Photosensitive coloring composition for organic el display devices, photosensitive coloring composition for micro-led display devices, cured film, organic el display device, and micro-led display device

Abstract

The present invention provides: a photosensitive coloring composition which has a high lightness and is capable of forming a cured film that has excellent light resistance, little change in lightness and excellent developability even if placed in a high temperature and high humidity environment for a long time; a cured film which has excellent light resistance; and an organic EL or Micro-LED display device which is provided with the cured film and has a high luminance and high color reproducibility. A photosensitive coloring composition according to the present disclosure contains a coloring agent, a polymerizable compound, a photopolymerization initiator and a resin. The coloring agent contains a green pigment and a yellow pigment, and the content of the green pigment in the coloring agent is 50% by mass to 80% by mass. The green pigment contains Pigment Green 36 and Pigment Green 62, and the content mass ratio of the Pigment Green 36 to the Pigment Green 62 in the green pigment is 85:15 to 65:35. The content of the Pigment Green 62 in the green pigment is 10% by mass to 20% by mass. The yellow pigment contains Pigment Yellow 185, and the polymerizable compound contains a trifunctional (meth)acryloyl group-containing aliphatic monomer.

Description

Photosensitive coloring composition for organic EL display device, photosensitive coloring composition for Micro-LED display device, cured film, organic EL display device and Micro-LED display device

[0001] The present disclosure relates to a photosensitive coloring composition for organic EL display devices, a photosensitive coloring composition for Micro-LED display devices, a cured film using the same, an organic EL display device, and a Micro-LED display device.

[0002] In recent years, in order to meet the demand for thinner, lighter, and curved displays in electronic devices such as mobile phones and personal digital assistants, the development and mass production of display devices using organic electroluminescence (OLED), a self-emitting element, has been progressing. Taking advantage of the thin and lightweight characteristics of these devices, they are expected to be applied to high-resolution, small displays of around 0.5 inches (hereinafter referred to as microdisplays) such as head-mounted displays and electronic viewfinders.

[0003] There are two main display methods for organic EL displays: one is to form a white light-emitting layer and use a color filter to display colors such as RGB, and the other is to vapor-deposit light-emitting layers that emit each color such as RGB. Since microdisplays have minute pixels, it is extremely difficult to selectively form RGB light-emitting layers. Therefore, the method of using a color filter for the white light-emitting layer is being actively adopted for microdisplays.

[0004] Since the pixel size of the microdisplay is as minute as 1 μm to 5 μm, the conventional method of fabricating the organic EL element and the color filter on separate substrates and then bonding them together can result in a decrease in precision and the risk of color misalignment. For this reason, a method of forming a color filter on the organic EL element has been proposed.

[0005] Color filters can be manufactured by inkjet printing, photolithography, or other methods, but photolithography, which uses a photosensitive coloring composition that allows for the formation of fine pixels, is increasingly being adopted.

[0006] Patent Document 1 discloses a pigment dispersion composition for color filters, which contains a pigment and a pigment dispersant made of a polymer having a specific structural unit in an organic solvent.

[0007] Japanese Patent Application Laid-Open No. 2008-9426

[0008] However, when a cured film formed using the composition described in Patent Document 1 is exposed to light for a long period of time in a high-temperature, high-humidity environment, a change in color may occur. Furthermore, the cured film is required to have high brightness, and an organic EL display device using the cured film is required to have high brightness and high color reproducibility. Furthermore, the photosensitive coloring composition used in the organic EL display device is required to have good developability. Similar demands have been made not only for organic EL display devices but also for Micro-LED display devices.

[0009] The present disclosure aims to provide a photosensitive coloring composition for organic EL display devices, a photosensitive coloring composition for Micro-LED display devices, a cured film having excellent light resistance and little change in lightness even when placed in a high-temperature, high-humidity environment for a long period of time, and capable of forming a cured film having excellent developability, and an organic EL display device and a Micro-LED display device having high brightness and high color reproducibility, which are provided with the composition and the cured film.

[0010] The photosensitive coloring composition for organic EL or Micro-LED display devices, the cured film, the organic EL display device, and the Micro-LED display device according to the present disclosure can have the following configurations [1] to [9]. [1] A photosensitive coloring composition for an organic EL display device, comprising: a colorant (A), a polymerizable compound (B), a photopolymerization initiator (C), and a resin (D), wherein the colorant (A) comprises a green pigment (A1) and a yellow pigment (A2), the content of the green pigment (A1) in the colorant (A) is 50 to 80 mass %, the green pigment (A1) comprises Pigment Green 36 and Pigment Green 62, the content mass ratio of Pigment Green 36 to Pigment Green 62 in the green pigment (A1) is 85:15 to 65:35, the content of Pigment Green 62 in the green pigment (A1) is 10 to 20 mass %, the yellow pigment (A2) comprises Pigment Yellow 185, and the polymerizable compound (B) comprises a trifunctional (meth)acryloyl group-containing aliphatic monomer (B1). [2] The photosensitive coloring composition for an organic EL display device according to [1], wherein the trifunctional (meth)acryloyl group-containing aliphatic monomer (B1) contains a compound represented by the following chemical formula 1: [3] The photosensitive coloring composition for an organic EL display device according to [1] or [2], wherein the photopolymerization initiator (C) contains an oxime ester compound. [4] A cured film formed from the photosensitive coloring composition for an organic EL display device according to any one of [1] to [3]. [5] An organic EL display device comprising the cured film according to [4]. [6] The organic EL display device according to [5], wherein the organic EL display device is a Micro-OLED display device. [7] A photosensitive coloring composition for a Micro-LED display device, comprising a colorant (A), a polymerizable compound (B), a photopolymerization initiator (C), and a resin (D), wherein the colorant (A) comprises a green pigment (A1) and a yellow pigment (A2), and the content of the green pigment (A1) in the colorant (A) is 50 to 80 mass%. The green pigment (A1) comprises Pigment Green 36 and Pigment Green 62, and the content mass ratio of Pigment Green 36 to Pigment Green 62 in the green pigment (A1) is 85:15 to 65:35. The content of Pigment Green 62 in the green pigment (A1) is 10 to 20 mass%. The yellow pigment (A2) comprises Pigment Yellow 185, and the polymerizable compound (B) comprises a trifunctional (meth)acryloyl group-containing aliphatic monomer (B1). This photosensitive coloring composition for a Micro-LED display device. [8] A cured film formed from the photosensitive coloring composition for a Micro-LED display device according to [7]. [9] A Micro-LED display device comprising the cured film according to [8].

[0011] According to the present disclosure, it is possible to provide a photosensitive coloring composition for organic EL display devices, a photosensitive coloring composition for Micro-LED display devices, a cured film having excellent light resistance and little change in lightness even when placed in a high-temperature, high-humidity environment for a long period of time, and capable of forming a cured film having excellent developability, and an organic EL display device and a Micro-LED display device having high brightness and high color reproducibility, which are provided with the composition.

[0012] 1 is a schematic cross-sectional view of an organic EL display device according to an embodiment of the present invention.

[0013] The following describes the photosensitive coloring composition for organic EL display devices (hereinafter also referred to as the present composition) and photosensitive coloring composition for Micro-LED display devices according to the present disclosure, as well as cured films formed therefrom, organic EL display devices (hereinafter also referred to as the present device), and Micro-LED display devices. The following description may focus particularly on the photosensitive coloring composition for organic EL display devices and the organic EL display device, but the present disclosure is not limited thereto. In this specification, the symbol "to" indicating a numerical range means that the numerical values ​​before and after it are included as the upper and lower limits. In numerical ranges described in stages in this specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described in this specification, the upper or lower limit of that numerical range may be replaced with a value shown in the examples. In this specification, unless otherwise specified, the terms "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamide" mean "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or methacrylamide," respectively. Furthermore, "C.I." in this specification refers to the Color Index (C.I.).

[0014] <<Photosensitive Coloring Composition for Organic EL Display Devices>> The composition includes a colorant (A), a polymerizable compound (B), a photopolymerization initiator (C), and a resin (D). The colorant (A) includes a green pigment (A1) and a yellow pigment (A2). The content of the green pigment (A1) in the colorant (A) is 50 to 80 mass%. The green pigment (A1) includes Pigment Green 36 and Pigment Green 62, and the mass ratio of Pigment Green 36 to Pigment Green 62 in the green pigment (A1) is 85:15 to 65:35. The content of Pigment Green 62 in the green pigment (A1) is 10 to 20 mass%. The yellow pigment (A2) includes Pigment Yellow 185. The polymerizable compound (B) includes a trifunctional (meth)acryloyl group-containing aliphatic monomer (B1).

[0015] The present composition having the above configuration uses a colorant containing a specific green pigment (A1) and a yellow pigment (A2) (specific amounts at a specific blend ratio for the green pigment) and a specific polymerizable compound (B), thereby enabling the formation of a cured film with excellent developability and a designed pattern shape, while also suppressing development residues. Furthermore, the cured film formed from the present composition has high brightness and can suppress brightness change even when placed in a high-temperature, high-humidity environment for a long period of time, thereby enabling the realization of an organic EL display device with excellent light resistance, high brightness, and high color reproducibility. The present composition can be used, for example, as a green photosensitive coloring composition for an organic EL display device.

[0016] The present composition contains at least a colorant (A), a polymerizable compound (B), a photopolymerization initiator (C), and a resin (D), and may further contain other components as necessary within the scope of solving the problems of the present disclosure. Each component that can be contained in the present composition will be described below.

[0017] <Colorant (A)> The colorant (A) contains a green pigment (A1) and a yellow pigment (A2), and may contain, for example, a blue pigment, as necessary. These colorants and pigments may be used alone or in combination of two or more.

[0018] The green pigment (A1) contains at least C.I. Pigment Green 36 and Pigment Green 62. Furthermore, in this green pigment (A1), the mass ratio of Pigment Green 36 to Pigment Green 62 is 85:15 to 65:35. When the mass ratio of Pigment Green 36 to Pigment Green 62 is within the above range, the following is possible: It has high lightness, and even when exposed to light (ultraviolet rays) for a long period of time (e.g., 200 hours) in a high-temperature, high-humidity environment (e.g., a temperature of 65°C and a relative humidity of 90%), it is possible to suppress changes in color (e.g., green) (changes in lightness). Furthermore, by using a specific amount of Pigment Green 62, which has strong coloring power, in combination with Pigment Green 36, it is possible to reduce the total amount of green pigment used, thereby suppressing development residues in the development process. From the viewpoints of suppressing development residues and color tone, the mass ratio of Pigment Green 36 to Pigment Green 62 contained in the green pigment (A1) is preferably 85:15 to 75:25.

[0019] The green pigment (A1) may contain other green pigments as long as the effects of the present disclosure are achieved. Examples of other green pigments include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 45, 48, 50, 51, 54, 55, 58, 59, and 63.

[0020] The content of the green pigment (A1) in the colorant (A) is 50 to 80% by mass. When the content of the green pigment (A1) in the colorant (A) is 50% by mass or more, a spectrum with good brightness and transmittance can be obtained. Furthermore, when the content of the green pigment (A1) in the colorant (A) is 80% by mass or less, color change can be suppressed to a low level even when exposed to light in a high-temperature, high-humidity environment for a long period of time. Furthermore, in order to obtain high brightness, the content of the green pigment (A1) in the colorant (A) is preferably 55% by mass or more. Similarly, from the viewpoint of obtaining good transmittance, the content of the green pigment (A1) in the colorant (A) is preferably 60% by mass or less.

[0021] Furthermore, in this composition, the content of Pigment Green 62 in the green pigment (A1) is 10 to 20% by mass. When the content of Pigment Green 62 in the green pigment (A1) is 10% by mass or more, color change can be suppressed even when exposed to light in a high-temperature, high-humidity environment for a long period of time, and development residues in the development step can also be suppressed. Furthermore, when the content of Pigment Green 62 in the green pigment (A1) is 20% by mass or less, good transmittance and high brightness can be obtained. From the viewpoint of obtaining a spectrum with good transmittance, the content of Pigment Green 62 in the green pigment (A1) is preferably 15% by mass or more.

[0022] The yellow pigment (A2) contains at least C.I. Pigment Yellow 185, and may contain other yellow pigments as long as the effects of the present disclosure are obtained. Specific examples of other yellow pigments include C.I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136 , 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, etc.

[0023] The content of the yellow pigment (A2) in the colorant (A) can be appropriately set within a range in which the effects of the present disclosure can be obtained, but is preferably, for example, 20 to 50% by mass. When the content of the yellow pigment (A2) in the colorant (A) is 20% by mass or more, color change can be suppressed even when exposed to light in a high-temperature, high-humidity environment for a long period of time. When the content of the yellow pigment (A2) in the colorant (A) is 50% by mass or less, transmittance is improved and high brightness can be obtained. From the viewpoint of obtaining a spectrum with good transmittance, the content of the yellow pigment (A2) in the colorant (A) is more preferably 30 to 45% by mass.

[0024] Specific examples of blue pigments that can be contained in the colorant (A) include C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. The content of the blue pigment can be appropriately set within a range in which the effects of the present disclosure can be obtained, and is not particularly limited.

[0025] When using the pigments of the above colors, it is preferable to pulverize them. The method for pulverizing the pigments can be appropriately selected from known methods, such as wet grinding, dry grinding, and solution precipitation, and salt milling treatment using a kneader method, which is a type of wet grinding, can also be used.

[0026] Salt milling is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded under heating using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill, 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 high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment with an extremely fine primary particle size and a narrow, sharp particle size distribution.

[0027] Examples of water-soluble inorganic salts that can be used include sodium chloride, barium chloride, potassium chloride, and sodium sulfate, but sodium chloride (table salt) is preferred from the standpoint of cost. From the standpoints of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2,000 parts by mass, and most preferably 300 to 1,000 parts by mass, per 100 parts by mass of the pigment.

[0028] The water-soluble organic solvent functions to moisten the pigment and water-soluble inorganic salt. It is not particularly limited as long as it is soluble (miscible) in water and does not substantially dissolve the inorganic salt used. However, because 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 from a safety standpoint. 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 1,000 parts by weight, and most preferably 50 to 500 parts by weight, per 100 parts by weight of the pigment.

[0029] When the pigment is subjected to salt milling, a resin may be added as needed. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc. can be used. The resin used is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in the above organic solvents. The amount of resin used is preferably in the range of 5 to 200 parts by mass per 100 parts by mass of the pigment.

[0030] The primary particle diameter of the pigment is preferably 20 nm or more because it disperses well in the composition. Furthermore, it is preferably 100 nm or less because it allows the formation of a color filter with a high contrast ratio. A particularly preferred range is 25 to 85 nm. The primary particle diameter of the pigment is measured by directly measuring the size of the primary particles from an electron micrograph of the pigment taken with a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of each primary particle of the pigment are measured, and the average is taken as the particle diameter of the pigment particle. Next, the volume of each of 100 or more pigment particles is calculated by approximating it to the cube of the calculated particle diameter, and the volume-average particle diameter is taken as the average primary particle diameter.

[0031] <Polymerizable Compound (B)> The polymerizable compound (B) is a compound having a polymerizable unsaturated group. In the present composition, the polymerizable compound (B) contains at least a trifunctional (meth)acryloyl group-containing aliphatic monomer (B1). The polymerizable compound (B) may further contain other polymerizable compounds as needed. In this specification, the polymerizable unsaturated group refers to an ethylenically unsaturated double bond such as a vinyl group, a (meth)allyl group, or a (meth)acryloyl group. The trifunctional (meth)acryloyl group-containing aliphatic monomer (B1) is not particularly limited, and for example, a compound represented by the following general formula (1) can be used. General formula (1) [CH ２ =CR １ C(=O)-(OC ｍ H ２ｍ ) ｎ -OCH ２ ] ３ -CCH ２ CH ３ (In general formula (1), m represents an integer of 1 to 3, n represents an integer of 0 to 2, and multiple m's and multiple n's may be the same or different. R １ is -H or -CH ３ Represents.)

[0032] By using the compound represented by general formula (1), both adhesion to the substrate and resolution of the resist pattern can be achieved.

[0033] Specific examples of the compound represented by general formula (1) include trimethylolpropane tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, etc. The compound represented by general formula (1) can be used alone or in combination of two or more.

[0034] Among these, the trifunctional (meth)acryloyl group-containing aliphatic monomer (B1) preferably contains a compound represented by the following chemical formula (1) (trimethylolpropane triacrylate) or trimethylolpropane PO-modified triacrylate, from the viewpoints of forming a fine pattern and suppressing development residues. Furthermore, the trifunctional (meth)acryloyl group-containing aliphatic monomer (B1) more preferably contains a compound represented by the following chemical formula (1), from the viewpoints of suppressing development residues.

[0035] Other polymerizable compounds include known (meth)acrylate monomers. Specific examples of the acrylates 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, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, Examples of the acrylic acid ester include various acrylic acid esters and methacrylic acid esters such as dipentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid esters 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.

[0036] Commercially available polymerizable compounds include KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, and DPCA-120 (all trade names) manufactured by Nippon Kayaku Co., Ltd., and Aronix M-303, M-305, M-306, M-309, M-310, M-321, and M-322 manufactured by Toagosei Co., Ltd. Examples of other polymerizable compounds include M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, and M-101A (all trade names), Viscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, and #405 (all trade names) manufactured by Osaka Organic Chemical Co., Ltd., and NK Ester A-9300 (trade name) manufactured by Shin-Nakamura Chemical Co., Ltd. One type of other polymerizable compound can be used alone, or two or more types can be used in combination.

[0037] The content of the polymerizable compound (B) relative to the total solids (non-volatile content) in the composition is preferably 5 to 40% by mass, and more preferably 20 to 30% by mass. By ensuring this range, peeling does not occur when forming a fine pattern, and the tapered portions of the pattern are prevented from being elongated, making it possible to form a highly precise, fine pixel pattern. Furthermore, the content of the compound represented by the general formula (1) contained in the polymerizable compound (B) is preferably 50 to 100% by mass, and more preferably 60% by mass or more, relative to the total amount of the polymerizable compound (B). By ensuring this range, excellent coating film adhesion to the substrate and chemical resistance during development are achieved.

[0038] <Photopolymerization initiator (C)> The photopolymerization initiator (C) can be appropriately selected from those that promote the polymerization reaction of the polymerizable compound described above by the action of light. In the present composition, the photopolymerization initiator (C) preferably contains a compound having an oxime ester group (>C═N—OC(═O)—) (oxime ester compound) in view of excellent UV curability, color properties, chemical resistance, and developability. In particular, the photopolymerization initiator (C) more preferably contains an oxime ester compound having two or more oxime ester groups in one molecule. Furthermore, the photopolymerization initiator (C) may contain other photopolymerization initiators as necessary.

[0039] When an oxime ester compound absorbs ultraviolet light, the N-O bond of the oxime undergoes cleavage, generating an iminyl radical and an alkyloxy radical. These radicals further decompose to generate highly active radicals, allowing for pattern formation with a small amount of exposure. Furthermore, because the oxime ester compound has high quantum efficiency, it exhibits excellent curability even when the colorant in the composition is present at a high concentration. This composition can be used to form a cured film with a fine pattern that exhibits excellent developability and patterning properties through photolithography. Furthermore, the oxime ester compound provides the cured film with excellent light-blocking properties and chemical resistance.

[0040] Examples of the oxime ester compound include oxime ester photopolymerization initiators represented by the following general formulas (2) to (4). Among these, the oxime ester compound is preferably an oxime ester photopolymerization initiator represented by the following general formula (2) or (3), and more preferably an oxime ester photopolymerization initiator represented by general formula (2).

[0041] (Oxime ester photopolymerization initiator represented by general formula (2))

[0042] (In general formula (2), Z represents a direct bond or a —C(═O)— group, and R １ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, and R ２represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, R ３ ~R １０ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group which may have a substituent, a nitro group, or R １１ represents a —C(═O)— group. １１ represents an aryl group which may have a substituent.

[0043] R １ ~R １０ Examples of the alkyl group having 1 to 20 carbon atoms in R include linear alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, and dodecyl groups. ２ ~R １１ Examples of the aryl group in include a phenyl group, a naphthyl group, an anthracenyl group, etc. Note that when Z is a direct bond, this means that Z does not have any atoms, and the two atoms connected to Z in general formula (2) are directly bonded.

[0044] The substituents that the alkyl group and aryl group may have refer to the fact that the alkyl group or aryl group may have a substituent in place of a hydrogen atom that the alkyl group or aryl group has. Examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a tert-butoxy group; aryloxy groups such as a phenoxy group and a p-tolyloxy group; alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group, and a phenoxycarbonyl group; acyloxy groups such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; acyl groups such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, and a methoxalyl group; alkylsulfanyl groups such as a methylsulfanyl group and a tert-butylsulfanyl group; arylsulfanyl groups such as a phenylsulfanyl group and a p-tolylsulfanyl group; alkylamino groups such as a methylamino group and a cyclohexylamino group; arylamino groups such as a phenylamino group and a p-tolylamino group; alkyl groups such as a methyl group, an ethyl group, a tert-butyl group, a dodecyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclooctadecyl group; aryl groups such as a phenyl group, a p-tolyl group, a xylyl group, a cumenyl group, a naphthyl group, an anthryl group, and a phenanthryl group; heterocyclic groups such as a furyl group and a thienyl group, as well as a hydroxy group, a carboxy group, a formyl group, a mercapto group, a sulfo group, a mesyl group, a p-toluenesulfonyl group, an amino group, a nitro group, a cyano group, a trifluoromethyl group, a trichloromethyl group, a trimethylsilyl group, a phosphinico group, a phosphono group, a trimethylammonium group, a dimethylsulfoniumyl group, and a triphenylphenacylphosphoniumyl group. Furthermore, one or more of these substituents may be present, or one or more types of these substituents may be present, and furthermore, the hydrogen atoms of these substituents may be further substituted with other substituents.

[0045] Among the oxime ester photopolymerization initiators represented by general formula (2), Z is a direct bond or a —C(═O)— group, and R １is an alkyl group having 1 to 20 carbon atoms which may have a substituent, and R ２ is an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and R ３ ~R １０ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group which may have a substituent, a nitro group, or R １１ A —CO— group is preferred. ４ ~R ６ and R ８ ~R １０ is a hydrogen atom, and R ７ is a hydrogen atom, or R １１ is a —CO— group, and R １１ However, it is more preferably an aryl group which may have a substituent.

[0046] Of the oxime ester photopolymerization initiators represented by general formula (2), compounds represented by the following chemical formula (2-1) or (2-2) are preferred.

[0047]

[0048]

[0049] (Oxime ester photopolymerization initiator represented by general formula (3))

[0050] (In general formula (3), W １ and W ２ each independently represents a carbonyl bond (—CO—) or a single bond, W １ and W ２ At least one of R is a carbonyl bond (—CO—). ａ is an alkyl group having 2 to 6 carbon atoms, and R ｂ is an alkyl group having 4 to 10 carbon atoms, and R ｃ is a group that contains at least a hydrocarbon ring or a heterocyclic ring and may further contain at least one divalent linking group selected from an alkylene chain having 1 to 4 carbon atoms, a thioether bond (—S—), an ether bond (—O—), and a carbonyl bond (—CO—), and R ｂ and R ｃare different substituents. ｄ and R ｅ are each independently an alkyl group having 1 to 6 carbon atoms.

[0051] R ａ Examples of the alkyl group in R include linear alkyl groups such as an ethyl group, a propyl group, a butyl group, and a hexyl group. ｂ Examples of the alkyl group in R include a straight-chain alkyl group such as a butyl group, a hexyl group, an octyl group, and a dodecyl group. ｃ Examples of the hydrocarbon ring in R include an aliphatic hydrocarbon ring such as a cyclohexyl group, and an aromatic hydrocarbon ring such as a phenyl group, a naphthyl group, and an anthracenyl group. ｃ Examples of the heterocyclic ring in R include a ring in which one or more carbon atoms of the hydrocarbon ring are replaced with a nitrogen atom, an oxygen atom, or a sulfur atom. ｄ and R ｅ Examples of the alkyl group include a straight-chain alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group.

[0052] Of the oxime ester photopolymerization initiators represented by general formula (3), compounds represented by the following chemical formula (3-1) are preferred.

[0053]

[0054] (Oxime ester photopolymerization initiator represented by general formula (4))

[0055] (In general formula (4), R ２１ and R ２２ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and R ２３ and R ２４ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and R ２５ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group which may have a substituent, or R ２６is a —CO— group, and R ２６ is an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group.

[0056] R ２１ ~R ２６ The alkyl group having 1 to 20 carbon atoms in the R １ ~R １０ The alkyl group may be the same as the alkyl group having 1 to 20 carbon atoms in R ２１ ~R ２６ The aryl group in ２ ~R １１ The aryl group in R ２６ Examples of the heterocyclic ring in the heterocyclic group include furan, thiophene, pyrrole, oxazole, thiazole, imidazole, pyrazole, pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine, pyrazine, benzofuran, thionaphthene, indole, carbazole, coumarin, quinoline, phthalazine, quinoxaline, etc. The substituents that the alkyl group and aryl group may have may be the same as those in the general formula (2).

[0057] The oxime ester photopolymerization initiator represented by general formula (4) is R ２１ is an aryl group which may have a substituent, and R ２２ is an alkyl group having 1 to 20 carbon atoms which may have a substituent, and R ２３ and R ２４ is a hydrogen atom, and R ２５ is a hydrogen atom, or R ２６ A —CO— group is preferred.

[0058] Of the oxime ester photopolymerization initiators represented by general formula (4), compounds represented by the following chemical formula (4-1) are preferred.

[0059]

[0060] (Other Photopolymerization Initiators) The photopolymerization initiator (C) may further contain other photopolymerization initiators in addition to the oxime ester-based compounds. Examples of other photopolymerization initiators include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin, benzoin methyl benzoin-based compounds such as benzoyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzil dimethyl ketal; benzophenone-based compounds such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone-based compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and 2,4-diethylthioxanthone;2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-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) Examples of suitable photopolymerization initiators include triazine-based compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone-based compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate-based compounds; carbazole-based compounds; imidazole-based compounds; and titanocene-based compounds. These photopolymerization initiators can be used alone or in combination of two or more types in any desired ratio, as needed. Commercially available photopolymerization initiators include, as acetophenone-based compounds, "IRGACURE 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one), "IRGACURE 369" (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone), and "IRGACURE 379" 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, all manufactured by BASF Japan Ltd.; and as phosphine-based compounds, "IRGACURE 819" (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide) and "IRGACURE TPO" (2,4,6-trimethylbenzoyldiphenylphosphine oxide), all manufactured by BASF Japan Ltd.

[0061] The content of the photopolymerization initiator (C) is preferably 0.5 to 50 parts by mass relative to 100 parts by mass of the colorant (A), and more preferably 1 to 30 parts by mass from the viewpoint of photocurability and developability. When the content of the photopolymerization initiator (C) is 0.5 parts by mass or more, excellent adhesion to the substrate is achieved. Furthermore, when the content of the photopolymerization initiator (C) is 50 parts by mass or less, excellent resolution is achieved. Furthermore, the blending ratio of the oxime ester compound in the photopolymerization initiator (C) is preferably 80% by mass or more, more preferably 90% by mass or more, of the total amount of the photopolymerization initiator (C).

[0062] <Resin (D)> The present composition contains resin (D). Resin (D) is preferably a transparent resin that, when formed into a 2 μm-thick coating, exhibits a transmittance of 80% or more across the entire wavelength range of 400 to 700 nm, and preferably has a transmittance of 95% or more. Resin (D) is preferably one or more types selected from thermoplastic resins and photosensitive resins. Resin (D) is also preferably alkali-soluble. This allows the coating formed from the present composition to be patterned by photolithography. The alkali-insoluble photosensitive resin and the alkali-soluble resin may have a thermosetting group. Examples of the thermosetting group include an epoxy group and an oxetanyl group. This is described in detail below.

[0063] (Alkali-Soluble Resin) Examples of alkali-soluble resins include resins having an acidic group such as a carboxyl group or a sulfonic group. Examples of alkali-soluble thermoplastic resins include acrylic resins having an acidic group, α-olefin / maleic acid (anhydride) copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, and isobutylene / maleic acid (anhydride) copolymers. Among these, acrylic resins having an acidic group and styrene / styrene sulfonic acid copolymers are preferred in terms of improving developability, heat resistance, and transparency.

[0064] (Thermoplastic Resin) The thermoplastic resin may include one that is not alkali-soluble. Examples of the thermoplastic resin that is not alkali-soluble include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin.

[0065] (Alkali-soluble photosensitive resin) The alkali-soluble photosensitive resin has photosensitivity due to the presence of a polymerizable unsaturated group. Any known resin can be used as the alkali-soluble photosensitive resin as long as it is alkali-soluble and photosensitive, but resins synthesized by the following methods (i) and (ii) are preferred. When an alkali-soluble photosensitive resin is used, it undergoes three-dimensional crosslinking upon irradiation with light, increasing the crosslink density and improving the chemical resistance of the coating.

[0066] [Method (i)] In method (i), for example, a polymer of an epoxy group-containing monomer and other monomers is first synthesized. Next, a monocarboxyl group-containing monomer is added to the epoxy group of the polymer, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to obtain an alkali-soluble photosensitive resin. The monocarboxyl group-containing monomer is a monomer having one carboxyl group.

[0067] Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

[0068] Examples of the monocarboxyl group-containing monomer 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.

[0069] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. The polybasic acid anhydride may have a carboxyl group that does not form an acid anhydride.

[0070] Examples of other monomers include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and ethoxypolyethylene glycol (meth)acrylate; Examples of the vinyl vinyl compound include (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and vinyl acetate and vinyl propionate.

[0071] Also, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylene dimaleimide, N,N'-1,4-phenylene dimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide N-substituted maleimides such as N-isopropyl acrylate, ...

[0072] [Method (ii)] In the method (ii), for example, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers are synthesized to prepare a polymer, and then the hydroxyl group of the polymer is reacted with an isocyanate group of an isocyanate group-containing monomer to synthesize an alkali-soluble photosensitive resin.

[0073] Examples of the hydroxyl group-containing monomer include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3-, or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. Other examples include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to a hydroxyalkyl (meth)acrylate, and polyester mono(meth)acrylates obtained by addition polymerization of poly-γ-valerolactone, poly-ε-caprolactone, and / or poly-12-hydroxystearic acid. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred, with glycerol mono(meth)acrylate being more preferred.

[0074] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0075] Monomers that can be used other than the above-mentioned monomers include the other monomers exemplified in the above method (i) as well as phosphate ester group-containing monomers.

[0076] The phosphate ester group-containing monomer is, for example, a compound obtained by reacting the hydroxyl group of a hydroxyl group-containing monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

[0077] The above-mentioned raw materials for the resin (D) can be used alone or in combination of two or more kinds. The resin (D) can be used alone or in combination of two or more kinds.

[0078] The content of the resin (D) is preferably 10 to 400 parts by mass, more preferably 20 to 400 parts by mass, and even more preferably 50 to 250 parts by mass, relative to 100 parts by mass of the colorant (A). An amount of 10 parts by mass or more is preferred because film-forming properties and various resistances are good, and an amount of 400 parts by mass or less is preferred because the colorant concentration is high and good color properties can be expressed.

[0079] The weight average molecular weight (Mw) of the resin (D) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The value of Mw / Mn is preferably 10 or less. Mn is the number average molecular weight.

[0080] The acid value of the resin (D) is preferably 50 to 200 mgKOH / g, more preferably 70 to 180 mgKOH / g, and even more preferably 90 to 170 mgKOH / g. A suitable acid value allows for a high level of balance between alkali solubility, adhesion, and residue suppression.

[0081] <Optional Components> The present composition may contain other components as needed in addition to the colorant (A), the polymerizable compound (B), the photopolymerization initiator (C), and the resin (D). Each component that can be contained in the present composition will be described below.

[0082] (Sensitizer) The present composition may further contain a sensitizer. Examples of sensitizers include unsaturated ketones such as chalcone derivatives and dibenzalacetone; 1,2-diketone derivatives such as 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, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, and phthalo Examples of the compound include cyanine 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, 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, and 4,4'-bis(diethylamino)benzophenone.

[0083] Among the above sensitizers, particularly suitable sensitizers include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. More specific examples include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, and 3,6-dibenzoyl-N-ethylcarbazole.

[0084] Commercially available sensitizers include "KAYACURE DETX-S" (2,3-diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.) and "EAB-F" (4,4'-bis(diethylamino)benzophenone, manufactured by Hodogaya Chemical Co., Ltd.). In addition, sensitizers that absorb light in the ultraviolet to near-infrared region can also be added. The sensitizers can be used alone or in combination of two or more in any ratio as needed.

[0085] The content of the sensitizer when used is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass, relative to 100 parts by mass of the photopolymerization initiator (C) contained in the coloring composition, from the viewpoint of photocurability and developability.

[0086] (Thermosetting Compound) The present composition may contain a thermosetting compound. This improves the crosslink density during the heating step after forming a pattern on the coating by photolithography when producing a color filter, thereby improving heat resistance. In addition, the colorant (A) is less likely to aggregate during the heating step, thereby further improving the contrast ratio.

[0087] Thermosetting compounds are low-molecular-weight compounds or polymers (thermosetting resins) and are not limited by molecular weight. In the present disclosure, thermosetting resins are included in the thermosetting compounds. Examples of thermosetting compounds include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenolic compounds. Among these, epoxy compounds and oxetane compounds are preferred.

[0088] ((Epoxy Compound)) Examples of epoxy compounds include polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene ... Examples of suitable epoxy resins include polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine epoxy resins, and glycidyl ester epoxy resins.

[0089] Commercially available epoxy compounds include, for example, Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, and Epicoat 191P (trade names, manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004 and Epicoat 1256 (trade names, manufactured by Japan Epoxy Resins Co., Ltd.), TECHMORE VG3101L (trade name, manufactured by Mitsui Chemicals, Inc.), EPPN-501H and 502H (trade names, manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name, manufactured by Japan Epoxy Resins Co., Ltd.), and JER 157S65, 157S70 (trade names; manufactured by Japan Epoxy Resins Co., Ltd.), EPPN-201 (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER152, JER154 (all trade names; manufactured by Japan Epoxy Resins Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (all trade names; manufactured by Nippon Kayaku Co., Ltd.), Celloxide 2021, EHPE- 3150 (all trade names; manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 (all trade names; manufactured by Nagase ChemteX Corporation), TEPIC-L, TEPIC-H, TEPIC-S (manufactured by Nissan Chemical Industries, Ltd.), and the like.

[0090] The content of the epoxy compound is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is added, the heat resistance of the coating and the pattern shape are further improved.

[0091] (Oxetane Compound) The oxetane compound is a compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher functional oxetane compounds.

[0092] Examples of monofunctional oxetane compounds include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 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 OXT-212 manufactured by Toagosei Co., Ltd.

[0093] Examples of the bifunctional oxetane compound 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-methyl-3-oxetanyl ... -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 1,4-bis(3-ethyl-3-oxetanylmethyl)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, ethylene oxide (EO) modified Examples of such a bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether include 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 products include OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

[0094] Examples of oxetane groups having three or more functional 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 a polymer 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 an oxetane group (for example, the oxetane-modified phenol novolak resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of a (meth)acrylic monomer such as the above-mentioned OXE-30.

[0095] The content of the oxetane compound is preferably 1 to 20% by mass, more preferably 5 to 15% by mass, based on 100% by mass of the nonvolatile content of the composition. When an appropriate amount is contained, the solvent resistance of the coating film is further improved.

[0096] ((Melamine Compound)) A melamine compound is a compound having a melamine ring structure. Melamine compounds include low molecular weight compounds and high molecular weight compounds. In this specification, the melamine compound is preferably a compound in which a methylol group or an ether group is bonded to a melamine ring. The average number of methylol groups and / or ether groups bonded per melamine ring is preferably 5.0 or more. When there is an appropriate number of bonds, the solvent resistance of the coating is further improved and the contrast ratio is less likely to decrease.

[0097] Commercially available melamine compounds include, for example, Nikalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, and MX-410 (manufactured by Sanwa Chemical Co., Ltd.), and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 (manufactured by Nippon Cytec Industries Co., Ltd.).

[0098] Among these, Nikalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, and MX-45 (manufactured by Sanwa Chemical Co., Ltd.) and Cymel 232, 235, 236, 238, 300, 301, 303, and 350 (manufactured by Nippon Cytec Industries Co., Ltd.) are preferred in that they have an average of 5.0 or more methylol groups and / or ether groups per melamine ring, thereby further improving the crosslink density of the coating.

[0099] (Antioxidant) The composition may contain an antioxidant. The antioxidant prevents the photopolymerization initiator or the thermosetting compound from being oxidized and yellowed by the thermal process of thermal curing or ITO annealing, thereby increasing the transmittance of the pixel.

[0100] The "antioxidant" may be any compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. 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.

[0101] Among these antioxidants, from the viewpoint of achieving both the transmittance and sensitivity of the coating film, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred, and hindered phenol-based antioxidants, hindered amine-based antioxidants, and phosphorus-based antioxidants are more preferred.

[0102] Examples of 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-triazine, 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'-butyl Examples of suitable phenols include 2,2'-methyl-4-hydroxyphenyl-5-methylphenol, 2,2'-thiodiethyl-bis-(2-t-butyl-5-methylphenol), 2,2'-thiodiethyl-bis-(6-t-butyl-4-methylphenol), 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, and N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide). Other examples include oligomer and polymer compounds having a hindered phenol structure.

[0103] Examples of the hindered amine antioxidant 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, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amine, and 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amine. 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}hexame butyl{(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}], a polycondensate 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. In addition, oligomer type and polymer type compounds having a hindered amine structure may also be used.

[0104] Examples of 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, and di(2,4-di-t-butylphenyl)pentaerythritol. Examples of suitable phosphate phosphates include tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol)diphosphite, hexatridecyl 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butanetriphosphite, 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 suitable phosphate phosphate phosphates include oligomer and polymer compounds having a phosphite structure.

[0105] Examples of sulfur-based antioxidants include 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, 2,4-bis[(laurylthio)methyl]-o-cresol, etc. Oligomeric and polymeric compounds having a thioether structure may also be used.

[0106] Benzotriazole-based antioxidants include oligomer-type and polymer-type compounds having a benzotriazole structure.

[0107] Examples of benzophenone-based 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, 2-hydroxy-4-chlorobenzophenone, etc. Oligomeric and polymeric compounds having a benzophenone structure may also be used.

[0108] 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 may also be used.

[0109] 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 may also be used.

[0110] These antioxidants can be used alone or in combination of two or more kinds in any ratio as required.

[0111] The content of the antioxidant is preferably 0.5 to 5.0% by mass of the total solid content (total nonvolatile content) of the photosensitive coloring composition from the viewpoint of brightness and sensitivity.

[0112] (Adhesion Improver) The present composition may contain an adhesion improver such as a silane coupling agent to improve adhesion to the substrate. The improved adhesion due to the adhesion improver improves the reproducibility of fine lines and improves resolution.

[0113] Examples of the adhesion improver include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; (meth)acrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane; epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane and N-2-(aminoethyl)-3- Examples of silane coupling agents include aminosilanes such as aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride; mercapto compounds such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryl compounds such as p-styryltrimethoxysilane; ureido compounds such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatepropyltriethoxysilane. The content of the adhesion improver is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the colorant (A). When an appropriate amount is contained, adhesion, resolution, and sensitivity are improved in a well-balanced manner.

[0114] (Leveling Agent) The photosensitive coloring composition can contain a leveling agent. As the leveling agent, dimethylsiloxane having a polyether structure or polyester structure in the main chain is preferred. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray Co., Ltd. and BYK-333 manufactured by BYK-Chemie. Specific examples of dimethylsiloxane having a polyester structure include BYK-310 and BYK-370 manufactured by BYK-Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can also be used in combination. The content of the leveling agent is preferably 0.003 to 0.5 mass% of the total solids content (total non-volatile content) of the photosensitive coloring composition.

[0115] Anionic, cationic, nonionic, or amphoteric surfactants may be added to the leveling agent as an auxiliary. Two or more surfactants may be used in combination. Examples of anionic surfactants that may be added to the leveling agent as an auxiliary 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.

[0116] Examples of cationic surfactants to be added auxiliary to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Examples of nonionic surfactants to be added auxiliary to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, etc.; alkyl betaines such as alkyl dimethylaminoacetic acid betaine, amphoteric surfactants such as alkyl imidazolines, and fluorine-based and silicone-based surfactants.

[0117] (Curing Agent, Curing Accelerator) The present composition may contain a curing agent or a curing accelerator as needed to assist in the curing of the thermosetting resin. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc. are effective, but are not particularly limited thereto, and any curing agent may be used as long as it can react with the thermosetting resin. Among these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferred. Examples of the curing accelerator include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivative bicyclic amidine compounds and salts thereof (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, etc.), Examples of compounds that can be used include imidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), guanamine compounds (e.g., melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct, etc.). These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by mass per 100 parts by mass of the thermosetting resin.

[0118] (Storage Stabilizer) The present composition may contain a storage stabilizer to stabilize the viscosity over time. 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, t-butylpyrocatechol, organic phosphines such as tetraethylphosphine and tetraphenylphosphine, and phosphites. The storage stabilizer can be used in an amount of 0.1 to 10 parts by mass per 100 parts by mass of the colorant.

[0119] (Solvent) The present composition may contain a solvent. This makes it easy to adjust the viscosity of the photosensitive coloring composition, making it easy to form a coating with a smooth surface. The solvent may be appropriately selected depending on the purpose of use, and an appropriate amount may be contained.

[0120] Examples of the solvent 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 but not -O-, -CO-, or -COO-), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

[0121] Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0122] Examples of the ether solvent include ether solvents having no hydroxyl group and ether alcohol solvents (solvents containing -OH and -O- in the molecule). Examples of the ether alcohol solvent include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, and 3-methoxy-3-methylbutanol. Examples of ether solvents having no hydroxyl group include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, anisole, phenetole, and methylanisole.

[0123] Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl 3-ethoxy ... Examples of such solvents include methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol diacetate, etc. Among these, it is preferred that the present composition contains an ether ester solvent from the viewpoint of compatibility and coatability of the photosensitive coloring composition.

[0124] Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0125] Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, and glycerin.

[0126] Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

[0127] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0128] Among these, solvents having a boiling point of 120° C. or higher and 245° C. or lower at 1 atm are preferred in terms of coating and drying properties. For example, 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, cyclohexanone, tripropylene glycol monomethyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and the like are more preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, cyclohexanone, tripropylene glycol monomethyl ether, 3-methoxy-1-butanol, and the like are even more preferred.

[0129] In addition, these solvents can adjust the viscosity of the photosensitive coloring composition to an appropriate level and form a coating film with the desired uniform thickness. Therefore, it is preferable to use the solvent in an amount of 200 to 900 parts by mass, more preferably 300 to 570 parts by mass, relative to 100 parts by mass of the solid content (non-volatile content) of the photosensitive coloring composition.

[0130] (Dispersing Aid) When dispersing the colorant, a dispersing aid such as a dye derivative, a resin-type dispersant, a surfactant, etc. may be appropriately contained. The dispersing aid has a significant effect of preventing reagglomeration of the colorant after dispersion, and therefore, a coloring composition in which the colorant is dispersed using the dispersing aid has good brightness and viscosity stability.

[0131] ((Dye Derivatives)) Examples of dye derivatives include compounds in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent has been introduced into an organic pigment, an anthraquinone, an acridone, or a triazine, and for example, those disclosed in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and JP-A-2001-335717 Those described in JP-A-2003-128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094873, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916, Japanese Patent No. 4585781, etc. can be used, and these can be used alone or in combination of two or more types.

[0132] The content of the dye derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and most preferably 3 parts by mass or more, relative to 100 parts by mass of the colorant from the viewpoint of improving dispersibility, and is preferably 40 parts by mass or less, more preferably 35 parts by mass or less, from the viewpoint of heat resistance and light fastness.

[0133] ((Resin-Type Dispersant)) The resin-type dispersant has a colorant-affinity moiety that adsorbs to the colorant (A) and a relaxation moiety that has high affinity with components other than the colorant (A) and causes steric repulsion between dispersed particles. Resin-type dispersants, in terms of resin type, for example, urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof, poly (lower alkylene imine) and free carboxyl group-containing polyester amides formed by reaction with polyesters and their salts, oil-based dispersants such as (meth) acrylic acid - styrene copolymers, (meth) acrylic acid - (meth) acrylic acid ester copolymers, styrene - maleic acid copolymers, polyvinyl alcohol, water-soluble resins and water-soluble polymer compounds such as polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, phosphate esters, and the like.

[0134] In terms of the type of functional group, examples of the resin-type dispersant include an acidic functional group-containing resin-type dispersant and a basic functional group-containing resin-type dispersant.

[0135] Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, and 2155 manufactured by BYK Japan Co., Ltd. Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS, or Bykumen, etc., and SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, etc. manufactured by Lubrizol Japan. 000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., and EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402 manufactured by BASF Japan Ltd. , 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajisper PA111, PB711, PB821, PB822, PB824 manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0136] ((Surfactant)) Examples of the surfactant include anionic surfactants such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of 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 ethylene oxide adducts thereof; alkyl betaines such as alkyldimethylaminoacetic acid betaine, and amphoteric surfactants such as alkylimidazolines. These can be used alone or in combination of two or more, but are not necessarily limited to these.

[0137] When a resin-type dispersant or surfactant is added, the amount is preferably 0.1 to 55 parts by mass, and more preferably 0.1 to 45 parts by mass, relative to 100 parts by mass of the colorant. When the blending amount of the resin-type dispersant or surfactant is 0.1 part by mass or more, the effect of adding the resin-type dispersant or surfactant can be easily obtained, and when the content is 55 parts by mass or less, an appropriate amount of dispersant has a favorable effect on dispersion.

[0138] (Thiol-based chain transfer agent) The composition may contain a chain transfer agent. The chain transfer agent is preferably a thiol-based chain transfer agent. When the thiol-based chain transfer agent is used in combination with a photopolymerization initiator, a thiyl radical that is resistant to polymerization inhibition by oxygen is generated during radical polymerization after light irradiation, thereby improving the sensitivity of the photosensitive coloring composition.

[0139] The thiol chain transfer agent is preferably a polyfunctional thiol having two or more thiol groups (SH groups), more preferably four or more SH groups. As the number of functional groups increases, photocuring becomes easier from the surface to the deepest part of the coating.

[0140] Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, Examples of the thiol chain transfer agent include thritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, and preferred examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate. The thiol chain transfer agent can be used alone or in combination of two or more.

[0141] The content of the thiol chain transfer agent is preferably 0.5 to 10 mass %, more preferably 1 to 8 mass %, of the total solid content (total nonvolatile content) of the colored composition. When an appropriate amount is contained, the taper shape, wrinkles, film shrinkage rate, photosensitivity, and pattern shape are further improved.

[0142] <Method for producing photosensitive coloring composition> The photosensitive coloring composition can be prepared by mixing the above-mentioned components. When preparing the composition, the components may be blended together, or the components may be dissolved or dispersed in an organic solvent and then blended sequentially. For example, a dispersion is produced by adding a colorant, a resin, an organic solvent, etc. and performing a dispersion treatment. Then, a polymerizable compound, a photopolymerization initiator, etc. are blended and mixed with the dispersion, thereby producing the composition. The components to be blended and the timing of blending them are arbitrary. The dispersion process can also be performed multiple times.

[0143] 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.

[0144] The composition is preferably subjected to removal of coarse particles of 5 μm or larger, preferably coarse particles of 1 μm or larger, more preferably coarse particles of 0.5 μm or larger, and particularly preferably coarse particles of 0.3 μm or larger, as well as contaminated dust, by means of centrifugation, filtration using a sintered filter or a membrane filter, or the like.

[0145] <<Organic EL Display Device>> Next, the configuration of an organic EL display device according to the present disclosure (hereinafter also referred to as the present device) will be described with reference to FIG. 1. FIG. 1 is a schematic cross-sectional view of the present device. The present device (organic EL display device 10) has an organic EL layer 2 and a color filter 3 on a substrate 1 (e.g., a silicon substrate) on which driving elements are formed. If necessary, a sealing layer 4 and a cover glass 5 may be further provided on the color filter 3, and a flat layer (planar) may be provided between the organic EL layer 2 and the color filter 3 (not shown). The present organic EL display device may be a Micro-OLED (Organic Light-Emitting Diode) display device. Details of each component of the organic EL display device will be described below.

[0146] [Color Filter] The color filter 3 shown in FIG. 1 is formed on the organic EL layer 2 and includes at least a red pixel, a green pixel, and a blue pixel (3a, 3b, 3c). As described above, the present composition can be used as a green photosensitive coloring composition. Therefore, the pixel (e.g., the green pixel) can be configured with a cured film formed from the above-described photosensitive coloring composition. In other words, the pixel is a cured product of the above-described photosensitive coloring composition, and the present device includes a cured film formed from the present composition. The color filter 3 may further include magenta pixels, cyan pixels, yellow pixels, or other pixels.

[0147] <Method for manufacturing color filters> The color filters are formed on the organic EL layer 2 or on a planarizing layer provided as needed. By providing the planarizing layer, the finely uneven surface of the organic EL layer 2 can be planarized. For the planarizing layer, a known curable resin can be used, and an ultraviolet-curable resin is preferred, and a thermosetting resin may be used in combination as needed. The ultraviolet-curable resin is not particularly limited, but an acrylic resin that is sensitive to i-line (wavelength 365 nm) is preferred.

[0148] The method for forming the pixels constituting the color filter 3 is not particularly limited, but can be, for example, the following method. First, in addition to the above-described present composition, for example, each photosensitive coloring composition such as red or blue is applied to the organic EL layer 2 or the flat layer using a coating method such as spray coating, dip coating, bar coating, coal coating, or spin coating to form a coating film. The red photosensitive coloring composition and the blue photosensitive coloring composition may be any conventionally known composition as long as the effects of the present disclosure are obtained, and are not particularly limited. Next, the coating film is dried as needed, and then exposed to light through a mask with a predetermined pattern to photopolymerize the photopolymerizable monomer and photosensitive resin, resulting in a cured coating film. Examples of light sources used for exposure include ultraviolet light from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, electron beams, etc. The exposure dose may be adjusted appropriately depending on the light source used, the thickness of the coating film, etc. Furthermore, a heat treatment may be performed after exposure to promote the polymerization reaction. The photosensitive composition has low-temperature curing properties and can be sufficiently cured even with heat treatment at 100°C or below.

[0149] The film thickness of the pixels constituting the color filter 3 is preferably 0.5 μm to 2.0 μm, and more preferably 1.0 to 2.0 μm.

[0150] The organic EL layer may be formed as a single organic light-emitting layer containing a light-emitting substance, or as a multilayer. When formed as a multilayer, it may have, for example, a three-layer structure in which a typical hole transport layer, an electron transporting organic light-emitting layer, and an electron transport layer are sequentially laminated, or may have a multilayer structure in which a hole (electron) injection layer and a hole (electron) transport layer are provided, each layer having separate injection and transport functions, or a layer that blocks hole (electron) transport.

[0151] An example of the organic EL layer is a layer structure in which an anode, an organic layer, and a cathode are laminated in this order from the substrate side, and the layer is airtightly covered with a sealing layer.

[0152] The anode is provided on the substrate and is made of a conductive material with a large work function, such as nickel, silver, gold, platinum, palladium, selenium, rhodium, ruthenium, iridium, rhenium, tungsten, molybdenum, chromium, tantalum, niobium, alloys of these, tin oxide (SnO), indium tin oxide (ITO), zinc oxide, titanium oxide, etc.

[0153] The cathode is made of a conductive material with a small work function. Examples of such conductive materials include alloys of active metals such as Li, Mg, and Ca with metals such as Ag, Al, and In, or laminated structures of these. Alternatively, a thin compound layer of an active metal such as Li, Mg, or Ca with a halogen such as fluorine or bromine, or oxygen, may be inserted between the organic layer.

[0154] The anodes and cathodes are patterned into a shape appropriate for the driving method of the display device. For example, when the driving method of the organic EL display device is a simple matrix type, the anodes and cathodes are formed in stripes that intersect with each other, and the intersections form organic EL elements.

[0155] The organic layer has at least a white light-emitting layer, but is usually composed of multiple organic layers, and may have a charge injection layer such as a hole injection layer or an electron injection layer, a hole transport layer that transports holes to the white light-emitting layer, or a charge transport layer such as an electron transport layer that transports electrons to the white light-emitting layer.

[0156] The light-emitting layer may be any known layer that can emit white light. The white light-emitting characteristics require that the layer emit light in at least three regions: the red region (600 nm to 780 nm), the green region (475 nm to 600 nm), and the blue region (380 nm to 475 nm). Three or more emission peaks are not necessarily required; for example, two emission peaks may be sufficient as long as the layer emits light in the above-mentioned regions. However, in order to obtain a wide color reproducibility, it is preferable to use a white light-emitting layer that has three or more emission peaks, and it is preferable that the layer has an emission peak in at least one of the above-mentioned three color regions.

[0157] The material for forming such a white light-emitting layer is not particularly limited as long as it emits fluorescence or phosphorescence. The light-emitting material may have hole transport properties or electron transport properties. Examples of the light-emitting material include dye-based materials, metal complex-based materials, and polymer-based materials.

[0158] Examples of the dye-based materials include cyclopentamine derivatives, tetraphenylbutadiene derivatives, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, silole derivatives, thiophene ring compounds, pyridine ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, triphimanylamine derivatives, oxadiazole dimers, and pyrazoline dimers.

[0159] Examples of the metal complex material include aluminum quinolinol complexes, benzoquinolinol beryllium complexes, benzoxazole zinc complexes, benzothiazole zinc complexes, azomethyl zinc complexes, porphyrin zinc complexes, and europium complexes; and metal complexes having a central metal such as Al, Zn, or Be or a rare earth metal such as Tb, Eu, or Dy, and having an oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, or quinoline structure as a ligand.

[0160] Examples of the polymeric materials include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinylcarbazole derivatives, and polymerized versions of the above-mentioned dye-based materials and metal complex-based materials.

[0161] Examples of methods for forming the white light-emitting layer include vapor deposition, printing, inkjet printing, spin coating, casting, dipping, bar coating, blade coating, roll coating, gravure coating, flexographic printing, spray coating, and self-assembly methods (layer-by-layer adsorption, self-assembled monolayer), etc. In particular, vapor deposition, spin coating, and inkjet printing are preferred, and the film thickness of the white light-emitting layer is usually about 5 nm to 5 μm.

[0162] The organic EL layer may also have a hole injection layer formed between the white light-emitting layer and the anode. The provision of the hole injection layer stabilizes hole injection into the white light-emitting layer, thereby improving luminous efficiency. Materials generally used for hole injection layers in organic EL elements can be used as materials for forming the hole injection layer. The material for forming the hole injection layer may be any material that has either hole injection properties or electron barrier properties.

[0163] Specific examples of materials for forming the hole injection layer include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, polysilane-based and aniline-based copolymers, and conductive polymer oligomers such as thiophene oligomers.

[0164] Furthermore, materials for forming the hole injection layer include porphyrin compounds, aromatic tertiary amine compounds, styrylamine compounds, etc. The thickness of the hole injection layer is usually about 5 nm to 1 μm.

[0165] The organic EL layer may further include an electron injection layer between the white light-emitting layer and the cathode. By providing the electron injection layer, electron injection into the white light-emitting layer can be stabilized, thereby improving the luminous efficiency.

[0166] Examples of materials for forming the electron injection layer include nitro-substituted fluorene derivatives, anthraquinodimethane derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, heterocyclic tetracarboxylic acid anhydrides such as naphthalene perylene, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, thiazole derivatives in which the oxygen atom of the oxadiazole ring of an oxadiazole derivative is substituted with a sulfur atom, quinoxaline derivatives having a quinoxaline ring known as an electron-withdrawing group, metal complexes of 8-quinolinol derivatives such as tris(8-quinolinol)aluminum, phthalocyanines, metal phthalocyanines, and distyrylpyrazine derivatives.

[0167] <<Micro-LED Display Device>> The Micro-LED display device according to the present disclosure includes a cured film formed from a photosensitive coloring composition for a Micro-LED display device having the same configuration as the photosensitive coloring composition for an organic EL display device. The Micro-LED display device according to the present disclosure can also include a color filter on a (silicon) substrate on which drive elements are formed. The substrate and color filter can be similarly applied to the organic EL display device described above. The other components of the Micro-LED display device can be appropriately selected from the various components of conventionally known Micro-LED display devices and are not particularly limited. In this way, the technology of the organic EL display device can be applied to a Micro-LED display device.

[0168] The present invention will be described below with reference to examples. However, the present invention is not limited to these examples. In the examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

[0169] <Colorant (A)> (Green pigment (A1))

[0170] <Pigment Green 62> 200 parts of a green pigment C.I. Pigment Green 62 (manufactured by Toyocolor Co., Ltd.), 1,400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 80°C. Next, this kneaded mixture was added to 8,000 parts of warm water, and stirred for 2 hours while heating to 80°C to form a slurry. After repeated filtration and washing with water to remove the sodium chloride and diethylene glycol, the slurry was dried at 85°C for one day to obtain a phthalocyanine-based finely divided green pigment (PG-1).

[0171] <Pigment Green 36> 120 parts of a green pigment C.I. Pigment Green 36 ("Lionol Green 6YK" manufactured by Toyocolor Co., Ltd.), 1,600 parts of sodium chloride, and 270 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 5,000 parts of warm water, and the mixture was stirred for 1 hour while heated to about 70°C to form a slurry. The slurry was filtered and washed repeatedly with water to remove the salt and solvent, and then dried overnight at 80°C to obtain 117 parts of a finely divided green pigment (PG-2).

[0172] (Yellow Pigment (A2)) <Pigment Yellow 139> 100 parts of the yellow pigment C.I. Pigment Yellow 139 (PY139) ("Irgaphor Yellow 2R-CF" manufactured by BASF Japan 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.) and kneaded for 6 hours at 70 ° C. This kneaded mixture was added to 3000 parts of warm water, heated to 70 ° C. and stirred for 1 hour to form a slurry, filtered and washed repeatedly to remove the sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight to obtain 98 parts of a finely divided yellow pigment (PY-1). The average primary particle diameter was 40.2 nm.

[0173] <Pigment Yellow 185> 100 parts of a yellow pigment C.I. Pigment Yellow 185 (PY185) (BASF Japan Ltd. "PALIOTOL YELLOW D1155"), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 80 ° C. This mixture was added to 2000 parts of hot water, heated to 80 ° C. and stirred for 1 hour to form a slurry, filtered, and washed repeatedly with water to remove the salt and solvent, and then dried at 80 ° C. overnight to obtain 95 parts of a finely divided yellow pigment (PY-2).

[0174] (Red Pigment) <Pigment Red 254> 100 parts of red pigment C.I. Pigment Red 254 (PR254) ("Irgaphor Red B-CF" manufactured by BASF Japan 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 at 60 ° C. for 6 hours, and subjected to salt milling. The resulting kneaded mixture was added to 3 liters of warm water, heated to 70 ° C. and stirred for 1 hour to form a slurry, filtered, and washed repeatedly with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight to obtain 98 parts of a finely divided red pigment (PR-1). The average primary particle diameter was 33 nm.

[0175] <Pigment Red 177> 97 parts of a finely divided red pigment (PR-2) was obtained in the same manner as in the production of the red colorant (PR-29), except that the red pigment C.I. Pigment Red 254 was changed to C.I. Pigment Red 177 (PR177) ("Cromophtal Red A2B" manufactured by BASF Japan Ltd.). The average primary particle diameter was 27.6 nm.

[0176] (Blue Pigment) <Pigment Blue 15:6> Blue pigment C.I. Pigment Blue 15:6 ("LIONOL BLUE ES" manufactured by TOYOCOLOR Co., Ltd., specific surface area 60 m ２ 200 parts of hydroxybenzoate (1 / g), 1,400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 80° C. Next, this kneaded mixture was poured into 8,000 parts of warm water and stirred for 2 hours while heating to 80° C. to form a slurry. After repeatedly filtering and washing with water to remove the sodium chloride and diethylene glycol, the slurry was dried at 85° C. for one day to obtain a phthalocyanine-based finely divided blue pigment (PB-1).

[0177] (Purple Pigment) <Pigment Violet 23> 200 parts of a purple pigment C.I. Pigment Violet 23 ("LIONOGEN VIOLET RL" manufactured by Toyocolor Co., Ltd.), 1,400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 80°C. Next, this kneaded mixture was added to 8,000 parts of warm water, and the mixture was stirred for 2 hours while heated to 80°C to form a slurry. The mixture was then filtered and washed repeatedly with water to remove the sodium chloride and diethylene glycol, and then dried overnight at 85°C to obtain a dioxazine-based finely divided purple pigment (PV-1).

[0178] <Production of Resin-Type Dispersant Solution> (Resin-Type Dispersant Solution 1): Photosensitive Resin-Type Dispersant A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 8 parts of 3-mercapto-1,2-propanediol, 12 parts of pyromellitic anhydride, 80 parts of propylene glycol monomethyl ether acetate (PGMAc), and 0.2 parts of monobutyltin oxide as a catalyst, and the atmosphere was replaced with nitrogen gas, followed by reaction at 120 ° C. for 5 hours (first step). Measurement of the acid value confirmed that 95% or more of the acid anhydride was half-esterified. Next, 15 parts of methyl methacrylate (MMA), 10 parts of tert-butyl acrylate (tBA), 10 parts of ethyl acrylate (EA), 5 parts of methacrylic acid (MAA), 10 parts of benzyl methacrylate (BzMA), 50 parts of 2-hydroxyethyl methacrylate (HEMA) were charged, and the reaction vessel was heated to 80 ° C., and 1 part of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the reaction was carried out for 12 hours (second step). It was confirmed that 95% had reacted by measuring the nonvolatile content. Next, the atmosphere in the flask was replaced with air, and 54.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), 0.1 parts of hydroquinone were charged, and the reaction was carried out at 70 ° C. for 4 hours (third step). After confirming the disappearance of the peak at 2270 cm-1 due to the isocyanate group by IR, the reaction solution was cooled and the nonvolatile content was adjusted with PGMAc to obtain a photosensitive resin with a nonvolatile content of 40%: Resin-type dispersant solution 1. The acid value of the obtained resin-type dispersant was 36 mgKOH / g, and the weight-average molecular weight was 12,000.

[0179] (Resin-type dispersant solution 2): Non-photosensitive resin-type dispersant. A reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer was charged with 30 parts of ethyl acrylate, 20 parts of tert-butyl acrylate, and 40 parts of 2-methyl methacrylate, and the atmosphere was replaced with nitrogen gas. The reaction vessel was heated to 80°C, and a solution of 6 parts of 3-mercapto-1,2-propanediol and 0.1 parts of 2,2'-azobisisobutyronitrile dissolved in 45.7 parts of cyclohexanone was added and reacted for 10 hours. Measurement of the nonvolatile content confirmed that 95% had reacted. At this time, the weight-average molecular weight was 4000. Next, 9.7 parts of pyromellitic dianhydride, 70 parts of PGMAc, and 0.20 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 120°C for 7 hours. The reaction was terminated when it was confirmed by measuring the acid value that 98% or more of the acid anhydride had been half-esterified. After the reaction was completed, the nonvolatile content was adjusted to 40% by mass, and a PGMAc solution of a resin-type dispersant (resin-type dispersant solution 2) having a weight-average molecular weight of 8,100, an acid value of 50 mgKOH / g, and a glass transition temperature of the vinyl polymerization site of 22.5°C was obtained.

[0180] <Production of binder resin> (Acrylic resin solution (D)): Photosensitive resin A separable four-necked flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer. 100 parts of propylene glycol monomethyl ether acetate was placed in a reaction vessel, and the vessel was heated to 120 ° C. while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 1.0 parts of azobisisobutyronitrile was added dropwise over 2.5 hours from the dropping tube to carry out a polymerization reaction. Next, the atmosphere in the flask was replaced with air, and 17.0 parts of acrylic acid, 0.3 parts of trisdimethylaminomethylphenol, and 0.3 parts of hydroquinone were added. The reaction was continued for 5 hours at 120 ° C. until the acid value reached 0.8 mg KOH / g, and the reaction was terminated. A resin solution having a weight average molecular weight of about 12,000 (measured by GPC) was obtained. Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine were added and reacted at 120°C for 4 hours, and propylene glycol monomethyl ether acetate was added so that the nonvolatile content became 20% to prepare an acrylic resin solution (D-1).

[0181] <Preparation of Pigment Dispersion> (Pigment Dispersion (P-1)) The following mixture was stirred and mixed to a uniform consistency, and then dispersed for 3 hours in an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm. The mixture was then filtered through a 5.0 μm filter to prepare a pigment dispersion (P-1) having a non-volatile content of 18% by mass. Green pigment (PG-1): 11.7 parts Resin-type dispersant solution 2: 15.8 parts Propylene glycol monomethyl ether acetate (PGMAc): 72.5 parts

[0182] (Pigment Dispersions (P-2 to P-4)) Pigment dispersions (P-2 to P-4) were prepared in the same manner as for the pigment dispersion (P-1), except that the materials and blending amounts of the pigment dispersion (P-1) were changed as shown in Table 1.

[0183] (Pigment Dispersions (P-5 to P-8)) Pigment dispersions (P-5 to P-8) were prepared in the same manner as for pigment dispersion (P-1), except that the materials and blending amounts of the pigment dispersion (P-1) were changed as shown in Table 2. Note that the blending ratio of each component (pigment, resin-type dispersant solution, and PGMAc) in Tables 1 and 2 is expressed in parts by mass, and the unit of the nonvolatile content is expressed in % by mass.

[0184] <Green Photosensitive Coloring Composition> [Example 1] (Photosensitive Coloring Composition (G-1)) The following mixture was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to obtain a photosensitive coloring composition (G-1). Pigment dispersion (P-1): 7.91 parts Pigment dispersion (P-2): 29.63 parts Pigment dispersion (P-4): 32.41 parts Polymerizable compound (B-1): 7.05 parts Photopolymerization initiator (C-1): 0.66 parts Acrylic resin solution (D): 9.75 parts Leveling agent (non-volatile content 1%): 1.00 parts Propylene glycol monomethyl ether acetate (PGMAc): 11.59 parts

[0185] [Examples 2 to 6 and Comparative Examples 1 to 4] (Photosensitive coloring compositions (G-2) to (G-10)) The materials and blending amounts of the photosensitive coloring composition (G-1) were changed as shown in Tables 3 and 4, except that the photosensitive coloring composition (G-2 to G-10) was prepared in the same manner as the photosensitive coloring composition (G-1). Note that the units in the blending ratio of each component (pigment dispersion, polymerizable compound, photopolymerization initiator, acrylic resin solution, leveling agent and PGMAc) in Tables 3 to 6 described below are parts by mass.

[0186] The abbreviations in the table are as follows: <Polymerizable Compounds (B)> Polymerizable compound B-1: trimethylolpropane triacrylate (manufactured by Toagosei Co., Ltd., trade name: "Aronix M-309") Polymerizable compound B-2: trimethylolpropane EO-modified triacrylate (manufactured by Toagosei Co., Ltd., trade name: "Aronix M-350") Polymerizable compound B-3: dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd., trade name: "Aronix M-402") <Photopolymerization initiator (C)>

[0187]

[0188] <Leveling Agent> Leveling agent: a solution prepared by dissolving 1 part of FZ-2122 (trade name, manufactured by Dow Corning Toray Co., Ltd.) in 99 parts of propylene glycol monomethyl ether acetate (PGMAc)

[0189] <Evaluation of Photosensitive Coloring Composition> (Brightness Evaluation) The obtained photosensitive coloring composition was applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C for 20 minutes, and exposed to ultraviolet light through a photomask using an ultra-high pressure mercury lamp. The substrate was then spray-developed with a 0.2% by mass aqueous sodium carbonate solution at 23 ° C for 30 seconds, washed with ion-exchanged water, and air-dried. The substrate was then post-baked in a clean oven at 230 ° C for 30 minutes to form a pixel pattern with a film thickness of 1.5 μm on the substrate. Subsequently, a resin solution was obtained by adding 2.0 g of a silicone surfactant (KF351A, manufactured by Shin-Etsu Silicones Co., Ltd.) to 1 kg of commercially available polyvinyl alcohol (concentration 5%) and stirring for 10 minutes. The resin solution was then coated on the pixel pattern to a film thickness of 1 μm using the same coating method as above and dried. The brightness (Y) of the resulting coating film was measured using a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). After that, the coating was irradiated with LED lighting for 200 hours in an environment of 70°C and 85% humidity using an Espec Corporation high temperature and humidity device ARS-1430-15, and the brightness (Y) was evaluated again. The change in brightness before and after the test was judged according to the following criteria. The target value for the initial brightness is 65.0 or more, and anything less than 65.0 is not practical. A: The brightness change before and after the lightfastness test is less than 0.5 points, which is excellent. B: The brightness change before and after the lightfastness test is 0.5 points or more but less than 1.0 point, which is practical. C: The brightness change before and after the lightfastness test is 1.0 points or more but less than 5.0 points, which is difficult to use. D: The brightness change before and after the lightfastness test is 5.0 points or more, which is not practical.

[0190] (Residue Evaluation) The surface of the substrate developed by the above method was observed under a microscope to evaluate residues. A: No residues at all, usable for practical use. B: Slight residues present, but no practical impediment. C: Residues present, not usable for practical use.

[0191] [Red photosensitive coloring composition] The materials and blending amount of photosensitive coloring composition (G-1) are changed as shown in Table 5, except that, the same process as the photosensitive coloring composition (G-1) is carried out to obtain photosensitive coloring composition (R-1).

[0192] [Blue photosensitive coloring composition] The materials and blending amount of photosensitive coloring composition (G-1) are changed as shown in Table 6, except that the same procedure as for photosensitive coloring composition (G-1) is carried out to obtain photosensitive coloring composition (B-1).

[0193] Examples 7 to 12 Organic EL display devices were fabricated as follows using the obtained green photosensitive coloring composition, red photosensitive coloring composition, and blue photosensitive coloring composition.

[0194] <Manufacture of OLED Element> A TFT layer was formed on a silicon substrate by a known method such as etching. Furthermore, an ITO (Indium Tin Oxide) film serving as an anode, a light-emitting organic layer including a light-emitting layer, and an MgAg alloy film serving as a cathode were formed in this order on the TFT layer by a known method such as vapor deposition to form a white organic EL element, and then a passivation layer made of silicon nitride was formed by plasma CVD (Chemical Vapor Deposition) to seal the element, thereby forming an organic EL element substrate.

[0195] <Production of Color Filter and Organic EL Display Device> A green photosensitive resin composition was applied onto the OLED element using a spinner so that the film thickness after curing would be 1.5 μm, and the composition was irradiated with i-line (wavelength: 365 nm) from a high-pressure mercury lamp through a pattern mask at an illuminance of 20,000 W / m ２ The green layer (G) of the color filter was formed by exposure to light at 400 K, development using an organic alkaline developer containing tetramethylammonium hydroxide as an alkaline agent, washing with water, and drying. Thereafter, the green layer (G) of the color filter was cured by heating at 80° C. for 10 minutes in a heating oven, thereby completing the formation of the green layer (G) of the color filter.

[0196] Next, in the same manner as in the method for forming the green layer (G) of the color filter described above, a red photosensitive resin composition was applied with a spinner so that the film thickness after curing would be 1.5 μm, and the red photosensitive resin composition was irradiated with i-line (wavelength: 365 nm) from a high-pressure mercury lamp through a pattern mask at an illuminance of 20,000 W / m ２ The resist was exposed to light at 1000 K, developed using an organic alkaline developer containing tetramethylammonium hydroxide as an alkaline agent, washed with water, and dried to temporarily form a red layer (R) of the color filter. Thereafter, the resist was heated in a heating oven at 80° C. for 10 minutes to harden the resist, completing the formation of the red layer (R) of the color filter.

[0197] Furthermore, in the same manner as in the method for forming the green layer (G) of the color filter described above, a blue photosensitive resin composition was applied with a spinner so that the film thickness after curing would be 1.5 μm, and the composition was irradiated with i-line (wavelength: 365 nm) from a high-pressure mercury lamp through a pattern mask at an illuminance of 20,000 W / m ２ The blue layer (B) of the color filter was temporarily formed through the steps of exposure to light at 400°C, development using an organic alkaline developer containing tetramethylammonium hydroxide as an alkaline agent, washing with water, and drying. Thereafter, the blue layer (B) of the color filter was cured by heating at 80°C for 10 minutes in a heating oven, completing the formation of the blue layer (B) of the color filter and producing a color filter.

[0198] After forming the green, red, and blue layers, they were attached to a cover glass using a sealant, Structbond XMF-T107 (manufactured by Mitsui Chemicals, Inc.), to prepare an organic EL display device.

[0199] <Chromaticity of Organic EL Display Device> The chromaticities of the obtained organic EL display devices when displaying red, green, and blue were measured using an Olympus CS-1000 spectroradiometer. The NTSC area ratio (the ratio of the color gamut of the organic EL display device of the Example or Comparative Example to the color gamut defined by the NTSC standard) was calculated from the obtained red, green, and blue chromaticities. NTSC area ratios of 94% or more were evaluated as A, those of 90% or more but less than 94% as B, and those of less than 90% as C. Those with an NTSC area ratio of less than 90% were judged to be impractical because the image displayed on the organic EL display device appeared to be insufficiently clear. Furthermore, the DCI-P3 area ratio (the ratio of the color gamut of the organic EL display device of the Example or Comparative Example to the color gamut defined by the DCI-P3 standard) was calculated from the obtained red, green, and blue chromaticities. Those with a DCI-P3 area ratio of 94% or more were evaluated as A, those of 90% or more but less than 94% as B, and those of less than 90% as C. Those with a DCI-P3 area ratio of less than 90% were judged to be impractical because the image displayed as an organic EL display device appeared to be insufficiently clear. When all three pixels of red, green, and blue were lit and displayed, and the luminance (W-L) when white was displayed was 330 cd / m2 or more, it was evaluated as A+, 300 cd / m2 or more but less than 330 cd / m2 as A, 280 cd / m2 or more but less than 300 cd / m2 as B, and less than 280 cd / m2 as C. When the luminance was less than 280 cd / m2, the image displayed appeared too dark, and it was judged to be impractical as an organic EL display device.

[0200]

[0201] The present disclosure can be used as a photosensitive coloring composition for organic EL or Micro-LED display devices for electronic devices such as smart glasses, head-mounted displays, and electronic viewfinders.

[0202] This application claims priority based on Japanese Patent Application No. 2023-59310, filed March 31, 2023, the disclosure of which is incorporated herein in its entirety by reference.

[0203] REFERENCE SIGNS LIST 1 Silicon wafer 2 Organic EL layer 3 Color filter 4 Sealing layer 5 Cover glass 10 Organic EL display device 3a, 3b, 3c Pixels

Claims

1. A photosensitive coloring composition for an organic EL display device, comprising a colorant (A), a polymerizable compound (B), a photopolymerization initiator (C), and a resin (D), the colorant (A) contains a green pigment (A1) and a yellow pigment (A2), and the content of the green pigment (A1) in the colorant (A) is 50 to 80 mass %, the green pigment (A1) contains Pigment Green 36 and Pigment Green 62, the mass ratio of Pigment Green 36 to Pigment Green 62 in the green pigment (A1) is 85:15 to 65:35, and the content of Pigment Green 62 in the green pigment (A1) is 10 to 20 mass%, The yellow pigment (A2) includes Pigment Yellow 185, The polymerizable compound (B) contains a trifunctional (meth)acryloyl group-containing aliphatic monomer (B1), Photosensitive coloring composition for organic EL display devices.

2. 2. The photosensitive coloring composition for an organic EL display device according to claim 1, wherein the trifunctional (meth)acryloyl group-containing aliphatic monomer (B1) comprises a compound represented by the following chemical formula 1: 【Chemistry 1】

3. The photosensitive coloring composition for an organic EL display device according to claim 1 or 2, wherein the photopolymerization initiator (C) comprises an oxime ester compound.

4. A cured film formed from the photosensitive coloring composition for an organic EL display device according to claim 1 or 2.

5. An organic electroluminescence display device comprising the cured film according to claim 4 .

6. 6. The organic EL display device according to claim 5, wherein the organic EL display device is a Micro-OLED display device.

7. A photosensitive coloring composition for a Micro-LED display device, comprising a colorant (A), a polymerizable compound (B), a photopolymerization initiator (C), and a resin (D), the colorant (A) contains a green pigment (A1) and a yellow pigment (A2), and the content of the green pigment (A1) in the colorant (A) is 50 to 80 mass %, the green pigment (A1) contains Pigment Green 36 and Pigment Green 62, the mass ratio of Pigment Green 36 to Pigment Green 62 in the green pigment (A1) is 85:15 to 65:35, and the content of Pigment Green 62 in the green pigment (A1) is 10 to 20 mass%, The yellow pigment (A2) includes Pigment Yellow 185, The polymerizable compound (B) contains a trifunctional (meth)acryloyl group-containing aliphatic monomer (B1), Photosensitive coloring composition for Micro-LED display devices.

8. A cured film formed from the photosensitive coloring composition for a Micro-LED display device according to claim 7.

9. A Micro-LED display device comprising the cured film according to claim 8.

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