1 hour to form a slurry, which was then filtered and washed repeatedly to remove the sodium chloride and diethylene glycol, and then dried at 80° C. overnight to obtain colorant (A2-2).

[0080] (Colorant (A2-3)) 100 parts of CI Pigment Yellow 231 (manufactured by Toyo Color Co., Ltd.), 1200 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.), kneaded for 6 hours at 60° C., and subjected to salt milling treatment. The kneaded product obtained was poured into 3 liters of warm water, heated to 70° C. and stirred for 1 hour to form a slurry, which was then filtered and washed repeatedly to remove the sodium chloride and diethylene glycol, and then dried at 80° C. for one day to obtain colorant (A2-3).

[0081] (Colorant (A2-4)) 100 parts of CI Pigment Yellow 138 (BASF Japan "Paliotol Yellow K0961HD"), 800 parts of ground salt, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Manufacturing Co., Ltd.) and kneaded for 4 hours at 70° C. This mixture was added to 3000 parts of warm water, heated to about 80° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly with water to remove the salt and solvent, and then dried at 80° C. for 24 hours to obtain colorant (A2-4).

[0082] (Colorant (A2-5)) 100 parts of CI Pigment Yellow 150 (Yellow Pigment E4GN manufactured by Lanxess), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 10 hours at 60° C. Next, this mixture was poured into 3 liters of warm water, and stirred with a high-speed mixer for about 1 hour while heating to about 80° C. to form a slurry. After repeatedly filtering and washing with water to remove the sodium chloride and the solvent, the mixture was dried at 80° C. for one day and night to obtain colorant (A2-5).

[0083] (Colorant (A3)) 100 parts of CI Pigment Blue 15:6 ("Leonol Blue ES" manufactured by Toyo Color Co., Ltd.), 1000 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 50° C. This mixture was poured into 3000 parts of warm water, heated to about 70° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, which was then repeatedly filtered and washed with water to remove the salt and solvent, and then dried at 80° C. for 24 hours to obtain colorant (A3).

[0084] <Dye derivative (a)> The following basic pigment derivatives were used: Dye derivative (a-1) [ka] Dye derivative (a-2) [ka] Dye derivative (a-3) [ka] Dye derivative (a-4) [ka] Dye derivative (a-5) [ka] Dye derivatives (a-6) [ka]

[0085] (Example of manufacturing dispersion resin (B-1) liquid) A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 20.0 parts of tert-butyl acrylate, 45.0 parts of methyl methacrylate, 30.0 parts of ethyl acrylate, and 5.0 parts of methacrylic acid, and the atmosphere was replaced with nitrogen gas. The reaction vessel was heated to 80°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile dissolved in 70.7 parts of PGMAc was added to 6.0 parts of 3-mercapto-1,2-propanediol, and the reaction was carried out for 10 hours. It was confirmed that 95% or more had reacted by measuring the non-volatile content. Next, 14.5 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), 38.0 parts of PGMAc, and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 120 ° C for 5 hours. After that, 12.1 g of 3-methoxybutanol was added, and the mixture was reacted at 120 ° C for 3 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. After the reaction was completed, PGMAc was added so that the non-volatile content was 40% by mass, and a dispersion resin (B-1) liquid with an acid value of 105 mg KOH / g and a weight average molecular weight of 9400 was obtained.

[0086] (Example of manufacturing dispersion resin (B-2) liquid) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 50.0 parts of t-butyl acrylate, 45.0 parts of methyl methacrylate, and 5.0 parts of methacrylic acid were charged and replaced with nitrogen gas. The reaction vessel was heated to 80°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile dissolved in 70.7 parts of PGMAc was added to 6.0 parts of 3-mercapto-1,2-propanediol, and reacted for 10 hours. It was confirmed that more than 95% had reacted by measuring the non-volatile content. Next, 14.5 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), 38.0 parts of PGMAc, and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 120 ° C for 5 hours. After that, 12.1 g of 3-methoxybutanol was added, and the mixture was reacted at 120 ° C for 3 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. After the reaction was completed, PGMAc was added so that the non-volatile content was 40% by mass, and a dispersion resin (B-2) liquid with an acid value of 110 mg KOH / g and a weight average molecular weight of 9000 was obtained.

[0087] (Example of manufacturing dispersion resin (B-3) liquid) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 6 parts of 3-mercapto-1,2-propanediol, 14.5 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), and 70.8 parts of PGMAc were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 100°C and reacted for 5 hours. Then, 12.1 g of 3-methoxybutanol was added and reacted at 120°C for 3 hours. After confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, the temperature of the reaction system was cooled to 70°C, 50.0 parts of t-butyl acrylate and 50.0 parts of methyl methacrylate were charged, and 38.0 parts of PGMAc in which 0.1 parts of 2,2'-azobisisobutyronitrile had been dissolved was added and reacted for 10 hours. It was confirmed that 95% or more of the monomer had reacted by measuring the non-volatile content, and the reaction was terminated. After the reaction was completed, PGMAc was added so that the non-volatile content became 40% by mass, and a dispersion resin (B-3) liquid having an acid value of 93 mgKOH / g and a weight average molecular weight of 10,800 was obtained.

[0088] (Preparation of dispersion resin (B-4) liquid) A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer. 106 parts of cyclohexanone was charged into the reaction vessel, which was then heated to 80°C and replaced with nitrogen. From the dropping tube, a mixture of 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), and 1.1 parts of 2,2'-azobisisobutyronitrile was dropped over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content. Next, PGMAc was added so that the non-volatile content of the obtained resin solution was 40%, to prepare a dispersion resin (B-4) liquid. The weight average molecular weight (Mw) was 26,000.

[0089] <Method of producing colored composition> [Example 1] (Preparation of Coloring Composition (X-1)) The coloring composition (X-1-1) and the coloring composition (X-1-2) shown below were stirred and mixed. A colored composition (X-1) was prepared.

[0090] (Preparation of Coloring Composition (X-1-1)) The mixture below was stirred and mixed until homogeneous, and then dispersed in an Eiger mill (Eiger Japan's "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm for 3 hours. The mixture was then filtered through a filter with a pore size of 5.0 μm to produce a colored composition (X-1-1) with a non-volatile content of 20.0 mass %. Pigment (A1): 11.0 parts Pigment derivative (a-1): 1.0 part Dispersion resin ((B-1): non-volatile content 40%) solution: 10.0 parts Solvent (PGMAc): 80.0 parts

[0091] (Preparation of Coloring Composition (X-1-2)) The mixture below was stirred and mixed until homogeneous, and then dispersed in an Eiger mill (Eiger Japan's "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm for 3 hours. The mixture was then filtered through a filter with a pore size of 5.0 μm to produce a colored composition (X-1-1) with a non-volatile content of 20.0 mass %. Pigment (A2-1): 7.0 parts Pigment derivative (a-4): 1.0 part Dispersion resin ((B-1): non-volatile content 40%) solution: 10.0 parts Solvent (PGMAc): 80.0 parts

[0092] [Examples 2 to 18, Comparative Examples 1 to 4] (Preparation of Colored Compositions (X-2 to X-22)) The same procedure as in Example 1 was carried out except that the material types and masses were changed as shown in Tables 1 and 2, to prepare colored compositions (X-2 to X-22).

[0093] (Evaluation of Coloring Composition) [Coating film preparation] The obtained colored composition was applied onto a glass substrate of 100 mm length×100 mm width and 0.7 mm thickness using a spin coater, then heated at 230° C. for 20 minutes and allowed to cool to obtain a coated substrate with a film thickness of 1.0 μm.

[0094] [Light transmittance measurement] The light transmittance of the obtained coating substrate at wavelengths of 400 to 1000 nm was measured using a microspectrophotometer (Hitachi High-Tech Science Corporation, "U-3900"), and the maximum light transmittance at wavelengths of 400 to 600 nm (Tmax (400-600 nm)), the minimum light transmittance at wavelengths of 700 to 1000 nm (Tmin (700-1000 nm)), and the difference in wavelength between the maximum wavelength λ1 at which the light transmittance is 30% and the minimum wavelength λ2 at which the light transmittance is 70% (λ2-λ1) were determined. The evaluation criteria were 1: unusable, 2: practical range, and 3: excellent. The results are shown in Table 1.

[0095] Condition (1) Evaluation criteria for the maximum light transmittance in the wavelength range of 400 to 600 nm (Tmax (400 to 600 nm)): 3: Tmax is less than 10% 2: Tmax is 10% or more and 20% or less 1: Tmax exceeds 20%

[0096] Condition (2) Evaluation criteria for the minimum light transmittance in the wavelength range of 700 to 1000 nm (Tmax (700 to 1000 nm)): 3: Tmin exceeds 80% 2: Tmin is 75% or more and 80% or less 1: Tmin is less than 75%

[0097] Condition (3) Evaluation criteria for the wavelength difference (λ2-λ1) between the maximum wavelength λ1 at which the light transmittance is 30% and the minimum wavelength λ2 at which the light transmittance is 70%: 3: (λ2-λ1) is less than 40 nm 2: (λ2-λ1) is 40nm or more and 60nm or less 1: (λ2-λ1) exceeds 60 nm

[0098] [Heat resistance] In the above coating film preparation, the chromaticity of the substrate was measured before and after heating at 230° C. for 20 minutes using a microspectrophotometer (manufactured by Olympus Optical Co., Ltd., “OSP-SP200”), and the difference in brightness between before and after the heating was measured. The evaluation criteria were as follows. Lightness difference (ΔY) = |(lightness Y after heating) - (lightness Y before heating)| 3: Less than 0.4 Good heat resistance 2: 0.4 or more but less than 0.8 Heat resistance is in the practical range 1:0.8 or more Heat resistance is not practical

[0099] [Table 1]

[0100] [Table 2]

[0101] <Preparation of Curable Composition> (Curable resin (C)) E-1: Epoxy resin (JER-827, manufactured by Japan Epoxy Resin Co., Ltd.) E-2: Epoxy resin synthesized by the following method In a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer, 79.5 parts (0.25 moles) of 1,1'-binaphthalene-2,2',7,7'-tetraol, 462 parts (5.0 moles) of epichlorohydrin, and 126 parts of n-butanol were charged and dissolved while purging with nitrogen gas. After heating to 40°C, 100 parts (1.20 moles) of 48% aqueous sodium hydroxide solution were added over 8 hours, and then the temperature was further raised to 50°C and reacted for another hour. After the reaction was completed, 150 parts of water was added and allowed to stand, and the lower layer was discarded. Then, unreacted epichlorohydrin was distilled off under reduced pressure at 150°C. 230 parts of methyl isobutyl ketone was added to the obtained crude epoxy resin and dissolved. Furthermore, 100 parts of 10% by mass aqueous sodium hydroxide solution was added to this solution and reacted at 80°C for 2 hours. The mixture was then washed three times with water until the pH of the washings became neutral. The system was then dehydrated by azeotropy, and after microfiltration, the solvent was distilled off under reduced pressure to obtain 135 parts of the desired epoxy resin, 2,2',7,7'-tetraglycidyloxy-1,1'-binaphthalene (A-1). The softening point of the obtained epoxy resin (A-1) was 61°C (B&R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150°C) was 1.1 dPa·s, and the epoxy equivalent was 144 g / equivalent. GPC measurement showed that more than 90% of the product was the desired product by area ratio, and MS measurement confirmed a peak at 542, which indicates 2,2',7,7'-tetraglycidyloxy-1,1'-binaphthalene (A-1).

[0102] S-1: Silicone resin synthesized by the following method A 5 L four-neck flask equipped with a stirrer, a condenser, a dropping funnel, and a thermometer was charged with 1,785 parts (14.88 moles) of vinylnorbornene (trade name: V0062, manufactured by Tokyo Chemical Industry Co., Ltd.; an isomer mixture of approximately equimolar amounts of 5-vinylbicyclo[2.2.1]hept-2-ene and 6-vinylbicyclo[2.2.1]hept-2-ene) and 455 parts of toluene, and the mixture was heated to 85° C. using an oil bath. To this was added 3.6 parts of carbon powder carrying 5% by mass of platinum metal, and 1,698 parts (8.75 moles) of 1,4-bis(dimethylsilyl)benzene was added dropwise over 180 minutes while stirring. After completion of the dropwise addition, the mixture was stirred at 110°C for 24 hours and then cooled to 25°C. The platinum metal-carrying carbon was then removed by filtration, and the toluene and excess vinylnorbornene were distilled off under reduced pressure to obtain 3,362 parts of a colorless, transparent, oily reaction product (A-1) (viscosity at 25°C: 12,820 mPa s). FT-IR, NMR, and GPC analyses of the reaction product showed that it was a mixture of about 41 mol % of the compound with n = 0, about 32 mol % of the compound with n = 1, and about 27 mol % of the compound with n = 2 in the following formula. The content of addition reactive carbon-carbon double bonds in the mixture was 0.36 mol / 100 g.

[0103] Curable resin formulation A: A mixture of 100 parts of E-2 epoxy resin, 99 parts of hardener NH-8210 (manufactured by Hitachi Chemical Co., Ltd.), and 1 part of hardener polycat8 (manufactured by San-Apro Co., Ltd.). Curable resin formulation B: A mixture of 46.5 parts of E-1 epoxy resin, 33.5 parts of curing agent Phenolite TD-2131 (manufactured by DIC Corporation), and 0.8 parts of curing accelerator triphenylphosphine. Curable resin formulation C: A mixture of 100 parts of S-1 silicone resin, 18.6 parts of an organohydrogenpolysiloxane represented by the following formula (9), 53.1 parts of an organohydrogenpolysiloxane represented by the following formula (10), 0.41 parts of a toluene solution of platinum hexachloride 1,3-divinyltetramethyldisiloxane (0.5 mass % in terms of platinum), 0.17 parts of ethynylmethyldecylcarbinol, 1.02 parts of a compound represented by the following formula (14), and 8 parts of a compound represented by the following formula (15).

[0104] [ka] [ka] [ka] [ka]

[0105] [Example 19] 100 parts of the colored composition X-1 and 900 parts of the curable resin blend A were blended and mixed with stirring to prepare a curable composition.

[0106] [Examples 20 to 36, Comparative Examples 5 to 8] The curable compositions of Examples 20 to 36 and Comparative Examples 5 to 8 were prepared in the same manner as in Example 19, except that the materials and blending amounts of the curable composition of Example 19 were changed to those shown in Table 3. In the table, the dye is Plast Black 8995.

[0107] (Evaluation of Curable Composition) The obtained curable composition was heated and molded at 150°C for 1 hour to a thickness of 1.0 mm after curing to produce a film-like cured product. The obtained cured product was measured for light transmittance at wavelengths of 600 nm and 700 nm. The light transmittance was measured using a light transmittance measuring device V-4100 (manufactured by Hitachi, Ltd.). The evaluation criteria were 1: unusable, 2: usable, and 3: excellent. The results are shown in Table 3. (Transmittance at 600 nm) 3: Less than 10% 2: 10% or more and 20% or less 1: More than 20% (Transmittance at 700 nm) 3: More than 80% 2: 75% or more and 80% or less 1: Less than 75%

[0108] [Table 3]

Claims

1. A thermosetting composition comprising an infrared-transmitting coloring composition and a thermosetting resin (C), wherein the infrared-transmitting coloring composition comprises a colorant (A) and a dispersing resin (B), The colorant (A) contains a purple pigment and a yellow pigment, The infrared transmitting coloring composition satisfies the following conditions (1) and (2) when a coating having a thickness of 1.0 μm is formed, The thermosetting resin (C) (excluding an alkali-soluble resin) is an epoxy resin or a silicone resin, The thermosetting composition satisfies the following condition (3) when a coating having a thickness of 1.0 mm is formed after curing: Condition (1): The maximum transmittance of light at wavelengths of 400 to 600 nm is 20% or less. Condition (2): The minimum transmittance of light at wavelengths of 700 to 1000 nm is 75% or more. Condition (3): Light transmittance at a wavelength of 700 nm is 75% or more.

2. The purple pigment is C.I. Pigment Violet 23, and is contained in an amount of 50 to 85% by mass in 100% by mass of the colorant (A); 2. The thermosetting composition of claim 1, wherein the yellow pigment is an isoindoline pigment.

3. A coating formed from the thermosetting composition according to claim 1 or 2.

4. An optical semiconductor device comprising the coating according to claim 3 .

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