WO2024204797A1 - 有機ＥＬ表示装置用感光性着色組成物、Ｍｉｃｒｏ－ＬＥＤ表示装置用感光性着色組成物、硬化膜、有機ＥＬ表示装置およびＭｉｃｒｏ－ＬＥＤ表示装置 - Google Patents

有機ＥＬ表示装置用感光性着色組成物、Ｍｉｃｒｏ－ＬＥＤ表示装置用感光性着色組成物、硬化膜、有機ＥＬ表示装置およびＭｉｃｒｏ－ＬＥＤ表示装置 Download PDF

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Publication number
WO2024204797A1
WO2024204797A1 PCT/JP2024/013254 JP2024013254W WO2024204797A1 WO 2024204797 A1 WO2024204797 A1 WO 2024204797A1 JP 2024013254 W JP2024013254 W JP 2024013254W WO 2024204797 A1 WO2024204797 A1 WO 2024204797A1
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Prior art keywords
pigment
green
group
organic
mass
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PCT/JP2024/013254
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English (en)
French (fr)
Japanese (ja)
Inventor
一道 原口
健人 小暮
新司 常川
美佳子 東
佑輝 廣田
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Toyo Visual Solutions Co Ltd
Toppan Holdings Inc
Artience Co Ltd
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Toyo Visual Solutions Co Ltd
Toppan Holdings Inc
Artience Co Ltd
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Priority to JP2025511704A priority Critical patent/JPWO2024204797A1/ja
Priority to KR1020257030770A priority patent/KR20250166902A/ko
Priority to CN202480020613.3A priority patent/CN120936914A/zh
Publication of WO2024204797A1 publication Critical patent/WO2024204797A1/ja
Anticipated expiration legal-status Critical
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/30—Devices specially adapted for multicolour light emission
    • H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]

Definitions

  • This disclosure relates to photosensitive coloring compositions for organic EL display devices, photosensitive coloring compositions for Micro-LED display devices, cured films using them, organic EL display devices, and Micro-LED display devices.
  • the pixel size of the above microdisplays is minute, ranging from 1 ⁇ m to 5 ⁇ m, so the conventional method of producing organic EL elements and color filters on separate substrates and bonding them together can result in reduced precision and color misalignment. For this reason, a method of forming color filters on organic EL elements has been proposed.
  • Color filters can be manufactured using a variety of methods, including the inkjet method and photolithography, but photolithography, which uses a photosensitive coloring composition that allows for the formation of minute pixels, is increasingly being adopted.
  • Patent Document 1 discloses a pigment dispersion composition for color filters that contains a pigment and a pigment dispersant made of a polymer having specific structural units in an organic solvent.
  • the cured film formed using the composition described in Patent Document 1 is exposed to light for a long time under a high temperature and high humidity environment, the color may change.
  • the cured film is required to have high brightness
  • the organic EL display device using the cured film is required to have high brightness and high color reproducibility.
  • the photosensitive coloring composition used in the organic EL display device is required to have good developability.
  • the objective of the present disclosure is to provide a photosensitive coloring composition for organic EL display devices, a photosensitive coloring composition for Micro-LED display devices, a cured film with excellent light resistance and little change in light resistance even when placed in a high-temperature, high-humidity environment for a long period of time, and capable of forming a cured film with excellent developability, and an organic EL display device and Micro-LED display device equipped with the same, which have high brightness and high color reproducibility.
  • a photosensitive coloring composition for an organic electroluminescence 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
  • Photosensitive coloring composition for an organic electroluminescence display device [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 electroluminescence display device comprising the cured film according to [4].
  • 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, and 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 (
  • a photosensitive coloring composition for organic EL display devices a photosensitive coloring composition for Micro-LED display devices, a cured film with excellent light resistance, little change in brightness, and excellent developability, which has high brightness and is capable of forming a cured film even when placed in a high-temperature, high-humidity environment for a long period of time, and an organic EL display device and a Micro-LED display device equipped with the same, which have high brightness and high color reproducibility.
  • FIG. 1 is a schematic cross-sectional view of an organic EL display device according to an embodiment of the present invention.
  • the photosensitive coloring composition for organic EL display devices (hereinafter also referred to as the present composition) and the photosensitive coloring composition for Micro-LED display devices according to the present disclosure, the cured film formed therefrom, the organic EL display device (hereinafter also referred to as the present device), and the Micro-LED display device will be described.
  • the photosensitive coloring composition for organic EL display devices and the organic EL display device may be particularly focused on, but the present disclosure is not limited thereto.
  • the term "to" indicating a range of values means that the values before and after it are included as the lower and upper limits.
  • the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in another stepwise manner.
  • the upper or lower limit value of the numerical range may be replaced with a value shown in the examples.
  • 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 The colorant (A) contains a yellow pigment (A2).
  • the content of the green pigment (A1) in the colorant (A) is 50 to 80 mass %.
  • the green pigment (A1) is Pigment Green 36 and Pigment Green 62, and in the green pigment (A1), the content mass ratio of Pigment Green 36 to Pigment Green 62 is 85:15 to 65:35.
  • the content of Green 62 is 10 to 20 mass %.
  • the yellow pigment (A2) contains Pigment Yellow 185.
  • the polymerizable compound (B) contains a trifunctional (meth)acryloyl group-containing Contains an aliphatic monomer (B1).
  • the present composition having the above configuration uses a colorant containing a specific green pigment (A1) and a yellow pigment (A2) (for the green pigment, a specific amount at a specific blending ratio) and a specific polymerizable compound (B), which allows the formation of a cured film with excellent developability and a designed pattern shape, while suppressing development residues.
  • the cured film formed from the present composition having this configuration has high brightness and can suppress brightness change to a low level even when placed in a high-temperature, high-humidity environment for a long period of time, thereby realizing 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 organic EL display devices.
  • the 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 to the extent that the problem of the present disclosure can be solved.
  • a colorant A
  • B polymerizable compound
  • C photopolymerization initiator
  • D resin
  • Each component that may be contained in the composition is described below.
  • the colorant (A) includes a green pigment (A1) and a yellow pigment (A2), and may include, for example, a blue pigment, as necessary. These colorants and pigments may be used alone or in combination of two or more.
  • the green pigment (A1) contains at least C.I. Pigment Green 36 and Pigment Green 62.
  • the content mass ratio of Pigment Green 36 to Pigment Green 62 is 85:15 to 65:35. If the content mass ratio of Pigment Green 36 to Pigment Green 62 is within the above range, the following is possible. That is, it has high brightness, and even when exposed to light (ultraviolet rays) for a long time (e.g., 200 hours) in a high temperature and high humidity environment (e.g., temperature 65°C, relative humidity 90%), it is possible to suppress the change in color (e.g., green) (change in brightness) to a low level.
  • a high temperature and high humidity environment e.g., temperature 65°C, relative humidity 90%
  • the mass ratio of Pigment Green 36 to Pigment Green 62 in the green pigment (A1) is preferably 85:15 to 75:25.
  • 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.
  • the content of the green pigment (A1) in the colorant (A) is 50 to 80% by mass. If 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, if 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.
  • the content of Pigment Green 62 in the green pigment (A1) is 10 to 20% by mass. If the content of Pigment Green 62 in the green pigment (A1) is 10% by mass or more, it is possible to suppress color change to a low level even when exposed to light in a high-temperature and high-humidity environment for a long period of time, and further, it is possible to suppress development residues in the development step. Furthermore, if 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 a good transmittance, the content of Pigment Green 62 in the green pigment (A1) is preferably 15 mass % or more.
  • 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,
  • the content of the yellow pigment (A2) in the colorant (A) can be set appropriately within a range in which the effects of the present disclosure can be obtained, but for example, it is preferable to set it to 20 to 50 mass%. If the content of the yellow pigment (A2) in the colorant (A) is 20 mass% or more, color change can be suppressed to a low level even when exposed to light in a high-temperature and high-humidity environment for a long period of time. If the content of the yellow pigment (A2) in the colorant (A) is 50 mass% or less, transmittance is improved and high brightness can be obtained. From the viewpoint of obtaining a spectrum with good transmittance, it is more preferable that the content of the yellow pigment (A2) in the colorant (A) is 30 to 45 mass%.
  • 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.
  • the method for micronizing the pigments can be appropriately selected from among known methods, such as wet grinding, dry grinding, and dissolution precipitation, and salt milling treatment can be performed using the kneader method, which is a type of wet grinding.
  • Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt, and water-soluble organic solvent is mechanically kneaded while being heated using a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, or other kneading machine, 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.
  • sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc. can be used as the water-soluble inorganic salt, but sodium chloride (table salt) is preferred from the standpoint of cost. From the standpoint of both processing efficiency and production efficiency, it is preferable to use 50 to 2000 parts by mass of the water-soluble inorganic salt per 100 parts by mass of the pigment, and it is most preferable to use 300 to 1000 parts by mass.
  • the water-soluble organic solvent is a solvent that moistens the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (is miscible with) water and does not substantially dissolve the inorganic salt used.
  • a high-boiling solvent with a boiling point of 120°C or higher is preferred from the standpoint of safety.
  • the water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by mass, and most preferably 50 to 500 parts by mass, per 100 parts by mass of the pigment.
  • a resin may be added as necessary.
  • the resin used is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in the organic solvents mentioned above.
  • 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.
  • the primary particle diameter of the pigment is preferably 20 nm or more, since this provides good dispersion in the composition. Also, since this allows the formation of a color filter with a high contrast ratio, it is preferably 100 nm or less. 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, for 100 or more pigment particles, the volume of each particle 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.
  • the polymerizable compound (B) is a compound having a polymerizable unsaturated group, and in the present composition, the polymerizable compound (B) contains at least a trifunctional (meth)acryloyl group-containing aliphatic monomer (B1). In addition, the polymerizable compound (B) may further contain other polymerizable compounds as necessary.
  • the polymerizable unsaturated group is a vinyl group, a (meth)allyl group, a tert-butyl ...
  • (meth)acryloyl refers to an ethylenically unsaturated double bond such as a cycloalkyl group or a (meth)acryloyl group.
  • the trifunctional (meth)acryloyl group-containing aliphatic monomer (B1) is not particularly limited, but for example, a compound represented by the following general formula (1) can be used.
  • m represents an integer of 1 to 3
  • n represents an integer of 0 to 2
  • multiple ms and multiple ns may be the same or different.
  • R1 represents -H or -CH3 .
  • 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, and pentaerythritol tri(meth)acrylate.
  • the compound represented by formula (1) can be used alone or in combination of two or more kinds.
  • the trifunctional (meth)acryloyl group-containing aliphatic monomer (B1) preferably contains a compound represented by the following chemical formula (1) (trimethylolpropane triacrylate) or a trimethylolpropane PO-modified triacrylate, from the viewpoint 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 viewpoint of suppressing development residues.
  • polymerizable compounds include known (meth)acrylate monomers.
  • the acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, ⁇ -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-mod
  • acrylates examples include taerythritol 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)acrylates, and various acrylic acid esters and methacrylic acid esters such as urethane acrylates, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether
  • 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, and M-30 manufactured by Toagosei Co., Ltd.
  • the content of the polymerizable compound (B) relative to the total solids (non-volatiles) in the composition is preferably 5 to 40% by mass, and more preferably 20 to 30% by mass.
  • 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).
  • the photopolymerization initiator (C) can be appropriately selected from among those that promote the polymerization reaction of the above-mentioned polymerizable compound by the action of light.
  • the photopolymerization initiator (C) contains an oxime ester compound having two or more oxime ester groups in one molecule.
  • the photopolymerization initiator (C) may contain other photopolymerization initiators as necessary.
  • Oxime ester compounds absorb ultraviolet light, causing the cleavage of the N-O bond of the oxime, generating iminyl radicals and alkyloxy radicals. These radicals further decompose to generate highly active radicals, making it possible to form patterns with a small amount of exposure.
  • oxime ester compounds have high quantum efficiency, and therefore have excellent curing properties even when the colorant in the composition is at a high concentration. This composition can be used to form a finely patterned cured film with excellent developability and patterning properties by photolithography.
  • the oxime ester compounds provide the cured film with excellent light blocking and chemical resistance.
  • oxime ester compounds include oxime ester photopolymerization initiators represented by the following general formulas (2) to (4). Of these, oxime ester compounds are preferably oxime ester photopolymerization initiators represented by the following general formulas (2) or (3), and more preferably oxime ester photopolymerization initiators represented by general formula (2).
  • R1 represents an alkyl group having 1 to 20 carbon atoms which may have a substituent
  • R2 represents an alkyl group having 1 to 20 carbon atoms which may have a substituent
  • R11 represents an aryl group which may have a substituent.
  • Examples of the alkyl group having 1 to 20 carbon atoms for R 1 to R 10 include straight-chain alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, and a dodecyl group.
  • Examples of the aryl group in R 2 to R 11 include a phenyl group, a naphthyl group, and an anthracenyl group.
  • Z is a direct bond means that Z has no atom, and the two atoms connected to Z in general formula (2) are directly bonded.
  • the substituent which the alkyl group and the aryl group may have means that the alkyl group or the aryl group may have a substituent in place of a hydrogen atom contained in the alkyl group or the aryl group.
  • the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups such as methoxy group, ethoxy group, and tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group, and benzoyloxy group; acyl groups such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, and methoxalyl group
  • R1 is an alkyl group having 1 to 20 carbon atoms which may have a substituent
  • R2 is an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group which may have a substituent
  • R3 to R10 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 an R11 -CO- group.
  • R4 to R6 and R8 to R10 are hydrogen atoms
  • R7 is a hydrogen atom or an R11 -CO- group
  • R11 is an aryl group which may have a substituent.
  • oxime ester photopolymerization initiators represented by general formula (2) compounds represented by the following chemical formula (2-1) or (2-2) are preferred.
  • W 1 and W 2 each independently represent a carbonyl bond (—CO—) or a single bond, and at least one of W 1 and W 2 is a carbonyl bond (—CO—).
  • R a is an alkyl group having 2 to 6 carbon atoms
  • R b is an alkyl group having 4 to 10 carbon atoms
  • R c is a group that contains at least a hydrocarbon ring or a heterocycle 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-)
  • R b and R c are different substituents.
  • R d and R e are each independently an alkyl group having 1 to 6 carbon atoms.
  • Examples of the alkyl group for R a include straight-chain alkyl groups such as an ethyl group, a propyl group, a butyl group, and a hexyl group.
  • Examples of the alkyl group for Rb include straight-chain alkyl groups such as a butyl group, a hexyl group, an octyl group, and a dodecyl group.
  • Examples of the hydrocarbon ring in Rc include an aliphatic hydrocarbon ring such as a cyclohexyl group, and an aromatic hydrocarbon ring such as a phenyl group, a naphthyl group, an anthracenyl group, etc.
  • Examples of the heterocyclic ring in Rc include a ring in which one or more carbon atoms of the above-mentioned hydrocarbon ring are replaced with a nitrogen atom, an oxygen atom, or a sulfur atom.
  • Examples of the alkyl group in R d and R e include straight-chain alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group.
  • the compound represented by the following chemical formula (3-1) is preferred.
  • 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;
  • 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;
  • 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 an R 26 -CO- group;
  • 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.
  • the alkyl group having 1 to 20 carbon atoms in R 21 to R 26 may be the same as the alkyl group having 1 to 20 carbon atoms in R 1 to R 10 described above.
  • the aryl group in R 21 to R 26 may be the same as the aryl group in R 2 to R 11 .
  • heterocyclic ring in the heterocyclic group of R 26 examples include furan, thiophene, pyrrole, oxazole, thiazole, imidazole, pyrazole, pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine, pyrazine, benzofuran, thionaphthene, indole, carbazole, coumarin, quinoline, phthalazine, and quinoxaline.
  • the substituents which the alkyl group and aryl group may have may be the same as those in the general formula (2).
  • R 21 is an aryl group which may have a substituent
  • R 22 is an alkyl group having 1 to 20 carbon atoms which may have a substituent
  • R 23 and R 24 are hydrogen atoms
  • R 25 is a hydrogen atom or R 26 -CO- group.
  • the compound represented by the following chemical formula (4-1) is preferred.
  • the photopolymerization initiator (C) may further contain other photopolymerization initiators in addition to the oxime ester compounds.
  • other photopolymerization initiators include acetophenones 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.
  • Non-based compounds benzoin-based compounds such as benzoin, benzoin methyl 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, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, and 2,4-diisopropylthioxanthone.
  • benzoin-based compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzo
  • thioxanthone compounds such as propylthioxanthone 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-naphtho triazine-based compounds such as bis(2,4,6-trimethylbenzoyl)pheny
  • photopolymerization initiators may be used alone or in combination of two or more kinds in any ratio as required.
  • Commercially available photopolymerization initiators include acetophenone-based compounds such as "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 of which are manufactured by BASF Japan Co., Ltd.; and phosphine-based compounds such as "IRGACURE 819” (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide) and "IRGACURE TPO" (2,4,6-trimethylbenzoy
  • 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 viewpoints of photocurability and developability.
  • the content of the photopolymerization initiator (C) is 0.5 parts by mass or more, the adhesion to the substrate is excellent.
  • the content of the photopolymerization initiator (C) is 50 parts by mass or less, the resolution is excellent.
  • the blending ratio of the oxime ester compound in the photopolymerization initiator (C) is preferably 80 mass % or more, and more preferably 90 mass % or more, based on the total amount of the photopolymerization initiator (C).
  • the composition contains a resin (D).
  • the resin (D) is preferably a transparent resin having a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm when a coating having a thickness of 2 ⁇ m is formed, and the transmittance is preferably 95% or more.
  • the resin (D) is preferably one or more selected from thermoplastic resins and photosensitive resins.
  • the resin (D) is preferably alkali-soluble. This allows the coating formed from the composition to be patterned by a photolithography method.
  • the photosensitive resin not having alkali solubility and the alkali-soluble resin may have a thermosetting group. Examples of the thermosetting group include an epoxy group and an oxetanyl group. This will be described in detail below.
  • Alkali-soluble resin examples include resins having an acidic group such as a carboxyl group or a sulfone group.
  • alkali-soluble thermoplastic resin examples include acrylic resins having an acidic group, ⁇ -olefin/maleic acid (anhydride) copolymers, styrene/styrenesulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, and isobutylene/maleic acid (anhydride) copolymers.
  • acrylic resins having an acidic group and styrene/styrenesulfonic acid copolymers are preferred in terms of improving developability, heat resistance, and transparency.
  • the thermoplastic resin may include one that is not alkali-soluble.
  • 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.
  • the alkali-soluble photosensitive resin has photosensitivity because it has a polymerizable unsaturated group.
  • the alkali-soluble photosensitive resin may be any known resin as long as it is alkali-soluble and photosensitive, but resins synthesized by the following methods (i) and (ii) are preferred.
  • the alkali-soluble photosensitive resin is used, it is three-dimensionally crosslinked by light irradiation to increase the crosslink density, improving the chemical resistance of the coating.
  • Method (i) is, for example, a method in which 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.
  • epoxy group-containing monomers examples include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate.
  • glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.
  • monocarboxyl group-containing monomers examples 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 ⁇ -position.
  • polybasic acid anhydrides examples 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.
  • Examples of the 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 ethoxypoly
  • 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.
  • hydroxyl group-containing monomer examples 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 hydroxyalkyl (meth)acrylates, and polyester mono(meth)acrylates obtained by addition of poly( ⁇ -valerolactone), poly( ⁇ -caprolactone, and/or poly(12-hydroxystearic acid).
  • 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred, and glycerol mono(meth)acrylate is more preferred.
  • isocyanate group-containing monomers examples include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.
  • Monomers that can be used other than the above monomers include the other monomers exemplified in method (i) above, as well as phosphate ester group-containing monomers, etc.
  • a 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.
  • the above-mentioned raw materials for resin (D) can be used alone or in combination of two or more kinds.
  • Resin (D) can also be used alone or in combination of two or more kinds.
  • the content of 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, per 100 parts by mass of colorant (A). 10 parts by mass or more is preferred because of good film-forming properties and various resistances, and 400 parts by mass or less is preferred because of the high colorant concentration and the ability to express good color characteristics.
  • the weight average molecular weight (Mw) of 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.
  • the acid value of 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 moderate acid value allows for a high level of balance between alkali solubility, adhesion, and residue suppression.
  • the composition may contain other components as necessary in addition to the colorant (A), the polymerizable compound (B), the photopolymerization initiator (C), and the resin (D). Each component that may be contained in the composition will be described below.
  • the composition may further contain a sensitizer.
  • 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, tetraphenylp
  • sensitizers include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, and 3,6-dibenzoyl-N-ethylcarbazole are listed.
  • 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.).
  • a sensitizer that absorbs light in the ultraviolet to near infrared range may be added.
  • the sensitizers may be used alone or in combination of two or more kinds in any ratio as required.
  • a sensitizer When a sensitizer is used, its content is preferably 3 to 60 parts by mass per 100 parts by mass of the photopolymerization initiator (C) contained in the coloring composition, and more preferably 5 to 50 parts by mass from the viewpoints of photocurability and developability.
  • the composition may contain a thermosetting compound. This improves the crosslinking density during the heating step after forming a pattern on the coating by photolithography during the preparation of 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.
  • thermosetting compound is a low molecular weight compound or a polymer (thermosetting resin) and is not limited by its molecular weight.
  • thermosetting resin is included in the thermosetting compound.
  • examples of the thermosetting compound include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.
  • epoxy compound examples 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, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polycondensates of phenols and various diene compounds (
  • epoxy resins examples include polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzene dimethanol, ⁇ , ⁇ , ⁇ ', ⁇ '-benzene dimethanol, biphenyl dimethanol, ⁇ , ⁇ , ⁇ ', ⁇ '-biphenyl dimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls ( ⁇ , ⁇ '-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, glycidyl amine epoxy resins, and glycidyl ester epoxy resins.
  • epoxy compounds include, for example, Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (all trade names: manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256 (all trade names: manufactured by Japan Epoxy Resins Co., Ltd.), TECHMORE VG3101L (trade name: manufactured by Mitsui Chemicals, Inc.), EPPN-501H, 502H (trade names: manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name: manufactured by Japan Epoxy Resins Co., Ltd.), JER 157S65, 157S70 (trade name: manufactured by Japan Epoxy Resins Co., Ltd.), EPPN-201 (trade name: manufactured by Nippon Kayaku Co., Ltd.), Examples include Nippon Kayaku Co., Ltd.), JER152, JER154 (all trade names; Japan Epoxy Resins Co., Ltd.), EO
  • the content of the epoxy compound is preferably 1 to 20 mass% and more preferably 2 to 15 mass% based on 100 mass% of the non-volatile content of the photosensitive coloring composition.
  • an appropriate amount is added, the heat resistance of the coating and the pattern shape are further improved.
  • 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.
  • Examples of the monofunctional oxetane compound 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, and 3-ethyl-3- ⁇ [3-(triethoxysilyl)propoxy]methyl ⁇ oxetane.
  • Examples of 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.
  • bifunctional oxetane compound examples 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, ...
  • oxetane groups with 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 include dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (such as the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30.
  • the content of the oxetane compound is preferably 1 to 20 mass% and more preferably 5 to 15 mass% based on 100 mass% of the nonvolatile content of the composition.
  • the solvent resistance of the coating is further improved.
  • the melamine compound is a compound having a melamine ring structure.
  • the melamine compound includes low molecular weight compounds and high molecular weight compounds.
  • the melamine compound is preferably a compound having a methylol group or an ether group bonded to a melamine ring.
  • the average number of methylol groups and/or ether groups bonded to one melamine ring is preferably 5.0 or more. If 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.
  • 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.).
  • Nikarak MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MX-45 (manufactured by Sanwa Chemical Co., Ltd.) and Cymel 232, 235, 236, 238, 300, 301, 303, 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, further improving the crosslink density of the coating.
  • the composition may contain an antioxidant, which prevents the photopolymerization initiator or the thermosetting compound from being oxidized and yellowed by the thermal process during heat curing or ITO annealing, thereby increasing the transmittance of the pixel.
  • the "antioxidant” may be any compound that has an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposition 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 absorbing agents, antioxidants, etc. can be used.
  • 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.
  • 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'- Butylidene-bis-(2-t-butyl-5-methylphenol), 2,2'-thio-bis-(6-t-buty
  • Hindered amine antioxidants include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(N-methyl-2,2,6,6-tetramethyl-4-piperidyl)sebacate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amine, imino-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,
  • 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(2,4-di-t-butylphenyl)phosphite, tris(biphenyl)phosphite, distearyl pent
  • Sulfur-based antioxidants include 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol.
  • Other oligomer and polymer type compounds having a thioether structure may also be used.
  • Benzotriazole-based antioxidants include oligomer and polymer type compounds that have a benzotriazole structure.
  • 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, and 2-hydroxy-4-chlorobenzophenone.
  • Other oligomer and polymer type compounds having a benzophenone structure may also be used.
  • Triazine-based antioxidants include 2,4-bis(allyl)-6-(2-hydroxyphenyl)1,3,5-triazine. Other oligomer and polymer compounds having a triazine structure may also be used.
  • salicylic acid ester antioxidants examples include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Other oligomer and polymer type compounds having a salicylic acid ester structure may also be used.
  • antioxidants can be used alone or in a mixture of two or more in any ratio as required.
  • the content of the antioxidant is preferably 0.5 to 5.0 mass % of the total solids (total non-volatile content) of the photosensitive coloring composition.
  • the composition may contain an adhesion improver such as a silane coupling agent to improve adhesion to the substrate.
  • 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.
  • Adhesion improvers 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-(amin
  • the content of the adhesion improver is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of colorant (A).
  • adhesion, resolution, and sensitivity are improved in a well-balanced manner.
  • the photosensitive coloring composition may contain a leveling agent.
  • a leveling agent dimethylsiloxane having a polyether structure or polyester structure in the main chain is preferable.
  • 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 Co., Ltd.
  • dimethylsiloxane having a polyester structure include BYK-310 and BYK-370 manufactured by BYK-Chemie Co., Ltd.
  • 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% by mass in the total solid content (total non-volatile content) of the photosensitive coloring composition.
  • the leveling agent may further contain an anionic, cationic, nonionic or amphoteric surfactant. Two or more types of surfactants may be mixed together.
  • anionic surfactants that are added auxiliary to the leveling agent 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, polyoxyethylene alkyl ether phosphates, and the like.
  • Cationic surfactants that can be added to the leveling agent as supplementary agents include alkyl quaternary ammonium salts and their ethylene oxide adducts.
  • Nonionic surfactants that can be added to the leveling agent as supplementary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, etc.; alkyl betaines such as alkyl dimethylamino acetate betaine, amphoteric surfactants such as alkyl imidazolines, and fluorine-based and silicone-based surfactants.
  • the present composition may contain a curing agent or a curing accelerator as necessary to assist the curing of the thermosetting resin.
  • a curing agent phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc. are effective, but are not limited to these, and any curing agent may be used as long as it can react with the thermosetting resin.
  • compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferred.
  • the curing accelerator examples include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4 ...
  • amine compounds e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenz
  • dazole 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.) can be used. These may be used alone or
  • the composition may contain a storage stabilizer to stabilize the viscosity over time.
  • storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl 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, phosphites, etc.
  • the storage stabilizer can be used in an amount of 0.1 to 10 parts by mass relative to 100 parts by mass of the colorant.
  • the composition may contain a solvent. This makes it easier to adjust the viscosity of the photosensitive coloring composition, making it easier 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.
  • solvents examples include ester solvents (solvents that contain -COO- in the molecule but do not contain -O-), ether solvents (solvents that contain -O- in the molecule but do not contain -COO-), ether ester solvents (solvents that contain -COO- and -O- in the molecule), ketone solvents (solvents that contain -CO- in the molecule but do not contain -COO-), alcohol solvents (solvents that contain OH in the molecule but do not contain -O-, -CO- or -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc.
  • ester solvent examples 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 ⁇ -butyrolactone.
  • ether solvent examples include ether solvents having no hydroxyl group and ether alcohol solvents (solvents containing -OH and -O- in the molecule).
  • ether alcohol solvent examples 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.
  • ether solvents having no hydroxyl group examples 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.
  • ether ester solvent examples 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, ethyl 3-methoxy ...
  • acetate acetate examples 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, and dipropylene glycol diacetate.
  • Ketone solvents include, for example, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.
  • alcohol solvents examples include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, and glycerin.
  • aromatic hydrocarbon solvents examples include benzene, toluene, xylene, and mesitylene.
  • amide solvents examples include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.
  • solvents with a boiling point of 120°C or higher and 245°C or lower at 1 atm are preferred in terms of application and drying properties.
  • solvents with a boiling point of 120°C or higher and 245°C or lower at 1 atm are preferred in terms of application and drying properties.
  • 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
  • propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, cyclohexanone, tripropylene glycol monomethyl ether, 3-methoxy-1-butanol, etc. are even more preferred.
  • 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, so they are preferably used in an amount of 200 to 900 parts by mass, and more preferably 300 to 570 parts by mass, per 100 parts by mass of the solids (non-volatile content) of the photosensitive coloring composition.
  • a dispersing aid such as a dye derivative, a resin-type dispersing agent, a surfactant, etc.
  • the dispersing aid has a large effect of preventing reagglomeration of the colorant after dispersion, so that the coloring composition in which the colorant is dispersed using the dispersing aid has good brightness and viscosity stability.
  • dye derivatives examples 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.
  • a basic substituent an acidic substituent
  • a phthalimidomethyl group which may have a substituent has been introduced into an organic pigment
  • an anthraquinone an acridone
  • triazine examples include 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.
  • 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.
  • 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, per 100 parts by mass of the colorant, from the viewpoint of improving dispersibility. Also, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by mass or less, and more preferably 35 parts by mass or less.
  • the resin type dispersant has a colorant affinity site that adsorbs to the colorant (A) and a relaxation site that has high affinity with components other than the colorant (A) and causes steric repulsion between dispersed particles.
  • the resin type dispersant may be, for example, a urethane-based dispersant such as polyurethane, a polycarboxylate ester such as polyacrylate, an unsaturated polyamide, a polycarboxylic acid, a polycarboxylate (partial) amine salt, an ammonium polycarboxylate salt, an alkylamine polycarboxylate salt, a polysiloxane, a long-chain polyaminoamide phosphate salt, a hydroxyl group-containing polycarboxylate ester, or a modified product thereof, an amide formed by the reaction of a poly(lower alkylene imine) with a polyester having a free carboxyl group, or an oil-based dispersant such as a salt thereof, a water-soluble resin or water-soluble polymer compound such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer,
  • resin-type dispersants include acidic functional group-containing resin-type dispersants and basic functional group-containing resin-type dispersants.
  • 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.
  • surfactant examples include anionic surfactants such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, 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 oleyl ether, poly
  • the amount is preferably 0.1 to 55 parts by mass, and more preferably 0.1 to 45 parts by mass, per 100 parts by mass of colorant.
  • the amount of resin-type dispersant or surfactant is 0.1 parts by mass or more, the effect of adding it is easily obtained, and when the content is 55 parts by mass or less, a moderate amount of dispersant has a good effect on dispersion.
  • the composition may contain a chain transfer agent.
  • the chain transfer agent is preferably a thiol-based chain transfer agent.
  • 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 not easily inhibited by oxygen during radical polymerization after irradiation with light is generated, and the sensitivity of the photosensitive coloring composition is improved.
  • the thiol chain transfer agent is preferably a multifunctional thiol having two or more thiol groups (SH groups), and more preferably has four or more SH groups. As the number of functional groups increases, the coating becomes easier to photocure from the surface to the deepest part.
  • polyfunctional thiols examples 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, and ethylene glycol bisthiopropionate.
  • thiopropionate examples include rhythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, and the like.
  • Preferred examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.
  • the thiol chain transfer agents can be used alone or in combination of two or more kinds.
  • the content of the thiol chain transfer agent is preferably 0.5 to 10 mass % of the total solids (total non-volatile content) of the coloring composition, and more preferably 1 to 8 mass %.
  • the taper shape, wrinkles, film shrinkage rate, photosensitivity, and pattern shape are further improved.
  • the photosensitive coloring composition can be prepared by mixing the above-mentioned components.
  • the components may be mixed at once, or may be mixed successively after dissolving or dispersing in an organic solvent.
  • 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 mixed and mixed in the dispersion to produce the composition.
  • the components to be mixed and the timing of mixing are arbitrary.
  • the dispersion process can also be performed multiple times.
  • the composition is preferably subjected to removal of coarse particles of 5 ⁇ m or more, preferably 1 ⁇ m or more, more preferably 0.5 ⁇ m or more, and particularly preferably 0.3 ⁇ m or more, as well as contaminated dust, by means of centrifugation, filtration using a sintered filter or membrane filter, or other such means.
  • FIG. 1 is a schematic cross-sectional view of the present device.
  • the 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 a driving element is formed. It may further include a sealing layer 4 and a cover glass 5, and may also include a flat layer (planar) between the organic EL layer 2 and the color filter 3 (not shown).
  • the organic EL display device may be a Micro-OLED (Organic Light-Emitting Diode) display device.
  • each component of the organic EL display device will be described in detail.
  • the color filter 3 shown in FIG. 1 is formed on the organic EL layer 2 and has at least a red pixel, a green pixel, and a blue pixel (3a, 3b, 3c).
  • the present composition can be used as a green photosensitive coloring composition. Therefore, the pixel (for example, a green pixel) can be composed of a cured film formed from the above-mentioned photosensitive coloring composition. That is, the pixel is a cured product of the above-mentioned photosensitive coloring composition, and the present device is equipped with a cured film formed from the present composition.
  • the color filter 3 may further have a magenta pixel, a cyan pixel, a yellow pixel, or other pixels.
  • the color filters are formed on the organic EL layer 2 or on a flat layer that is provided as necessary.
  • the flattening layer can be made of a known curable resin, preferably an ultraviolet-curable resin, and may be used in combination with a thermosetting resin if necessary.
  • the ultraviolet-curable resin is not particularly limited, but is preferably an acrylic resin that is sensitive to i-line (wavelength 365 nm).
  • each photosensitive coloring composition such as red and 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, spin coating, etc. to form a coating film.
  • a coating method such as spray coating, dip coating, bar coating, coal coating, spin coating, etc. to form a coating film.
  • the red photosensitive coloring composition and the blue photosensitive coloring composition are not particularly limited and may be appropriately selected from conventionally known compositions within the scope of the effects of the present disclosure.
  • the coating film is dried as necessary, and then exposed through a mask having a predetermined pattern to photopolymerize the photopolymerizable monomer and the photosensitive resin to form a cured coating film.
  • light sources used for exposure include ultraviolet light from a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and the like, and electron beams. The amount of exposure may be appropriately adjusted depending on the light source used and the thickness of the coating film.
  • a heat treatment may be carried out. Since the photosensitive composition has low-temperature curing properties, it can be sufficiently cured even by a heat treatment at 100° C. or less.
  • the thickness of the pixels that make up the color filter 3 is preferably 0.5 ⁇ m to 2.0 ⁇ m, and more preferably 1.0 to 2.0 ⁇ m.
  • the organic EL layer can be formed as an organic light-emitting single layer containing a light-emitting substance, or as a multilayer.
  • a multilayer structure for example, a three-layer structure in which a general hole transport layer, an electron transporting organic light-emitting layer, and an electron transport layer are sequentially laminated, or a multilayer structure in which a hole (electron) injection layer, a hole (electron) transport layer, and other layers having separate injection and transport functions, or a layer for blocking hole (electron) transport, may be provided.
  • an organic EL layer is one in which an anode, an organic layer, and a cathode are laminated in this order from the substrate side, and are hermetically covered with a sealing layer.
  • the anode is provided on the substrate and is made of a conductive material with a large work function.
  • conductive materials with a large work function include nickel, silver, gold, platinum, palladium, selenium, rhodium, ruthenium, iridium, rhenium, tungsten, molybdenum, chromium, tantalum, niobium, and alloys of these metals, as well as tin oxide (SnO2), indium tin oxide (ITO), zinc oxide, and titanium oxide.
  • the cathode is made of a conductive material with a small work function.
  • conductive materials can be, for example, alloys of active metals such as Li, Mg, Ca, etc. with metals such as Ag, Al, In, etc., or structures in which these are laminated.
  • a thin compound layer of an active metal such as Li, Mg, Ca, etc. with a halogen such as fluorine or bromine, or oxygen, etc., can be inserted between the organic layer.
  • the anodes and cathodes are patterned into a shape appropriate for the drive system of the display device.
  • the drive system 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 the organic EL elements.
  • the organic layer has at least a white light-emitting layer, but is usually composed of multiple organic layers, and can have charge injection layers such as a hole injection layer and an electron injection layer, and charge transport layers such as a hole transport layer that transports holes to the white light-emitting layer, and an electron transport layer that transports electrons to the white light-emitting layer.
  • charge injection layers such as a hole injection layer and an electron injection layer
  • charge transport layers such as a hole transport layer that transports holes to the white light-emitting layer, and an electron transport layer that transports electrons to the white light-emitting layer.
  • the light-emitting layer may be any known layer that can emit white light.
  • the white light-emitting characteristics require emission 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 will suffice as long as emission occurs in the above regions.
  • the material constituting such a white light-emitting layer is not particularly limited as long as it emits fluorescence or phosphorescence.
  • the light-emitting material may also have hole transport properties or electron transport properties. Examples of light-emitting materials include dye-based materials, metal complex-based materials, and polymer-based materials.
  • the above-mentioned 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, trifmanylamine derivatives, oxadiazole dimers, and pyrazoline dimers.
  • the above metal complex materials include aluminum quinolinol complexes, benzoquinolinol beryllium complexes, benzoxazole zinc complexes, benzothiazole zinc complexes, azomethyl zinc complexes, porphyrin zinc complexes, and europium complexes, or metal complexes having central metals such as Al, Zn, Be, etc. or rare earth metals such as Tb, Eu, Dy, etc., and having ligands such as oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, and quinoline structures, etc.
  • the above-mentioned polymeric materials include polyparaphenylenevinylene 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.
  • Methods for forming the white light-emitting layer include, for example, vapor deposition, printing, inkjet, or spin coating, casting, dipping, bar coating, blade coating, roll coating, gravure coating, flexographic printing, spray coating, and self-organization methods (layer-by-layer adsorption, self-assembled monolayer).
  • vapor deposition, spin coating, and inkjet methods are preferably used, and the thickness of the white light-emitting layer is usually about 5 nm to 5 ⁇ m.
  • the organic EL layer may also have a hole injection layer formed between the white light-emitting layer and the anode.
  • a hole injection layer formed between the white light-emitting layer and the anode.
  • the hole injection layer By providing the hole injection layer, the injection of holes into the white light-emitting layer can be stabilized, and the light-emitting efficiency can be increased.
  • Materials that are generally used for the hole injection layer of organic EL elements can be used as the material 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.
  • 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.
  • materials for forming the hole injection layer include porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds.
  • the thickness of the hole injection layer is usually about 5 nm to 1 ⁇ m.
  • the organic EL layer may also have an electron injection layer formed between the white light-emitting layer and the cathode.
  • an electron injection layer By providing the electron injection layer, the injection of electrons into the white light-emitting layer can be stabilized, and the luminous efficiency can be increased.
  • Materials for forming the electron injection layer include, for example, nitro-substituted fluorene derivatives, anthraquinodimethane derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, 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 replaced 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.
  • the Micro-LED display device includes a cured film formed from a photosensitive coloring composition for a Micro-LED display device having the same composition as that of the photosensitive coloring composition for an organic EL display device.
  • the Micro-LED display device according to the present disclosure may have a color filter on a (silicon) substrate on which the driving elements are formed. The substrate and the color filter are the same as those in the organic EL display device described above.
  • the other configurations of the present Micro-LED display device can be appropriately selected from the configurations of conventionally known Micro-LED display devices and are not particularly limited.
  • the display technology can be transferred to Micro-LED displays.
  • ⁇ Pigment Green 62 200 parts of green pigment C.I. Pigment Green 62 (manufactured by Toyo Color Co., Ltd.), 1400 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 product was put into 8000 parts of warm water, heated to 80° C. and stirred for 2 hours to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85° C. for one day to obtain a phthalocyanine-based fine green pigment (PG-1).
  • PG-1 phthalocyanine-based fine green pigment
  • PG-2 finely divided green pigment
  • Yellow Pigment (A2) ⁇ Pigment Yellow 139> Yellow pigment C.I. Pigment Yellow 139 (PY139) (BASF Japan "Irgaphor Yellow 2R-CF”) 100 parts, sodium chloride 1200 parts, and diethylene glycol 120 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 70 ° C. for 6 hours. This kneaded product was put into 3000 parts of warm water, heated to 70 ° C. and stirred for 1 hour to make a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours to obtain 98 parts of fine yellow pigment (PY-1). The average primary particle size was 40.2 nm.
  • PY185 Yellow pigment C.I. Pigment Yellow 185
  • BASF Japan "PALIOTOL YELLOW D1155" 100 parts, sodium chloride 700 parts, and diethylene glycol 180 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho Co., Ltd
  • Red pigment 100 parts of red pigment C.I. Pigment Red 254 (PR254) (BASF Japan "Irgaphor Red B-CF"), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C for 6 hours, and salt milled.
  • PR254 red pigment C.I. Pigment Red 254
  • Irgaphor Red B-CF 1200 parts of sodium chloride
  • diethylene glycol 120 parts
  • the kneaded product obtained was put into 3 liters of warm water, heated to 70 ° C and stirred for 1 hour to make a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C for 24 hours to obtain 98 parts of finely divided red pigment (PR-1).
  • the average primary particle size was 33 nm.
  • ⁇ Pigment Red 177> The same procedure as for the production of the red colorant (PR-29) was carried out except that the red pigment C.I. Pigment Red 254 was changed to C.I. Pigment Red 177 (PR177) ("Chromophthal Red A2B" manufactured by BASF Japan Ltd.), to obtain 97 parts of a finely divided red pigment (PR-2).
  • the average primary particle diameter was 27.6 nm.
  • Blue pigment ⁇ Pigment Blue 15:6> 200 parts of blue pigment C.I. Pigment Blue 15:6 ("LIONOL BLUE ES" manufactured by Toyocolor Co., Ltd., specific surface area 60 m2 /g), 1400 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.
  • this kneaded mixture was put into 8000 parts of warm water, heated to 80°C and stirred for 2 hours to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85°C for a whole day and night to obtain a phthalocyanine-based fine blue pigment (PB-1).
  • PB-1 phthalocyanine-based fine blue pigment
  • Resin-type dispersant solution 1 Photosensitive resin-type dispersant In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 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 were charged, and after replacing with nitrogen gas, the reaction was carried out at 120 ° C. for 5 hours (first step). It was confirmed by measuring the acid value that 95% or more of the acid anhydride was half-esterified.
  • PGMAc propylene glycol monomethyl ether acetate
  • MMA methyl methacrylate
  • tBA tert-butyl acrylate
  • EA ethyl acrylate
  • MAA methacrylic acid
  • BzMA benzyl methacrylate
  • HEMA 2-hydroxyethyl methacrylate
  • Resin-type dispersant solution 2 Non-photosensitive resin-type dispersant A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 30 parts of ethyl acrylate, 20 parts of tert-butyl acrylate, and 40 parts of 2-methyl methacrylate, and replaced with nitrogen gas. The reaction vessel was heated to 80°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile dissolved in 45.7 parts of cyclohexanone was added to 6 parts of 3-mercapto-1,2-propanediol, and reacted for 10 hours.
  • the non-volatile 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.
  • 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.
  • Photosensitive resin 100 parts of propylene glycol monomethyl ether acetate was put into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer in a separable 4-neck flask, and heated to 120 ° C. while injecting nitrogen gas into the vessel, and 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 dropped from the dropping tube at the same temperature over 2.5 hours to carry out a polymerization reaction.
  • Pigment Dispersion (P-1) ⁇ Production of Pigment Dispersion> (Pigment Dispersion (P-1))
  • the mixture below was stirred and mixed to become uniform, and then dispersed 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 for 3 hours.
  • the mixture was then filtered through a 5.0 ⁇ m filter to prepare a pigment dispersion (P-1) having a non-volatile component content of 18% by mass.
  • Resin type dispersant solution 2 15.8 parts
  • 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.
  • 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 units for the blending ratio of each component (pigment, resin-type dispersant solution, and PGMAc) in Tables 1 and 2 are parts by mass, and the unit for the non-volatile content is % by mass.
  • Photosensitive coloring compositions (G-2) to (G-10) Photosensitive coloring compositions (G-2 to G-10) were prepared in the same manner as the photosensitive coloring composition (G-1), except that the materials and blending amounts of the photosensitive coloring composition (G-1) were changed as shown in Tables 3 and 4.
  • the units in the blending ratios 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.
  • Leveling agent a solution obtained by dissolving 1 part of "FZ-2122" (manufactured by Dow Corning Toray Co., Ltd.) in 99 parts of propylene glycol monomethyl ether acetate (PGMAc)
  • 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. Thereafter, the substrate was spray-developed with a 0.2 mass% sodium carbonate aqueous solution at 23 ° C for 30 seconds, washed with ion-exchanged water, and air-dried. Further, post-baking was performed for 30 minutes at 230 ° C in a clean oven to form a pixel pattern with a film thickness of 1.5 ⁇ m on the substrate.
  • a resin solution obtained by adding 2.0 g of a silicon-based surfactant (KF351A, Shin-Etsu Silicone Co., Ltd.) to 1 kg of commercially available polyvinyl alcohol (concentration 5%) and stirring for 10 minutes was used to coat the pixel pattern with a film thickness of 1 ⁇ m using the same coating method as above, and dried.
  • the lightness (Y) of the obtained coating film was measured with a microspectrophotometer (Olympus Optical Co., Ltd. "OSP-SP200"). After that, the sample 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 amount of 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 a value less than 65.0 is not practical.
  • D The change in brightness before and after the light fastness test is 5.0 points or more, and the product is not suitable for practical use.
  • a photosensitive coloring composition (R-1) was prepared in the same manner as the photosensitive coloring composition (G-1), except that the materials and amounts of the photosensitive coloring composition (G-1) were changed as shown in Table 5. ) was obtained.
  • a photosensitive coloring composition (B-1) was prepared in the same manner as the photosensitive coloring composition (G-1), except that the materials and amounts of the photosensitive coloring composition (G-1) were changed as shown in Table 6. ) was obtained.
  • a TFT layer was formed on a silicon substrate by using a known method such as an etching method. 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 using a known method such as a vapor deposition method to form a white organic EL element, and then a passivation layer made of silicon nitride was formed and sealed by using a plasma CVD (Chemical Vapor Deposition) method to form an organic EL element substrate.
  • a plasma CVD Chemical Vapor Deposition
  • 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 ⁇ m, and the composition was exposed to i-line (wavelength: 365 nm) using a high pressure mercury lamp through a pattern mask at an illuminance of 20,000 W/ m2 , developed using an organic alkaline developer containing tetramethylammonium hydroxide as an alkaline agent, washed with water, and dried to form a green layer (G) of a color filter. After that, the composition was heated in a heating oven at 80° C. for 10 minutes for curing, completing the formation of the green layer (G) of a color filter.
  • the blue photosensitive resin composition was applied with a spinner so that the film thickness after curing was 1.5 ⁇ m, and exposed to i-line (wavelength: 365 nm) using a high-pressure mercury lamp through a pattern mask at an illuminance of 20,000 W/m 2 , developed using an organic alkaline developer containing tetramethylammonium hydroxide as an alkaline agent, washed with water, and dried to temporarily form the blue layer (B) of the color filter. After that, it was heated at 80 ° C. for 10 minutes in a heating oven to harden, and the formation of the blue layer (B) of the color filter was completed to produce a color filter.
  • 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 and less than 94% were evaluated as B, and those of less than 90% were evaluated as C.
  • 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 with a DCI-P3 area ratio of 90% or more but less than 94% were evaluated as B, and those with a DCI-P3 area ratio of less than 90% were evaluated as C.
  • 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.

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PCT/JP2024/013254 2023-03-31 2024-03-29 有機ＥＬ表示装置用感光性着色組成物、Ｍｉｃｒｏ－ＬＥＤ表示装置用感光性着色組成物、硬化膜、有機ＥＬ表示装置およびＭｉｃｒｏ－ＬＥＤ表示装置 Ceased WO2024204797A1 (ja)

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WO2021149596A1 (ja) * 2020-01-21 2021-07-29 富士フイルム株式会社 着色組成物、膜、光学フィルタ、固体撮像素子及び画像表示装置
WO2022224779A1 (ja) * 2021-04-22 2022-10-27 東洋インキＳｃホールディングス株式会社 有機ｅｌ表示装置
WO2023136028A1 (ja) * 2022-01-17 2023-07-20 富士フイルム株式会社 着色組成物、膜、構造体、カラーフィルタおよび表示装置

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WO2021149596A1 (ja) * 2020-01-21 2021-07-29 富士フイルム株式会社 着色組成物、膜、光学フィルタ、固体撮像素子及び画像表示装置
WO2022224779A1 (ja) * 2021-04-22 2022-10-27 東洋インキＳｃホールディングス株式会社 有機ｅｌ表示装置
WO2023136028A1 (ja) * 2022-01-17 2023-07-20 富士フイルム株式会社 着色組成物、膜、構造体、カラーフィルタおよび表示装置

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JPWO2022224779A1 (https=) * 2021-04-22 2022-10-27
JP7826296B2 (ja) 2021-04-22 2026-03-09 ａｒｔｉｅｎｃｅ株式会社 有機ｅｌ表示装置

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