Photocurable composition, pixel production method, film, optical filter, solid-state imaging element, and image display device

Abstract

This photocurable composition contains a photopolymerization initiator, a polymerizable compound, a colorant, a resin, and a polymerization inhibitor, wherein the photopolymerization initiator contains a compound represented by formula (1), and the resin includes a resin having an acid group. Further provided are a pixel production method, a film, an optical filter, a solid-state imaging element, and an image display device using the aforementioned photocurable composition.

Description

Photocurable composition, method for manufacturing pixels, film, optical filter, solid-state image sensor, and image display device.

[0001] This invention relates to a photocurable composition comprising a photopolymerization initiator and a polymerizable compound. Furthermore, this invention relates to a method for manufacturing pixels using the photocurable composition, a film, an optical filter, a solid-state image sensor, and an image display device.

[0002] Optical filters, such as color filters, have patterns (pixels) of films containing colorants. These patterns (pixels) are manufactured by forming patterns using a photocurable composition containing a colorant, a photopolymerization initiator, and a polymerizable compound, using a photolithography method.

[0003] Oxime compounds are known as photopolymerization initiators. Furthermore, Patent Document 1 describes a photocurable composition using a predetermined oxime ester compound as a photopolymerization initiator.

[0004] Chinese Patent Application Publication No. 117510396 Specification

[0005] According to the inventors' research, the photopolymerization initiator described in Patent Document 1 has high sensitivity, but the decomposition rate (radical generation amount) differs greatly depending on the exposure intensity. For example, even when exposed at the same exposure intensity, the amount of radicals generated tends to fluctuate greatly depending on the exposure intensity. Thus, the photopolymerization initiator described in Patent Document 1 was difficult to use effectively. For this reason, when a photocurable composition using the photopolymerization initiator described in Patent Document 1 is exposed at high intensity, a large amount of radicals are generated by the exposure, and the excess radicals diffuse through the film, tending to thicken the pattern line width. There was room for improvement in terms of exposure intensity dependence.

[0006] Therefore, an object of the present invention is to provide a photocurable composition that has good sensitivity and low dependence on exposure illuminance. Another object of the present invention is to provide a method for manufacturing pixels, a film, an optical filter, a solid-state image sensor, and an image display device.

[0007] Through the inventors' research, it was discovered that the above objective can be achieved by a photocurable composition described later, and thus the present invention was completed. Therefore, the present invention provides the following.

[0008] <1> A photocurable composition comprising a photopolymerization initiator, a polymerizable compound, a colorant, a resin, and a polymerization inhibitor, wherein the photopolymerization initiator comprises a compound represented by formula (1), and the resin comprises a resin having an acid group; In formula (1), R １ and R ２ Each of these independently represents a substituent, where m represents 1 or 0, n represents 1 or 0, x represents 1 or 0, y represents 1 or 0, and z represents 1 or 0. <2> R in formula (1) above １ and R ２ The photocurable composition according to <1>, wherein each of the elements independently represents an alkyl group, an aryl group, or a heteroaryl group. <3> The R of formula (1) above １ and R ２ The photocurable composition according to <1>, wherein each of the groups independently represents a methyl group, an ethyl group, or a phenyl group. <4> The photocurable composition according to <1>, wherein the compound represented by formula (1) is a compound represented by any of the formulas (A-1) to (A-13). <5> The photocurable composition according to <4>, wherein the compound represented by formula (1) is a compound represented by any of the formulas (A-1) to (A-3). <6> The photocurable composition according to any one of <1> to <5>, wherein the acid value of the resin having the acid group is 50 to 100 mg KOH / g. <7> The photocurable composition according to any one of <1> to <6>, wherein the polymerization inhibitor contains an N-oxy radical compound having a six-membered ring structure. <8> A method for manufacturing a pixel, comprising the steps of: forming a composition layer on a support using the photocurable composition according to any one of <1> to <7>; irradiating the composition layer with light of a wavelength of 150 to 400 nm to expose it in a pattern; and developing and removing the unexposed parts of the composition layer. <9> A film obtained by curing the photocurable composition according to any one of <1> to <7>. <10> An optical filter containing the film according to <9>. <11> A solid-state image sensor containing the film according to <9>. <12> An image display device containing the film described in <9>.

[0009] According to the present invention, it is possible to provide a photocurable composition that has good sensitivity and low dependence on exposure illuminance. Furthermore, the present invention can provide a method for manufacturing pixels, a film, an optical filter, a solid-state image sensor, and an image display device.

[0010] The present invention will be described in detail below. In this specification, "~" is used to mean that the numerical values ​​before and after it are included as the lower and upper limits. In the notation of groups (atomic groups) in this specification, notations that do not specify substituted or unsubstituted include both groups (atomic groups) with substituents and groups (atomic groups) without substituents. For example, "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. In addition, examples of light used for exposure include the emission line spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light or radiation. In this specification, "(meth)acrylate" refers to both acrylate and methacrylate, or either of them; "(meth)acrylic" refers to both acrylic and methacrylic, or either of them; and "(meth)acryloyl" refers to both acryloyl and methacryloyl, or either of them. In this specification, Me in structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, weight-average molecular weight and number-average molecular weight are polystyrene equivalent values ​​measured by GPC (gel permeation chromatography). In this specification, total solids refer to the total mass of components of a composition excluding the solvent. In this specification, pigment refers to a colorant that is poorly soluble in solvents. In this specification, the term "process" includes not only independent processes, but also processes that cannot be clearly distinguished from other processes, as long as the intended function of that process is achieved.

[0011] <Photocurable Composition> The photocurable composition of the present invention comprises a photopolymerization initiator, a polymerizable compound, a resin, a colorant, and a polymerization inhibitor, wherein the photopolymerization initiator comprises a compound represented by formula (1), and the resin comprises a resin having an acid group.

[0012] The photocurable composition of the present invention exhibits good sensitivity and low dependence on exposure illuminance, enabling the formation of pixels with the desired pattern line width even when exposed at low or high illuminance. The reason for these effects is presumed to be as follows.

[0013] The compound represented by formula (1) has two ketoxime structures in one molecule, so it can efficiently generate radicals upon exposure. For this reason, the photocurable composition of the present invention containing the compound represented by formula (1) has excellent sensitivity. On the other hand, the compound represented by formula (1) has a large difference in decomposition rate (amount of radical generation) depending on the exposure intensity, and even with the same exposure intensity, exposure at high intensity tends to generate a large amount of radicals compared to exposure at low intensity. However, since the photocurable composition of the present invention further contains a polymerization inhibitor, even when exposed at high intensity, the excess radicals generated can be deactivated by the polymerization inhibitor. For this reason, the photocurable composition of the present invention can suppress the occurrence of pattern line width thickening even when exposed at high intensity. In addition, since the photocurable composition of the present invention contains a resin having an acid group, its developability is improved, so the pattern edges hardened by excess radicals can be removed by development, further suppressing pattern line width thickening at high intensity. Furthermore, since the compound represented by formula (1) has excellent sensitivity, it can generate sufficient radicals even when exposed at low intensity. Therefore, even when exposed to low light, the film in the exposed area can be sufficiently cured, and the narrowing of the pattern line width can be suppressed. For these reasons, the photocurable composition of the present invention has good sensitivity and low dependence on exposure light intensity.

[0014] Furthermore, since the photocurable composition of the present invention contains a resin having an acidic group, it has good affinity with developing solutions and excellent developability. In particular, when developing with an alkaline developing solution, the generation of developing residue can be further suppressed, and even when using an alkaline developing solution with a low alkali concentration, the generation of developing residue can be suppressed. Therefore, even if there is variation in the alkali concentration of the alkaline developing solution, the generation of developing residue can be suppressed.

[0015] The photocurable composition of the present invention is preferably used as a photocurable composition for optical filters. Examples of optical filters include color filters, infrared transmission filters, and infrared cut filters, with color filters being preferred.

[0016] Examples of color filters include filters having colored pixels that transmit light of a specific wavelength. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. The colored pixels of a color filter can be formed using a photocurable composition containing a chromatic colorant.

[0017] The maximum absorption wavelength of the infrared cut filter is preferably in the range of 700 to 1800 nm, more preferably in the range of 700 to 1300 nm, and even more preferably in the range of 700 to 1000 nm. Furthermore, the transmittance of the infrared cut filter over the entire range of wavelengths from 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. Furthermore, the transmittance at at least one point in the range of wavelengths from 700 to 1800 nm is preferably 20% or less. In addition, the ratio of the absorbance Amax at the maximum absorption wavelength of the infrared cut filter to the absorbance A550 at a wavelength of 550 nm (absorbance Amax / absorbance A550) is preferably 20 to 500, more preferably 50 to 500, even more preferably 70 to 450, and particularly preferably 100 to 400. The infrared cut filter can be formed using a photocurable composition containing an infrared absorbing colorant.

[0018] An infrared transmission filter is a filter that transmits at least a portion of infrared light. Preferably, an infrared transmission filter is a filter that blocks at least a portion of visible light and transmits at least a portion of infrared light. Preferred infrared transmission filters include filters that satisfy spectral characteristics such as a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1300 nm. Preferably, an infrared transmission filter is a filter that satisfies any of the following spectral characteristics (1) to (5): (1): A filter in which the maximum transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the minimum transmittance in the wavelength range of 800 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more). (2) A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 750 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 900 to 1500 nm. (3) A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 830 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1000 to 1500 nm. (4) A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 950 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1500 nm. (5) A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 1050 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1200 to 1500 nm.

[0019] The photocurable composition of the present invention can also be used for a light-shielding film or the like.

[0020] The solid content concentration of the photocurable composition of the present invention is preferably 5 to 30% by mass. The lower limit is preferably 7.5% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.

[0021] The photocurable composition of the present invention can obtain high sensitivity when exposed to light having a wavelength of 150 to 400 nm. Therefore, the photocurable composition of the present invention is preferably used as a photocurable composition for exposure with light having a wavelength of 150 to 400 nm. Examples of the light having a wavelength of 150 to 400 nm include i-line (wavelength 365 nm), KrF line (wavelength 248 nm), ArF line (wavelength 193 nm), etc., and it is preferably i-line (wavelength 365 nm) or KrF line (wavelength 248 nm). The light having a wavelength of 150 to 400 nm is preferably excimer laser light having a wavelength of 150 to 400 nm.

[0022] Hereinafter, each component used in the photocurable composition of the present invention will be described.

[0023] <<Photopolymerization initiator>> The photocurable composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is preferably a photo radical polymerization initiator.

[0024] (Specific compound) In the photocurable composition of the present invention, the photopolymerization initiator used is one containing a compound represented by formula (1). Hereinafter, the compound represented by formula (1) is also referred to as a specific compound.

[0025]

[0026] In formula (1), R １ and R ２ each independently represent a substituent, m represents 1 or 0, n represents 1 or 0, x represents 1 or 0, y represents 1 or 0, and z represents 1 or 0.

[0027] R １ and R ２The substituents represented by include alkyl groups, alkenyl groups, aryl groups, and heteroaryl groups.

[0028] The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 or 2, and particularly preferably 1. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have substituents, but is preferably an unsubstituted alkyl group. Examples of substituents include aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthio groups, arylthio groups, heteroarylthio groups, alkylamino groups, arylamino groups, nitro groups, halogen atoms, acyl groups, and acyloxy groups.

[0029] The number of carbon atoms in the above alkenyl group is preferably 2 to 10, and more preferably 2 to 5. The alkenyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The above alkenyl group may have substituents, but is preferably an unsubstituted alkenyl group. Examples of substituents include aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthio groups, arylthio groups, heteroarylthio groups, alkylamino groups, arylamino groups, nitro groups, halogen atoms, acyl groups, acyloxy groups, and the like.

[0030] The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12, and even more preferably 6. The aryl group may be a monocyclic or fused ring. The aryl group may have substituents, but it is preferable that it be an unsubstituted aryl group. Examples of substituents include alkyl groups, alkenyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthio groups, arylthio groups, heteroarylthio groups, alkylamino groups, arylamino groups, nitro groups, halogen atoms, acyl groups, acyloxy groups, and the like.

[0031] The number of carbon atoms constituting the ring of the heteroaryl group described above is preferably 1 to 15, and more preferably 1 to 10. Examples of heteroatoms constituting the ring of the heteroaryl group include nitrogen atoms, oxygen atoms, and sulfur atoms. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3, and more preferably 1 to 2. The heteroaryl group may be a monoring or a fused ring. The heteroaryl group described above may have substituents, but it is preferable that it be an unsubstituted heteroaryl group. Examples of substituents include alkyl groups, alkenyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthio groups, arylthio groups, heteroarylthio groups, alkylamino groups, arylamino groups, nitro groups, halogen atoms, acyl groups, acyloxy groups, and the like.

[0032] R in equation (1) １ and R ２ From the viewpoint of sensitivity, each is preferably an alkyl group, an aryl group, or a heteroaryl group, more preferably an alkyl group or an aryl group, and even more preferably an alkyl group. １ and R ２ From the viewpoint of sensitivity, each of these groups is independently preferably a methyl group, an ethyl group, or a phenyl group, more preferably a methyl group or a phenyl group, and even more preferably a methyl group.

[0033] In formula (1), m represents 1 or 0, and is preferably 1. In formula (1), n ​​represents 1 or 0, and is preferably 1. In formula (1), x represents 1 or 0, and is preferably 1. In formula (1), y represents 1 or 0, and is preferably 1. In formula (1), z represents 1 or 0, and is preferably 1.

[0034] The specific compound can be synthesized by the method described in paragraphs 0033-0038 and 0044-0080 of Chinese Patent Application Publication No. 117510396. Specific examples of the specific compound include compounds represented by formulas (A-1) to (A-13) shown below, preferably compounds represented by any of formulas (A-1) to (A-3), and more preferably compounds represented by formula (A-1).

[0035] The photocurable composition of the present invention may use only one of the above-mentioned specific compounds, or it may use two or more in combination.

[0036] (Other Photopolymerization Initiators) The photocurable composition of the present invention may further contain photopolymerization initiators other than the specified compounds described above (hereinafter also referred to as other photopolymerization initiators). When the specified compounds described above and other photopolymerization initiators are used in combination, the content of the other photopolymerization initiators is preferably 1 to 1,000 parts by mass per 100 parts by mass of the specified compounds. The upper limit is preferably 500 parts by mass or less, and more preferably 200 parts by mass or less. The lower limit is preferably 10 parts by mass or more, and more preferably 50 parts by mass or more.

[0037] Other photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, and glyoxylate compounds. Other photopolymerization initiators are preferably trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, hexaarylbiimidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, glyoxylate compounds, halomethyloxadiazole compounds, or 3-arylsubstituted coumarin compounds; more preferably oxime compounds, α-hydroxyketone compounds, α-aminoketone compounds, glyoxylate compounds, or acylphosphine compounds; even more preferably α-aminoketone compounds, glyoxylate compounds, or oxime compounds; and particularly preferably oxime compounds.

[0038] Other photopolymerization initiators include the compounds described in paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, the compounds described in Japanese Patent Publication No. 6301489, and MATERIAL STAGE 37-60p, vol. 19, No. 3. Peroxide-based photopolymerization initiators described in 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in JP 2019-043864, photopolymerization initiators described in JP 2019-044030, peroxide-based initiators described in JP 2019-167313, aminoacetophenone-based initiators having an oxazolidine group described in JP 2020-055992, JP 2013- Oxime-based photopolymerization initiator described in Japanese Patent Publication No. 190459, polymer described in Japanese Patent Application Publication No. 2020-172619, compound represented by formula 1 described in International Publication No. 2020 / 152120, compound described in Japanese Patent Application Publication No. 2021-181406, photopolymerization initiator described in Japanese Patent Application Publication No. 2022-013379, compound represented by formula (1) described in Japanese Patent Application Publication No. 2022-015747, fluorine-containing fluorene oxime ester-based photoinitiator described in Japanese Patent Application Publication No. 2021-507058, Chinese Patent Application Publication No. 11 Initiators described in Specification No. 0764367, initiators described in Japanese Patent Publication No. 2022-518535, initiators described in International Publication No. 2021 / 175855, compounds described in Taiwan Patent Application Publication No. 202200534, compounds described in Japanese Patent Application Publication No. 2022-078550, compounds described in Korean Published Patent No. 10-2017-0087330, compounds described in International Publication No. 2022 / 075452, oxime ester compounds described in Chinese Patent Application Publication No. 110066225, Korean Compounds described in Japanese Patent Publication No. 10-2022-0076157, compounds described in paragraphs 0042-0062 of International Publication No. 2019 / 013112 having a triarylamine or N-arylcarbazole skeleton, oxime ester-based photopolymerization initiators described in Japanese Patent Publication No. 7219378, photopolymerization initiators described in Korean Published Patent No. 10-2021-0146174, photopolymerization initiators described in International Publication No. 2019 / 013112, photopolymerization initiators described in Japanese Patent Publication No. 2023-033731,Initiators described in Japanese Patent Publication No. 2022-515524, initiators described in Japanese Patent Publication No. 2023-517304, initiators described in Chinese Patent Application Publication No. 114149517, aminoketone compounds described in Chinese Patent Application Publication No. 115925596, compounds described in Japanese Patent Application Publication No. 2023-159489, compounds described in Japanese Patent Application Publication No. 2023-159487, compounds described in Taiwan Patent Application Publication No. 202336003, compounds described in Chinese Patent Application Publication No. 113527138, organosilicon compounds described in Japanese Patent Publication No. 2022-502526, Korean Published Patent Examples include the oxime compound described in Japanese Patent Publication No. 10-2017-0009794, the photopolymerization initiator described in Korean Published Patent Publication No. 10-2023-0033862, the oxime ester compound described in Japanese Patent Publication No. 2019-519518, the polyfunctional polymer photopolymerization initiator described in Japanese Patent Publication No. 2024-517534, the photopolymerization initiator described in International Publication No. 2024 / 085227, the compound described in Japanese Patent Publication No. 2024-521379, the photopolymerization initiator described in Japanese Patent Publication No. 2024-523053, and the oxime ester initiator described in Chinese Patent Application Publication No. 117510396.

[0039] Specific examples of hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole.

[0040] Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins B.V.), and Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (all manufactured by BASF). Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins B.V.), and Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG (all manufactured by BASF). Commercially available acylphosphine compounds include Omnirad 819 and Omnirad TPO (both manufactured by IGM Resins B.V.), and Irgacure 819 and Irgacure TPO (both manufactured by BASF). Examples of commercially available glyoxylate compounds include Esacure 563 (manufactured by IGM Resins B.V.).

[0041] Examples of oxime compounds include the compounds described in paragraph 0142 of International Publication No. 2022 / 085485, the compounds described in Japanese Patent No. 5430746, the compounds described in Japanese Patent No. 5647738, the compounds represented by general formula (1) and the compounds described in paragraphs 0022 to 0024 of Japanese Patent Publication No. 2021-173858, and the compounds represented by general formula (1) and the compounds described in paragraphs 0117 to 0120 of Japanese Patent Publication No. 2021-170089. Specific examples of oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one, and 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime). Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04, Irgacure OXE05 (all manufactured by BASF), TR-PBG-301, TR-PBG-304, TR-PBG-305, TR-PBG-309, TR-PBG-3054, TR-PBG-3057, TR-PBG-314, TR-PBG-327, TR-PBG-345, TR-PBG-346, TR- Examples include PBG-358, TR-PBG-365, TR-PBG-380, TR-PBG-610, TR-PBG-A, TR-PBG-B (all manufactured by TRONLY), and ADEKA Optomer N-1919 (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in Japanese Patent Publication No. 2012-014052). Furthermore, it is also preferable to use compounds that do not produce color or compounds that are highly transparent and resistant to discoloration as oxime compounds. Examples of commercially available products include ADEKA Arclus NCI-730, NCI-831, NCI-831E, and NCI-930 (all manufactured by ADEKA Corporation).

[0042] Other photopolymerization initiators may include oxime compounds having a fluorene ring, oxime compounds having a skeleton in which at least one benzene ring of the carbazole ring is replaced by a naphthalene ring, oxime compounds having a fluorine atom, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, oxime compounds in which a substituent having a hydroxyl group is attached to the carbazole skeleton, and compounds described in paragraphs 0143 to 0149 of International Publication No. 2022 / 085485.

[0043] As an alternative photopolymerization initiator, the compound represented by formula (OX-1) can also be used.

[0044] In formula (OX-1), X １ａ R represents a divalent linking group containing at least one selected from the group consisting of aromatic rings and heterocycles. １ａ R represents a hydrogen atom or an acyl group. ２ａ R represents an alkyl or aryl group. ３ａ and R ４ａ Each of these independently represents a hydrogen atom or an alkyl group, and Alk １ and Alk ２ Each of these independently represents an alkyl group, R ３ａ and R ４ａ They may be bonded together to form a ring, Alk １ and Alk ２ The elements may be joined together to form a ring, and n represents either 0 or 1.

[0045] X in equation (OX-1) １ａ Examples of divalent linking groups represented by include divalent aromatic ring groups, divalent heterocyclic groups, divalent groups formed by linking two or more aromatic ring groups via single bonds or linking groups, divalent groups formed by linking two or more heterocyclic groups via single bonds or linking groups, and divalent groups formed by linking an aromatic ring group and a heterocyclic group via single bonds or linking groups. Examples of linking groups that link aromatic ring groups to each other, heterocyclic groups to each other, or an aromatic ring group and a heterocyclic group include -CH ２ -, -O-, -CO-, -S-, -NR ｘ - And combinations thereof, etc. are examples. ｘThis represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.

[0046] X in equation (OX-1) １ａ It is preferably a group represented by any of formulas (X-1) to (X-13), more preferably a group represented by formula (X-1), formula (X-2), formula (X-4), formula (X-6), or formula (X-8), and even more preferably a group represented by formula (X-2) or formula (X-6).

[0047] In the formula R Ｘ１ ~R Ｘ９ Each of these independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, and * represents a bond.

[0048] R Ｘ１ ~R Ｘ９ The alkyl group represented by is preferably 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched, or cyclic. The alkyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, and heteroaryl groups.

[0049] R Ｘ１ ~R Ｘ９ The number of carbon atoms in the alkenyl group represented by is preferably 2 to 15, and more preferably 2 to 10. The alkenyl group may be linear, branched, or cyclic. The alkenyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, and heteroaryl groups.

[0050] R Ｘ１ ~R Ｘ９ The alkynyl group represented by is preferably 2 to 15 carbon atoms, and more preferably 2 to 10 carbon atoms. The alkynyl group may be linear, branched, or cyclic. The alkynyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, and heteroaryl groups.

[0051] R Ｘ１ ~R Ｘ９The number of carbon atoms in the aryl group represented by is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and heteroaryl groups.

[0052] R Ｘ１ ~R Ｘ９ The heteroaryl group represented by is preferably a five-membered or six-membered ring. The heteroatoms of the heteroaryl group are preferably oxygen, nitrogen, and sulfur atoms. The number of heteroatoms of the heteroaryl group is preferably 1 to 3. The heteroaryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

[0053] R in equation (OX-1) １ａ represents a hydrogen atom or an acyl group, and an acyl group is preferred.

[0054] R in equation (OX-1) ２ａ R represents an alkyl group or an aryl group, and is preferably an alkyl group because the generated radical is highly reactive. ２ａ The number of carbon atoms in the alkyl group represented by is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have substituents, but is preferably an unsubstituted alkyl group. ２ａ The alkyl group represented by is preferably an unsubstituted linear or branched alkyl group, and more preferably an unsubstituted linear alkyl group. ２ａ The number of carbon atoms in the aryl group represented by is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents, but it is preferably an unsubstituted aryl group.

[0055] R in equation (OX-1) ３ａ and R ４ａEach of these independently represents a hydrogen atom or an alkyl group, and a hydrogen atom is preferred. ３ａ and R ４ａ The number of carbon atoms in the alkyl group represented by is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have substituents, but is preferably an unsubstituted alkyl group. ３ａ and R ４ａ These may be bonded together to form a ring. The formed ring is preferably a five-membered or six-membered ring, and more preferably a five-membered or six-membered aliphatic hydrocarbon ring.

[0056] Alk in equation (OX-1) １ and Alk ２ Each of these independently represents an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have substituents, but is preferably an unsubstituted alkyl group. Alk １ and Alk ２ The elements may be bonded together to form a ring, and it is preferable that a ring is formed. The formed ring is preferably a five-membered or six-membered ring, more preferably a five-membered or six-membered aliphatic hydrocarbon ring, and even more preferably a cyclopentane ring or a cyclohexane ring.

[0057] In formula (OX-1), n ​​represents either 0 or 1, and is preferably 0.

[0058] Specific examples of compounds represented by formula (OX-1) include the compounds described in paragraphs 0092 to 0096 of Japanese Patent Publication No. 2012-113104 and the compounds described in paragraph 0041 of Japanese Patent Publication No. 2012-189997.

[0059] As an alternative photopolymerization initiator, the compound represented by formula (OX-2) can also be used.

[0060]

[0061] In formula (OX-2), R １ｂ and R ２ｂ Each of these independently represents a substituent, R ３ｂ ~R ７ｂ Each of these independently represents a hydrogen atom or a substituent, and Ar １ｂ represents an optionally substituted aryl group or an optionally substituted heteroaryl group, and n represents 0 or 1.

[0062] R １ｂ and R ２ｂ The substituents represented by include alkyl groups and aryl groups, with alkyl groups being preferred. The number of carbon atoms in the alkyl group is preferably 1 to 15, and more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic. The alkyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, alkenyl groups, alkynyl groups, and heteroaryl groups. The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and heteroaryl groups.

[0063] R ３ｂ ~R ７ｂ The substituents represented by include halogen atoms, alkyl groups, and aryl groups. Examples of alkyl groups and aryl groups are those mentioned above. ３ｂ ~R ７ｂ It is preferable that it is a hydrogen atom.

[0064] Ar １ｂ Ar represents an optionally substituted aryl group or an optionally substituted heteroaryl group. １ｂIt is preferable that the group is an aryl group which may have substituents. The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylthio groups, arylthio groups, nitro groups, and acyl groups, with acyl groups being preferred.

[0065] As an alternative photopolymerization initiator, the compound represented by formula (OX-3) can also be used.

[0066]

[0067] In formula (OX-3), Ar １ｃ Ar represents an aromatic ring group with (k+m+1) valency or a heterocyclic ring group with (k+m+1) valency. ２ｃ R represents a (k+2) valent aromatic ring group or a (k+2) valent heterocyclic group, １ｃ ~R ３ｃ Each of these independently represents a substituent, L １ｃ is a single bond or CR １１ｃ R １２ｃ Represents R １１ｃ and R １２ｃ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, X １ｃ ha-CH ２ It represents -, -N-, -O-, or -S-, where k represents 0 or 1, m represents an integer from 0 to 4, and n represents 0 or 1.

[0068] R １ｃ and R ２ｃExamples of the substituent represented by [ [ ID = 0 ] ] are an alkyl group and an aryl group, among which an alkyl group is preferred. The number of carbon atoms of the alkyl group is preferably 1 to 15, more preferably 1 to 10. The alkyl group may be linear, branched or cyclic. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkenyl group, an alkynyl group, a heteroaryl group, etc. The number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a heteroaryl group, etc. R [ [ END ] ] ２ｃ is preferably an alkyl group having a branched or cyclic structure.

[0069] R [ [ END ] ] ３ｃ Examples of the substituent represented by [ [ ID = 7 ] ] include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group and an acyl group, among which an acyl group is preferred.

[0070] L [ [ END ] ] １ｃ is a single bond or CR [ [ END ] ] １１ｃ R [ [ END ] ] １２ｃ represents, and R [ [ END ] ] １１ｃ and R [ [ END ] ] １２ｃ each independently represent a hydrogen atom, an alkyl group or an aryl group. R [ [ END ] ] １１ｃ and R [ [ END ] ] １２ｃ The alkyl group and aryl group in [ [ ID = 24 ] ] are synonymous with the alkyl group and aryl group in R [ [ END ] ] １ｃ and R [ [ END ] ] ２ｃ When k is 1, L [ [ END ] ] １ｃ is preferably a single bond.

[0071] X [ [ END ] ] １ｃ represents -CH [ [ END ] ]... ２ -, -N-, -O- or -S-, among which -O- or -S- is preferred.

[0072] Ar [ [ END ] ] １ｃrepresents a (k+m+1) valent aromatic ring group or a (k+m+1) valent heterocyclic group, and is preferably a (k+m+1) valent aromatic ring group. The aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.

[0073] Ar ２ｃ represents a (k+2) valent aromatic ring group or a (k+2) valent heterocyclic group, and is preferably a (k+2) valent aromatic ring group. The aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.

[0074] k represents 0 or 1, preferably 0. m represents an integer from 0 to 4, preferably 0 or 1, more preferably 1. n represents 0 or 1, preferably 0.

[0075] Other photopolymerization initiators that can be suitably used include ketoxime ester compounds having an allyl oil oxy group at the ortho position, represented by formula (OX-4). Examples of such compounds include those described in Chinese Patent Application Publication No. 117342977.

[0076] In formula (OX-4), R １ｄ and R ２ｄ Each of these independently represents an alkyl group, an aryl group, or a heterocyclic group; R ３ｄ , R ４ｄ , R ５ｄ , R ６ｄ These are, independently, hydrogen atoms, halogen atoms, CN, and NO. ２ CF ３ ,R,OR,SR,SOR,SO ２ R represents R or NRR', where R and R' each independently represent an alkyl group or an aryl group, and when R and R' are present together, R and R' may be bonded to form a ring, and one or more -CH groups in the alkyl group or aryl group represented by R and R' ２ Each of the hyphens may be independently substituted with -O-, -N-, -S-, -CO-, -COO-, -OCO-, or a benzene ring; R ７ｄ , R８ｄ and R ９ｄ Each of these independently represents either a hydrogen atom or a methyl group.

[0077] Other photopolymerization initiators that can be suitably used include compounds represented by formula (OX-5). Examples of such compounds include those described in International Publication No. 2024 / 101219.

[0078] In formula (OX-5), R １ｅ ~R ５ｅ Each of these independently represents a hydrocarbon group which may have substituents, and n represents an integer from 0 to 4.

[0079] Specific examples of oxime compounds used as other photopolymerization initiators include the following compounds.

[0080]

[0081] The content of the photopolymerization initiator in the total solid content of the photocurable composition is preferably 1 to 20% by mass. The lower limit is preferably 1.5% by mass or more, and more preferably 2% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less. In the photocurable composition of the present invention, only one type of photopolymerization initiator may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount is within the above range.

[0082] The content of the specific compound in the photopolymerization initiator is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

[0083] The content of the specific compound in the total solid content of the photocurable composition is preferably 0.1 to 50% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. In the photocurable composition of the present invention, only one specific compound may be used, or two or more may be used. When two or more are used, it is preferable that their total amount is within the above range.

[0084] <<Polymerizable Compounds>> The photocurable composition of the present invention contains polymerizable compounds. Examples of polymerizable compounds include compounds having an ethylenically unsaturated bond-containing group. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, allyl groups, and (meth)acryloyl groups. The polymerizable compound used in the present invention is preferably a radical polymerizable compound.

[0085] The polymerizable compound may be in any chemical form, such as monomer, prepolymer, or oligomer, but monomer is preferred. The molecular weight of the polymerizable compound is preferably 100 to 3000. The upper limit is more preferably 2000 or less, and even more preferably 1500 or less. The lower limit is more preferably 150 or more, and even more preferably 250 or more.

[0086] The polymerizable compound is preferably a compound containing two or more ethylenically unsaturated bond-containing groups, more preferably a compound containing two to fifteen ethylenically unsaturated bond-containing groups, and even more preferably a compound containing two to six ethylenically unsaturated bond-containing groups. Furthermore, the polymerizable compound is preferably a (meth)acrylate compound with 2 to 15 functions, and more preferably a (meth)acrylate compound with 2 to 6 functions. Specific examples of polymerizable compounds include the compounds described in paragraphs 0075 to 0083 of International Publication No. 2022 / 065215 and the compounds described in Taiwan Patent Application Publication No. 201832008.

[0087] Preferred polymerizable compounds include dipentaerythritol tri(meth)acrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and compounds in which the (meth)acryloyl groups of these compounds are linked via ethylene glycol and / or propylene glycol residues (for example, SR454 and SR499, commercially available from Sartomer).Furthermore, polymerizable compounds include diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available as M-460; manufactured by Toagosei), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., NK Ester A-TMMT), and 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD). HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.), 8UH-1 006, 8UH-1012 (both manufactured by Taisei Fine Chemical Co., Ltd.), Light Acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), Arronix MT-3041, 3042 (manufactured by Toagosei Co., Ltd., polymerizable compound containing amine), Arronix M-510, 520 (manufactured by Toagosei Co., Ltd., polymerizable compound having an acidic group), Etercure 6361-100 (Eternal Materials Inc. (a polymerizable compound with a hyperbranched structure), EBECRYL80 (a tetrafunctional monomer containing an amine, manufactured by Daicel-Orkenes Corporation), EBECRYL7100 (a difunctional monomer containing an amine, manufactured by Daicel-Orkenes Corporation), CN371NS (a difunctional monomer containing an amine, manufactured by Arkema Corporation), HOA-MPL (2-acryloyloxyethyl phthalate, manufactured by Kyoeisha Chemical Co., Ltd.), HOA-MPE (2-acryloyloxyethyl-2-hydroxyethyl phthalate, manufactured by Kyoeisha Chemical Co., Ltd.) Other polymerizable compounds that can be used include those described in Japanese Patent Publication No. 2023-043479 (manufactured by Daicel Ornex Co., Ltd.), polymerizable compounds that have a dendrimer structure or a hyperbranch structure, those described in Japanese Patent Publication No. 2023-529984, polymerizable compounds that contain a urethane bond as described in Japanese Patent Publication No. 2024-070237, EBECRYL 5129 (manufactured by Daicel Ornex Co., Ltd.), EBECRYL 220 (manufactured by Daicel Ornex Co., Ltd.), KUA-9N (manufactured by KSM Co., Ltd.), and polymerizable compounds described in Japanese Patent Publication No. 2024-085753.

[0088] As the polymerizable compound, a polymerizable compound having an ethylene oxide repeating chain can also be used. In this embodiment, the effects of the present invention are exhibited more significantly. Examples of polymerizable compounds having an ethylene oxide repeating chain include the compound represented by formula (EO-1).

[0089] R in equation (EO-1) Ｅ１ represents a hydrogen atom or a methyl group.

[0090] L in equation (EO-1) Ｅ１ L represents a linking group with m-valence. Ｅ１ The linking groups represented by m-valence are hydrocarbon groups, heterocyclic groups, -O-, -S-, and -NR Ａ１ -, -CO-, -COO-, -OCO-, -SO ２ - And groups formed by combining two or more of these groups, etc. Ａ１ The group represents a hydrogen atom, an alkyl group, or an aryl group, with a hydrogen atom being preferred. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be cyclic or acyclic. The acyclic aliphatic hydrocarbon group may be a straight-chain aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The hydrocarbon group may have substituents or may not have substituents. The cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be monocyclic or fused rings. The heterocyclic group may be monocyclic or fused rings. A five-membered ring or a six-membered ring is preferred for the heterocyclic group. The heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. Examples of heteroatoms constituting the heterocyclic group include nitrogen atoms, oxygen atoms, and sulfur atoms.

[0091] In formula (EO-1), n ​​represents an integer from 1 to 20, and m represents an integer from 2 to 10. Preferably, n is an integer from 1 to 15, and more preferably from 1 to 10. Preferably, m is an integer from 2 to 8, and more preferably from 2 to 6.

[0092] As polymerizable compounds, polymerizable compounds having a fluorene skeleton can also be used. The polymerizable compound having a fluorene skeleton is preferably a bifunctional polymerizable compound. Examples of commercially available polymerizable compounds having a fluorene skeleton include Ogusol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., (meth)acrylate monomers having a fluorene skeleton).

[0093] As polymerizable compounds, polymerizable compounds having an amino group and an ethylenically unsaturated bond-containing group (hereinafter also referred to as amine monomers) can also be used. By using amine monomers, the effects of the present invention are exhibited more significantly.

[0094] The amine monomer is preferably a compound containing 1 to 10 ethylenically unsaturated bond-containing groups, more preferably a compound containing 2 to 10 groups, and even more preferably a compound containing 3 to 10 groups.

[0095] The pKaH of the amine monomer is preferably 5.5 or higher, more preferably 6.5 or higher, and even more preferably 7.5 or higher, because this enhances the effect of suppressing oxygen inhibition by the amine and further increases the sensitivity of the photocurable composition. Note that pKaH is a value representing the pKa of the conjugate acid of the base. In this specification, the pKaH value of the amine monomer is the value calculated according to the method described in A Web Server for Small Molecular pKa Prediction Using a Graph-Convolutional Neural Network J. Chem. Inf. Model. 2021, 61, 7, 3159-3165.

[0096] The ethylenically unsaturated bond content value (C=C value) of the amine monomer is preferably 0.5 to 11 mmol / g. The upper limit is preferably 10 mmol / g or less, and more preferably 9 mmol / g or less. The lower limit is preferably 1 mmol / g or more, and more preferably 2 mmol / g or more. The ethylenically unsaturated bond content value of the amine monomer is a numerical value representing the molar amount of ethylenically unsaturated bond-containing groups per gram of solid content of the amine monomer.

[0097] The amine value of the amine monomer is preferably 1 to 150 mg KOH / g. The lower limit of the amine value is preferably 2.5 mg KOH / g or higher, and more preferably 5 mg KOH / g or higher. The upper limit of the amine value is preferably 125 mg KOH / g or lower, and more preferably 100 mg KOH / g or lower.

[0098] The hydroxyl value of the amine monomer is preferably 75 mg KOH / g or less, more preferably 50 mg KOH / g or less, and even more preferably 30 mg KOH / g or less.

[0099] The molecular weight of the amine monomer is preferably 100 to 5000, and more preferably 200 to 3000.

[0100] The content of polymerizable compounds in the total solids of the photocurable composition is preferably 1 to 30% by mass. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. The lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more. The photocurable composition of the present invention may contain only one polymerizable compound or two or more polymerizable compounds. If two or more polymerizable compounds are included, it is preferable that their total amount falls within the above range.

[0101] <<Resin>> The photocurable composition of the present invention contains a resin. The resin is used, for example, to disperse pigments and the like in the photocurable composition, or as a binder. A resin used primarily to disperse pigments and the like in the photocurable composition is also called a dispersant. However, such uses of the resin are just examples, and the resin can also be used for purposes other than those mentioned above.

[0102] The weight-average molecular weight (Mw) of the resin is preferably between 3,000 and 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 4,000 or more, and more preferably 5,000 or more.

[0103] Examples of resins include (meth)acrylic resins, epoxy resins, (meth)acrylamide resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene etherphosphine oxide resins, polyurethane resins, polyamide resins, polyimide resins, polyamic acid resins, polybenzoxazole resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and siloxane resins. Preferably, the resin is at least one selected from (meth)acrylic resins, polyester resins, polyurethane resins, polyamide resins, polyimide resins, polyamic acid resins, and polybenzoxazole resins. Polyimide resins and polyamic acid resins are obtained by polycondensation of aromatic acid dianhydrides or aliphatic acid dianhydrides with aromatic diamines or aliphatic diamines. Polyimide resins and polyamic acid resins may have crosslinkable groups. Examples of crosslinkable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, allyl groups, (meth)acryloyl groups, and styrene groups. Examples of cyclic ether groups include epoxy groups and oxetanyl groups. Polyimide resins and polyamic acid resins can also be resins obtained by introducing a crosslinkable group into a polyimide or polyamic acid having a carboxylic acid as described in Japanese Patent Publication No. 2023-166413, polyimide resins or polyamic acid resins as described in International Publication No. 2022 / 019253, block resins having poly(meth)acrylic, polyether, or polyester structures or combinations thereof at both ends of a polyimide resin or polyamic acid resin as described in International Publication No. 2022 / 019254, or resins having both a polyester substructure with a graft polymer portion and a polyamic acid substructure as described in International Publication No. 2022 / 019255.

[0104] The resins include the resins described in paragraphs 0091 to 0099 of International Publication No. 2022 / 065215, the blocked polyisocyanate resin described in Japanese Patent Publication No. 2016-222891, the resin described in Japanese Patent Publication No. 2020-122052, the resin described in Japanese Patent Publication No. 2020-111656, the resin described in Japanese Patent Publication No. 2020-139021, and Japanese Patent Publication No. 2017-138503. A resin comprising a structural unit having a ring structure in the main chain and a structural unit having a biphenyl group in the side chain as described in the publication, a resin described in paragraphs 0199 to 0233 of Japanese Patent Application Publication No. 2020-186373, an alkali-soluble resin described in Japanese Patent Application Publication No. 2020-186325, a resin represented by formula 1 described in Korean Published Patent No. 10-2020-0078339, and a resin described in International Publication No. 2022 / 030445 Copolymer containing epoxy groups and acid groups, resin described in Japanese Patent Publication No. 2018-135514, copolymer described in Japanese Patent Publication No. 2020-041046, resin described in Japanese Patent Publication No. 2023-033156, resin described in Japanese Patent Publication No. 2023-030386, resin described in Japanese Patent Publication No. 2023-027753, resin described in Japanese Patent Publication No. 2020-139021, Japanese Patent Publication No. 2023-074038 The resins described in the publications, the resins described in Japanese Patent Application Publication No. 2023-079666, the cardo resins described in Chinese Patent Application Publication No. 115947929, the copolymers described in Japanese Patent Application Publication No. 2024-014141, the resins described in Japanese Patent Application Publication No. 2024-050148, the copolymers described in International Publication No. 2024 / 134926, and the resins described in Japanese Patent Application Publication No. 2024-088596 may also be used.

[0105] The photocurable composition of the present invention uses a resin containing an acidic group. Examples of acidic groups include carboxyl groups, phosphate groups, sulfo groups, and phenolic hydroxyl groups, with carboxyl groups being preferred.

[0106] The acid value of the resin containing acidic groups is preferably 30 to 500 mg KOH / g. The lower limit is preferably 40 mg KOH / g or more, and more preferably 50 mg KOH / g or more. The upper limit is preferably 300 mg KOH / g or less, and more preferably 100 mg KOH / g or less. From the viewpoint of balancing developability and sensitivity, the acid value of the resin containing acidic groups is particularly preferably 50 to 100 mg KOH / g.

[0107] The weight-average molecular weight (Mw) of the resin having acid groups is preferably 5,000 to 100,000. The upper limit is preferably 80,000 or less, and more preferably 60,000 or less. The lower limit is preferably 6,000 or more, and more preferably 8,000 or more.

[0108] Resins having acidic groups preferably contain repeating units having acidic groups in their side chains, and more preferably contain repeating units having acidic groups in their side chains in an amount of 5 to 70 mol% of the total repeating units of the resin. The upper limit of the content of repeating units having acidic groups in their side chains is preferably 50 mol% or less, and more preferably 30 mol% or less. The lower limit of the content of repeating units having acidic groups in their side chains is preferably 10 mol% or more, and more preferably 20 mol% or more.

[0109] The resin having acidic groups is also preferably a resin having aromatic carboxyl groups. In a resin having aromatic carboxyl groups, the aromatic carboxyl groups may be included in the main chain of the repeating unit or in the side chain of the repeating unit. It is preferable that the aromatic carboxyl groups are included in the main chain of the repeating unit. In this specification, an aromatic carboxyl group is a group having a structure in which one or more carboxyl groups are bonded to an aromatic ring. In an aromatic carboxyl group, the number of carboxyl groups bonded to the aromatic ring is preferably 1 to 4, and more preferably 1 to 2. Examples of resins having aromatic carboxyl groups include the resins described in paragraphs 0082 to 0107 of International Publication No. 2021 / 166858.

[0110] Regarding resins having acid groups, reference can be made to paragraphs 0558-0571 of Japanese Patent Application Publication No. 2012-208494 (paragraphs 0685-0700 of the corresponding US Patent Application Publication No. 2012 / 0235099) and paragraphs 0076-0099 of Japanese Patent Application Publication No. 2012-198408, the contents of which are incorporated herein by reference. Furthermore, commercially available resins having acid groups can also be used. There are no particular restrictions on the method of introducing acid groups into the resin, but for example, the method described in Japanese Patent No. 6349629 can be cited. In addition, as a method of introducing acid groups into the resin, a method can be cited in which an acid anhydride is reacted with a hydroxyl group produced by a ring-opening reaction of an epoxy group to introduce an acid group.

[0111] The resin having acidic groups is preferably a resin having graft chains (hereinafter also referred to as an acidic graft resin). According to this embodiment, the occurrence of defects during pixel formation can be suppressed more effectively.

[0112] In this specification, a graft chain refers to a polymer chain that branches off from the main chain of repeating units. The graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and even more preferably 60 to 500 atoms excluding hydrogen atoms. The graft chain preferably contains repeating units of at least one structure selected from polyether, polyester, poly(meth)acrylic, polystyrene, polyurethane, polyurea, and polyamide structures, more preferably at least one structure selected from polyether, polyester, poly(meth)acrylic, and polystyrene structures, even more preferably a repeating unit of polyether or polyester, and particularly preferably a repeating unit of polyester.

[0113] Examples of repeating units for polyester structures include those represented by formulas (G-1), (G-4), or (G-5). Examples of repeating units for polyether structures include those represented by formula (G-2). Examples of repeating units for poly(meth)acrylic structures include those represented by formula (G-3). Examples of repeating units for polystyrene structures include those represented by formula (G-6).

[0114]

[0115] In the above formula, R Ｇ１ and R Ｇ２ Each of these independently represents an alkylene group. Ｇ１ The number of carbon atoms in the alkylene group represented by is preferably 1 to 20, more preferably 2 to 16, and even more preferably 2 to 12. The alkylene group is preferably linear or branched, and more preferably linear. Ｇ２ The number of carbon atoms in the alkylene group represented by is preferably 1 to 10, more preferably 1 to 5, even more preferably 2 to 5, and even more preferably 2 or 3. The alkylene group is preferably linear or branched, and more preferably linear.

[0116] In the above formula, R Ｇ３ Q represents a hydrogen atom or a methyl group. Ｇ１ represents -O- or -NH-, L Ｇ１ R represents a single bond or a divalent linking group. Ｇ４ represents a hydrogen atom or substituent.

[0117] L Ｇ１ The divalent linking groups represented by include alkylene groups (preferably alkylene groups having 1 to 12 carbon atoms), alkylene oxy groups (preferably alkylene oxy groups having 1 to 12 carbon atoms), oxyalkylene carbonyl groups (preferably oxyalkylene carbonyl groups having 1 to 12 carbon atoms), arylene groups (preferably arylene groups having 6 to 20 carbon atoms), -NH-, -SO-, and -SO ２Examples of groups include -, -CO-, -O-, -COO-, OCO-, -S-, and combinations of two or more of these.

[0118] R Ｇ４ Examples of substituents represented by include hydroxyl groups, carboxyl groups, alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthioether groups, arylthioether groups, heteroarylthioether groups, ethylenically unsaturated bond-containing groups, epoxy groups, oxetanyl groups, and blocked isocyanate groups.

[0119] R Ｇ５ R represents a hydrogen atom or a methyl group. Ｇ６ R represents an aryl group. Ｇ６ The number of carbon atoms in the aryl group represented by is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. Ｇ６ The aryl group represented by may have substituents. Examples of substituents include hydroxyl groups, carboxyl groups, alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthioether groups, arylthioether groups, heteroarylthioether groups, ethylenically unsaturated bond-containing groups, epoxy groups, oxetanyl groups, and blocked isocyanate groups.

[0120] The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. An example of a substituent is the group represented by formula (W-1).

[0121] -L ｗ１ -R ｗ１ ...(W-1) In the formula, L ｗ１ R represents a single bond or a divalent linking group. ｗ１ This represents an alkyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthioether group, arylthioether group, or heteroarylthioether group.

[0122] L ｗ１The divalent linking groups represented by include alkylene groups (preferably alkylene groups having 1 to 10 carbon atoms), arylene groups (preferably arylene groups having 6 to 20 carbon atoms), -NH-, -SO-, and -SO ２ -, -CO-, -O-, -COO-, OCO-, -CONR Ｌ１ Examples include -, -S-, and groups combining two or more of these groups. Ｌ１ represents a hydrogen atom, an alkyl group, or an aryl group.

[0123] R ｗ１ It is preferable that this is an alkyl group or an alkoxy group.

[0124] The graft chain is preferably structured as shown in formula (G-1a), formula (G-2a), formula (G-3a), formula (G-4a), formula (G-5a), or formula (G-6a), and more preferably as shown in formula (G-1a), formula (G-4a), or formula (G-5a).

[0125]

[0126] In the above formula, R Ｇ１ and R Ｇ２ Each of these represents an alkylene group, R Ｇ３ Q represents a hydrogen atom or a methyl group. Ｇ１ represents -O- or -NH-, L Ｇ１ R represents a single bond or a divalent linking group. Ｇ４ R represents a hydrogen atom or substituent. Ｇ５ R represents a hydrogen atom or a methyl group. Ｇ６ represents an aryl group, W １００ R represents a hydrogen atom or substituent, and n1 to n6 each independently represent an integer of 2 or more. Ｇ１ ~R Ｇ６ Q Ｇ１ , L Ｇ１ For this, see R explained in equations (G-1) to (G-6). Ｇ１ ~R Ｇ６ Q Ｇ１ , L Ｇ１ This is synonymous with the same thing, and the preferred range is also similar.

[0127] In equations (G-1a) to (G-6a), W １００It is preferable that the substituent is a substituent. Examples of substituents include the group represented by formula (W-1) described above.

[0128] In formulas (G-1a) to (G-6a), n1 to n6 are preferably integers from 2 to 100, more preferably integers from 2 to 80, and even more preferably integers from 8 to 60.

[0129] In formula (G-1a), when n1 is 2 or more, R in each repeating unit Ｇ１ The same elements may be identical or different. Also, R Ｇ１ When it contains two or more different repeating units, the arrangement of each repeating unit is not particularly limited and may be random, alternating, or block. The same applies to formulas (G-2a) to (G-6a). Furthermore, the graft chain has a structure represented by formula (G-1a), formula (G-4a), or formula (G-5a), and R Ｇ１ It is also preferable that the structure includes two or more different repeating units.

[0130] The acidic graft resin is preferably a resin having repeating units having graft chains and repeating units having acid groups. An example of a repeating unit having graft chains is the repeating unit represented by formula (e3).

[0131] In the formula, A ｅ３０ represents a trivalent linking group, L ｅ３０ represents a single bond or a divalent linking group, W ｅ３０ This represents a graft chain.

[0132] A ｅ３０ Examples of trivalent linking groups represented by include poly(meth)acrylic linking groups, polyalkyleneimine linking groups, polyester linking groups, polyurethane linking groups, polyurea linking groups, polyamide linking groups, polyether linking groups, and polystyrene linking groups. It is preferable that the linking group be a poly(meth)acrylic linking group or a polyalkyleneimine linking group, and more preferably a poly(meth)acrylic linking group.

[0133] L ｅ３０The divalent linking groups represented by include alkylene groups (preferably alkylene groups having 1 to 10 carbon atoms), arylene groups (preferably arylene groups having 6 to 20 carbon atoms), -NH-, -SO-, and -SO ２ -, -CO-, -O-, -COO-, OCO-, -CONR ｘ３ Examples include -, -S-, and groups combining two or more of these groups. ｘ３ represents a hydrogen atom, an alkyl group, or an aryl group. The alkylene group and arylene group may have substituents.

[0134] W ｅ３０ The graft chains represented by this include the graft chains mentioned above.

[0135] The content of repeating units having graft chains is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 3 mol% or more, of the total repeating units of the acidic graft resin. The upper limit may be 90 mol% or less, 80 mol% or less, or 70 mol% or less.

[0136] The content of repeating units having acid groups is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 3 mol% or more, of the total repeating units of the acid graft resin. The upper limit may be 90 mol% or less, 80 mol% or less, or 70 mol% or less.

[0137] The acidic graft resin may further contain repeating units having crosslinkable groups. Examples of crosslinkable groups include vinyl groups, allyl groups, (meth)acryloyl groups and other ethylenically unsaturated bond-containing groups, epoxy groups, and cyclic ether groups such as oxetanyl groups. The content of repeating units having crosslinkable groups is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 3 mol% or more, of the total repeating units of the acidic graft resin. The upper limit may be 90 mol% or less, 80 mol% or less, or 70 mol% or less.

[0138] As the acidic graft resin, a resin containing repeating units represented by formula (Ac-2) can also be used. In formula (Ac-2), Ar １０ L represents a group containing an aromatic carboxyl group. １１ represents -COO- or -CONH-, L １２ represents a trivalent linking group, P １０ represents a polymer chain.

[0139] Ar in equation (Ac-2) １０ Groups containing aromatic carboxyl groups represented by include structures derived from aromatic tricarboxylic acid anhydrides and structures derived from aromatic tetracarboxylic acid anhydrides. Examples of aromatic tricarboxylic acid anhydrides and aromatic tetracarboxylic acid anhydrides include compounds with the following structures.

[0140] In the above formula, Q １ These are single bonds, -O-, -CO-, -COOCH ２ CH ２ OCO-, -SO ２ -, -C(CF ３ ) ２ - represents a group represented by the following formula (Q-1) or a group represented by the following formula (Q-2).

[0141] Ar １０ The group containing the aromatic carboxyl group represented by Ar may also have a crosslinking group. １０ Specific examples of groups containing aromatic carboxyl groups represented by include the group represented by formula (Ar-11), the group represented by formula (Ar-12), and the group represented by formula (Ar-13).

[0142] In formula (Ar-11), n1 represents an integer from 1 to 4, preferably 1 or 2, and more preferably 2. In formula (Ar-12), n2 represents an integer from 1 to 8, preferably 1 to 4, more preferably 1 or 2, and even more preferably 2. In formula (Ar-13), n3 and n4 each independently represent an integer from 0 to 4, preferably 0 to 2, more preferably 1 or 2, and even more preferably 1. However, at least one of n3 and n4 is an integer of 1 or more. In formula (Ar-13), Q １ These are single bonds, -O-, -CO-, -COOCH ２ CH ２ OCO-, -SO ２ -, -C(CF ３ ) ２ - represents the group represented by formula (Q-1) or the group represented by formula (Q-2). In formulas (Ar-11) to (Ar-13), *1 is L １０ This indicates the connection point with [the other element].

[0143] L in equation (Ac-2) １１ This represents -COO- or -CONH-, and is preferably -COO-.

[0144] L in equation (Ac-2) １２ The trivalent linking group represented by includes hydrocarbon groups, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and groups combining two or more of these. Hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10. The hydrocarbon group may have substituents. Examples of substituents include hydroxyl groups. １２ The trivalent linking group represented by is preferably the group represented by formula (L12-1), and more preferably the group represented by formula (L12-2).

[0145] In formula (L12-1), L１２ｂ represents a trivalent linking group, X １ represents S, and *1 is L in equation (Ac-2). １１ This indicates the bonding position, and *2 is P in equation (Ac-2). １０ This indicates the connection position with L. １２ｂ Examples of trivalent linking groups represented by include hydrocarbon groups; groups formed by combining a hydrocarbon group with at least one selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-, and it is preferable that the group is a hydrocarbon group or a group formed by combining a hydrocarbon group with -O-.

[0146] In formula (L12-2), L １２ｃ represents a trivalent linking group, X １ represents S, and *1 is L in equation (Ac-2). １１ This indicates the bonding position, and *2 is P in equation (Ac-2). １０ This indicates the connection position with L. １２ｃ Examples of the trivalent linking group represented by include hydrocarbon groups; and groups formed by combining a hydrocarbon group with at least one selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-, with hydrocarbon groups being preferred.

[0147] P in equation (Ac-2) １０ The polymer chain represented by [formula] includes polymer chains containing repeating units of at least one structure selected from the group consisting of polyester structures, polyether structures, poly(meth)acrylic structures, polystyrene structures, polyurethane structures, polyurea structures, and polyamide structures. Examples of repeating units of polyester structures include repeating units of structures represented by formulas (G-1), (G-4), or (G-5) above. Examples of repeating units of polyether structures include repeating units of structures represented by formula (G-2) above. Examples of repeating units of poly(meth)acrylic structures include repeating units of structures represented by formula (G-3) above. Examples of repeating units of polystyrene structures include repeating units of structures represented by formula (G-6) above.

[0148] P １０ The polymer chain represented by may include repeating units having crosslinkable groups. １０If the polymer chain represented by contains repeating units having crosslinkable groups, P １０ The proportion of repeating units having crosslinkable groups among all repeating units constituting the structure is preferably 1 mol% or more, and more preferably 1 to 80 mol%. The upper limit is preferably 70 mol% or less, and more preferably 60 mol% or less. The lower limit is preferably 2 mol% or more, and more preferably 5 mol% or more.

[0149] P １０ The polymer chain represented by may contain repeating units containing acid groups. Examples of acid groups include carboxyl groups, phosphate groups, sulfo groups, and phenolic hydroxyl groups. １０ If the polymer chain represented by contains repeating units having acidic groups, P １０ The proportion of repeating units having acidic groups among all repeating units constituting the material is preferably 1 to 80 mol%, more preferably 5 to 80 mol%, and even more preferably 10 to 80 mol%.

[0150] P １０ The weight-average molecular weight of the polymer chain represented by is preferably 500 to 20000. The lower limit is preferably 1000 or more. The upper limit is preferably 10000 or less, more preferably 5000 or less, and even more preferably 3000 or less.

[0151] The weight-average molecular weight of the acidic graft resin is preferably 5,000 to 100,000. The upper limit is preferably 80,000 or less, and more preferably 60,000 or less. The lower limit is preferably 6,000 or more, and more preferably 8,000 or more.

[0152] The acid value of the acidic graft resin is preferably 30 to 500 mg KOH / g. The lower limit is preferably 40 mg KOH / g or more, and more preferably 50 mg KOH / g or more. The upper limit is preferably 300 mg KOH / g or less, and more preferably 100 mg KOH / g or less. From the viewpoint of balancing developability and sensitivity, the acid value of the acidic graft resin is particularly preferably 50 to 100 mg KOH / g.

[0153] The photocurable composition of the present invention may also use a resin having a basic group. The resin having a basic group is preferably a resin containing repeating units having a basic group in its side chain, more preferably a copolymer having repeating units having a basic group in its side chain and repeating units not having a basic group, and even more preferably a block copolymer having repeating units having a basic group in its side chain and repeating units not having a basic group. The resin having a basic group can also be used as a dispersant. The amine value of the resin having a basic group is preferably 5 to 300 mg KOH / g. The lower limit is preferably 10 mg KOH / g or more, and more preferably 20 mg KOH / g or more. The upper limit is preferably 200 mg KOH / g or less, and more preferably 100 mg KOH / g or less.

[0154] Commercially available resins containing basic groups include DISPERBY K-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919 (all manufactured by Bic Chemie), and Solspers 112. Examples include 00, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 7100 (all manufactured by Lubrizol Japan), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), etc. Furthermore, the resin having basic groups may also be the block copolymer (B) described in paragraphs 0063 to 0112 of Japanese Patent Application Publication No. 2014-219665, the block copolymer A1 described in paragraphs 0046 to 0076 of Japanese Patent Application Publication No. 2018-156021, or the vinyl resin having basic groups described in paragraphs 0150 to 0153 of Japanese Patent Application Publication No. 2019-184763, the details of which are incorporated herein by reference.

[0155] The photocurable composition of the present invention preferably contains a resin as a dispersant. Examples of dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, an acidic dispersant (acidic resin) refers to a resin in which the amount of acidic groups is greater than the amount of basic groups. As an acidic dispersant (acidic resin), it is preferable that the amount of acidic groups is 70 mol% or more when the total amount of acidic groups and basic groups is 100 mol%. The acidic group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mg KOH / g. Furthermore, a basic dispersant (basic resin) refers to a resin in which the amount of basic groups is greater than the amount of acidic groups. As a basic dispersant (basic resin), it is preferable that the amount of basic groups exceeds 50 mol% when the total amount of acidic groups and basic groups is 100 mol%. The basic group of the basic dispersant is preferably an amino group.

[0156] The resin used as a dispersant is preferably a graft resin. The resin used as a dispersant is also preferably the acidic graft resin described above.

[0157] The resin used as a dispersant is preferably a polyimine-based dispersant containing a nitrogen atom in at least one of its main chain and side chains. Preferably, the polyimine-based dispersant has a main chain having a substructure with functional groups having a pKa of 14 or less, and side chains with 40 to 10,000 atoms, and contains a basic nitrogen atom in at least one of its main chain and side chains. The basic nitrogen atom is not particularly limited as long as it exhibits basic properties. For polyimine-based dispersants, refer to paragraphs 0102 to 0166 of Japanese Patent Application Publication No. 2012-255128, the contents of which are incorporated herein by reference.

[0158] The resin used as a dispersant is preferably a resin with a structure in which multiple polymer chains are bonded to the core. Examples of such resins include dendrimers (including star-shaped polymers). Specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of Japanese Patent Application Publication No. 2013-043962.

[0159] The resin used as a dispersant is preferably a resin containing repeating units having ethylenically unsaturated bond-containing groups in their side chains. The content of repeating units having ethylenically unsaturated bond-containing groups in their side chains is preferably 10 mol% or more, more preferably 10 to 80 mol%, and even more preferably 20 to 70 mol% of the total repeating units of the resin.

[0160] As a dispersant, the resin described in Japanese Patent Publication No. 2018-087939, the block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6432077, polyethyleneimine having polyester side chains as described in International Publication No. 2016 / 104803, the block copolymer described in International Publication No. 2019 / 125940, the block polymer having acrylamide structural units as described in Japanese Patent Publication No. 2020-066687, and the acrylic polymer described in Japanese Patent Publication No. 2020-066688. Block polymers having lylamide structural units, dispersants described in International Publication No. 2016 / 104803, triazine compounds described in Korean Patent Publication No. 10-2017-0129400, dispersants described in Japanese Patent Application Publication No. 2024-050950, triazine compounds described in Korean Patent Publication No. 10-2017-0129416, aryl-modified branched reaction products described in Japanese Patent Application Publication No. 2024-510115, pigment dispersants described in Chinese Patent Application Publication No. 109554004, and the like can also be used.

[0161] Dispersants are also available commercially, and specific examples include the DISPERBYK series from BYK Chemie, the SOLSPERSE series from Lubrizol Nippon, the Efka series from BASF, and the Azisper series from Ajinomoto Fine Techno Co., Ltd. In addition, the products described in paragraph 0129 of Japanese Patent Publication No. 2012-137564 and paragraph 0235 of Japanese Patent Publication No. 2017-194662 can also be used as dispersants.

[0162] The resin content in the total solids of the photocurable composition is preferably 1 to 50% by mass. The upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less. The lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more.

[0163] The content of the resin having acid groups in the total solid content of the photocurable composition is preferably 1 to 50% by mass. The upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less. The lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more.

[0164] The content of the resin having acid groups in the resin contained in the photocurable composition is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and even more preferably 80% by mass or more.

[0165] The photocurable composition of the present invention may contain only one type of resin, or it may contain two or more types of resins. When it contains two or more types of resins, it is preferable that their total amount is within the above range.

[0166] <<Colorants>> The photocurable composition of the present invention contains colorants. Examples of colorants include white colorants, black colorants, chromatic colorants, and infrared absorbing colorants. In this invention, the white colorants include not only pure white but also light gray colorants that are close to white (e.g., off-white, light gray, etc.).

[0167] The colorant may be a pigment or a dye. A combination of pigments and dyes may also be used. The pigment may be either an inorganic or organic pigment, but organic pigments are preferred from the viewpoint of a wide range of color variations, ease of dispersion, and safety. It is preferable that the colorant contains a pigment.

[0168] The average primary particle diameter of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, and more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less. In this specification, the primary particle diameter of the pigment can be determined by observing the primary particles of the pigment with a transmission electron microscope and obtaining the resulting photograph. Specifically, the projected area of ​​the primary particles of the pigment is determined, and the corresponding equivalent circle diameter is calculated as the primary particle diameter of the pigment.

[0169] The crystallite size, determined from the full width at half maximum of the peaks originating from any crystal plane in the X-ray diffraction spectrum of the pigment when CuKα rays are used as the X-ray source, is preferably 0.1 to 100 nm, more preferably 0.5 to 50 nm, even more preferably 1 to 30 nm, and particularly preferably 5 to 25 nm.

[0170] The specific surface area of ​​the pigment is 1 to 300 m². ２ It is preferable that it be / g. The lower limit is 10m ２ It is preferable that it be 30m or more per gram. ２ It is more preferable that the amount is 1 / g or more. The upper limit is 250m ２ It is preferable that the amount is less than or equal to 200m ２ It is more preferable that the value be less than or equal to / g. The specific surface area can be measured according to the BET (Brunauer, Emmett, and Teller) method and DIN 66131: determination of the specific surface area of ​​solids by gas adsorption.

[0171] (Chromatic pigments) Examples of chromatic pigments include pigments that have a maximum absorption wavelength in the range of 400 to 700 nm. Examples include green pigments, red pigments, yellow pigments, purple pigments, blue pigments, and orange pigments.

[0172] Examples of red colorants include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, and thioindigo compounds. Diketopyrrolopyrrole compounds, anthraquinone compounds, and azo compounds are preferred, and diketopyrrolopyrrole compounds are more preferred. Furthermore, the red colorant is preferably a pigment (red pigment), and more preferably a diketopyrrolopyrrole pigment.

[0173] Specific examples of red pigments include C.I. (Color Index) Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, Examples of red pigments include 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, 279, 291, 294, 295, 296, and 297. In addition, as red colorants, compounds described in paragraph 0034 of International Publication No. 2022 / 085485 and brominated diketopyrrolopyrrole compounds described in Japanese Patent Application Publication No. 2020-085947 can also be used.

[0174] As the red colorant, C.I. Pigment Red 122, 177, 224, 254, 255, 264, 269, 272, and 291 are preferred, C.I. Pigment Red 254, 264, and 272 are more preferred, and C.I. Pigment Red 254 and 264 are even more preferred.

[0175] Examples of green colorants include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred. Furthermore, the green colorant is preferably a pigment (green pigment), and more preferably a phthalocyanine pigment.

[0176] Specific examples of green colorants include green pigments such as C.I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66. Alternatively, zinc phthalocyanine halides, which have an average of 10 to 14 halogen atoms, 8 to 12 bromine atoms, and 2 to 5 chlorine atoms per molecule, can be used as green colorants. Specific examples include the compounds described in International Publication No. 2015 / 118720. Furthermore, compounds described in paragraph 0029 of International Publication No. 2022 / 085485, aluminum phthalocyanine compounds described in Japanese Patent Publication No. 2020-070426, and diarylmethane compounds described in Japanese Patent Publication No. 2020-504758 can also be used as green colorants.

[0177] As for the green coloring agent, C.I. Pigment Green 7, 36, 58, 62, and 63 are preferred.

[0178] Examples of orange colorants include diketopyrrolopyrrole compounds and azo compounds. Preferably, the orange colorant is a pigment (orange pigment). Specific examples of orange colorants include C.I. Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, and 73 orange pigments.

[0179] Examples of yellow colorants include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds, and perylene compounds. The yellow colorant is preferably a pigment (yellow pigment). Specific examples of yellow colorants include C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125 Examples of yellow pigments include 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228, 231, 232, 233, 234, 235, and 236.

[0180] As a yellow coloring agent, a nickel azobarbiturate complex with the following structure can also be used.

[0181] As a yellow coloring agent, the compounds described in paragraphs 0031 to 0033 of International Publication No. 2022 / 085485, the methine dye described in Japanese Patent Publication No. 2019-073695, and the methine dye described in Japanese Patent Publication No. 2019-073696 can be used.

[0182] Examples of purple colorants include oxazine compounds, quinacridone compounds, perylene compounds, and indigo compounds, with oxazine compounds being preferred. The purple colorant is preferably a pigment (purple pigment). Specific examples of purple colorants include C.I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.

[0183] Examples of blue colorants include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred. The blue colorant is preferably a pigment (blue pigment). Specific examples of blue colorants include blue pigments such as C.I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, and 88. Furthermore, aluminum phthalocyanine compounds containing phosphorus atoms can also be used as blue colorants. Specific examples include the compounds described in paragraphs 0022-0030 of Japanese Patent Publication No. 2012-247591 and paragraph 0047 of Japanese Patent Publication No. 2011-157478.

[0184] Dyes can also be used as chromatic colorants. There are no particular restrictions on the dyes used, and known dyes can be used. Examples of dyes include pyrazole azo, anilino azo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, and pyromethene dyes.

[0185] A pigment polymer can also be used as a chromatic colorant. The pigment polymer is preferably a dye that is dissolved in a solvent before use. The pigment polymer may also form particles. When the pigment polymer is in particle form, it is usually used in a dispersed state in a solvent. Particle-form pigment polymers can be obtained, for example, by emulsion polymerization, and the compound and production method described in Japanese Patent Application Publication No. 2015-214682 are specific examples. The pigment polymer has two or more pigment structures in one molecule, and preferably three or more pigment structures. There is no particular upper limit, but it can be 100 or less. The multiple pigment structures in one molecule may be the same pigment structure or different pigment structures. The weight-average molecular weight (Mw) of the pigment polymer is preferably 2000 to 50000. The lower limit is more preferably 3000 or more, and even more preferably 6000 or more. The upper limit is more preferably 30000 or less, and even more preferably 20000 or less. The pigment polymer can also be a compound described in Japanese Patent Publication No. 2011-213925, Japanese Patent Publication No. 2013-041097, Japanese Patent Publication No. 2015-028144, Japanese Patent Publication No. 2015-030742, International Publication No. 2016 / 031442, etc.

[0186] As chromatic colorants, the following are used: the triarylmethane dye polymer described in Korean Published Patent No. 10-2020-0028160, the xanthene compound described in Japanese Patent Publication No. 2020-117638, the phthalocyanine compound described in International Publication No. 2020 / 174991, the isoindoline compound described in Japanese Patent Publication No. 2020-160279 or salts thereof, the compound represented by Formula 1 described in Korean Published Patent No. 10-2020-0069442, the compound represented by Formula 1 described in Korean Published Patent No. 10-2020-0069730, and the compound described in Korean Published Patent No. 10- Compound represented by formula 1 described in Japanese Patent Publication No. 2020-0069070, compound represented by formula 1 described in Korean Published Patent No. 10-2020-0069067, compound represented by formula 1 described in Korean Published Patent No. 10-2020-0069062, zinc halide phthalocyanine pigment described in Japanese Patent No. 6809649, isoindoline compound described in Japanese Patent Publication No. 2020-180176, phenothiazine compound described in Japanese Patent Publication No. 2021-187913, zinc halide phthalocyanine described in International Publication No. 2022 / 004261, International Publication Zinc halide phthalocyanine described in Japanese Patent Publication No. 2021 / 250883, quinophthalone compound represented by formula 1 in Korean Published Patent No. 10-2020-0030759, polymer dye described in Korean Published Patent No. 10-2020-0061793, chromatic colorant described in Japanese Patent Publication No. 2022-029701, isoindoline compound described in International Publication No. 2022 / 014635, aluminum phthalocyanine compound described in International Publication No. 2022 / 024926, compound described in Japanese Patent Publication No. 2022-045895, International Publication No. 2022 / 05005 The compound described in No. 1, the compound described in JP 2020-090676, the compound described in JP 2020-055956, the compound described in JP 2021-031681, the compound described in JP 2022-056354, the compound described in U.S. Patent Application Publication No. 2021 / 0355327, the compound described in International Publication No. 2022 / 065357, the compound described in JP 2020-045436, the compound described in Korean Published Patent No. 10-2021-0146726, the compound described in JP 2018-178039,Compounds described in Chinese Patent Application Publication No. 113881244, compounds described in Chinese Patent Application Publication No. 113881245, compounds described in Chinese Patent Application Publication No. 113881246, compounds described in Japanese Patent Publication No. 2022-104822, compounds described in Japanese Patent Publication No. 2022-096701, compounds described in Japanese Patent Publication No. 2020-023652, green pigments described on pages 80-84 of the Journal of the Color Materials Association (published in 2022), compounds described in Japanese Patent Publication No. 2022-143135, compounds described in Japanese Patent Publication No. 2022-140287, International Publication No. The compound described in JP 2022 / 136308, the perylene compound described in Chinese Patent Application Publication No. 113061349, the cyanide pigment described in Korean Published Patent No. 10-2017-0018993, the isoindoline compound described in JP 2020-180176, the compound described in JP 2023-013209, the compound described in JP 2023-013166, the xanthene compound described in International Publication No. 2023 / 286526, the compound described in JP 2021-155746, the compound described in JP 2021-155747, JP The compounds described in Japanese Patent Publication No. 2021-155748, the compounds described in Japanese Patent Application Publication No. 2021-155749, the compounds described in International Publication No. 2018 / 051876, the compounds described in Japanese Patent Application Publication No. 2020-083981, the compounds described in Japanese Patent Application Publication No. 2023-056463, the compounds described in Japanese Patent Publication No. 2023-515473, the dioxane compounds described in Japanese Patent Publication No. 2022-549530, the pigment preparations described in Japanese Patent Application Publication No. 2022-061494, the diketopyrrolopyrrole pigments described in Japanese Patent Application Publication No. 2023-057917, and the compounds described in Japanese Patent Application Publication No. 2023-061273 The diketopyrrolopyrrole compounds described, the phthalocyanine described in Japanese Patent Publication No. 2023-519314, the quinophthalone described in Japanese Patent Application Publication No. 2023-080419, the phthalocyanine compounds described in Japanese Patent Application Publication No. 2023-103177, the isoindoline compounds described in Japanese Patent Application Publication No. 2020-026521, the squarylium compounds described in Korean Published Patent No. 10-2023-0043000, the squarylium compounds described in Korean Published Patent No. 10-2023-0050069, the diketopyrrolopyrrole compounds described in Japanese Patent Application Publication No. 2023-127878,Triarylmethane compounds described in Japanese Patent Publication No. 2023-150459, Triarylmethane compounds described in Japanese Patent Publication No. 2023-149735, Core-shell dyes described in Japanese Patent Publication No. 2023-123349, Xanthene compounds described in Japanese Patent Publication No. 2023-543717, Compounds described in Chinese Patent Application Publication No. 116102441, Compounds described in Japanese Patent Publication No. 2023-150459, Compounds described in Japanese Patent Publication No. 2023-167345, Compounds described in Korean Published Patent No. 10-2023-0061078, Compounds described in Japanese Patent Publication No. 2024-043497, Japanese Patent Publication Compounds described in Japanese Patent Publication No. 2021-157040, azo pigments described in Japanese Patent Application Publication No. 2024-063075, compounds described in Japanese Patent Application Publication No. 2022-018967, quinophthalone pigments described in Japanese Patent Application Publication No. 2024-057558, compounds described in International Publication No. 2020 / 170957, compounds described in Chinese Patent Application Publication No. 117209388, isoindoline compounds described in Japanese Patent Application Publication No. 2024-079043, phthalocyanine dyes described in Korean Patent Publication No. 10-2022-0026920, compounds described in International Publication No. 2020 / 203514, etc. may also be used. Furthermore, the chromatic colorant may be a rotaxane. The pigment skeleton may be used in the cyclic structure of the rotaxane, in the rod-like structure, or in both structures.

[0187] Two or more chromatic pigments may be used in combination. Furthermore, when two or more chromatic pigments are used in combination, the combination of two or more chromatic pigments may form black. Examples of such combinations include the following embodiments (1) to (7). When the photocurable composition contains two or more chromatic pigments and exhibits black in combination with two or more chromatic pigments, the photocurable composition of the present invention can be preferably used as a photocurable composition for forming infrared transmission filters. (1) Embodiment containing a red pigment and a blue pigment. (2) Embodiment containing a red pigment, a blue pigment and a yellow pigment. (3) Embodiment containing a red pigment, a blue pigment, a yellow pigment and a purple pigment. (4) Embodiment containing a red pigment, a blue pigment, a yellow pigment, a purple pigment and a green pigment. (5) Embodiment containing a red pigment, a blue pigment, a yellow pigment and a green pigment. (6) An embodiment containing a red colorant, a blue colorant, and a green colorant. (7) An embodiment containing a yellow colorant and a purple colorant.

[0188] (White pigments) Examples of white pigments include inorganic pigments such as titanium dioxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, and zinc sulfide. White pigments can be those described in paragraphs 0040-0043 of International Publication No. 2022 / 085485.

[0189] (Black Colorant) The black colorant is not particularly limited and any known colorant may be used. The black colorant may be an inorganic black colorant or an organic black colorant. The black colorant is preferably a pigment. In this specification, the term "black colorant" refers to a colorant that exhibits absorption over the entire wavelength range of 400 to 700 nm.

[0190] Examples of inorganic black colorants include carbon black, titanium black, and graphite, with carbon black and titanium black being preferred, and titanium black being more preferred. Titanium black refers to black particles containing titanium atoms, with lower-order titanium oxide and titanium oxynitride being preferred. The titanium black used can be the titanium black described in paragraph 0044 of International Publication No. 2022 / 085485. Zirconium nitride powder described in Japanese Patent Application Publication No. 2023-048173 can also be used as the inorganic black colorant.

[0191] Examples of organic black colorants include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred. The organic black colorant can be a compound described in paragraph 0166 of International Publication No. 2022 / 065215. Alternatively, perylene black (such as Lumogen Black FK4280) described in paragraphs 0016-0020 of Japanese Patent Application Publication No. 2017-226821 or a black azo pigment described in Japanese Patent Application Publication No. 2022-121935 may be used as the organic black colorant.

[0192] For the black pigment, you can also use the black pigments listed in sections 294-307 of the Journal of the Japan Society of Colorants, Vol. 96, No. 9, 2023.

[0193] (Infrared Absorbing Colorants) The infrared absorbing colorant is preferably a compound having a maximum absorption wavelength longer than 700 nm. The infrared absorbing colorant is preferably a compound having a maximum absorption wavelength in the range of 700 nm to 1800 nm, more preferably a compound having a maximum absorption wavelength in the range of 700 nm to 1400 nm, even more preferably a compound having a maximum absorption wavelength in the range of 700 nm to 1200 nm, and particularly preferably a compound having a maximum absorption wavelength in the range of 700 nm to 1000 nm. Furthermore, the absorbance A of the infrared absorbing colorant at a wavelength of 500 nm is also specified. １ and absorbance A at the maximum absorption wavelength ２ Ratio A １ / A ２It is preferable that the ratio is 0.08 or less, and more preferably 0.04 or less. Furthermore, the infrared absorbing colorant is preferably a pigment, and more preferably an organic pigment.

[0194] Examples of infrared absorbing colorants include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, crokonium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyromethene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, and metal borides. Specific examples of these include the compounds described in paragraph 0114 of International Publication No. 2022 / 065215. Furthermore, examples of infrared absorbing colorants include the compounds described in paragraph 0121 of International Publication No. 2022 / 065215, and the squarylium compounds described in Japanese Patent Publication No. 2020-075959. Copper complex described in Korean Published Patent No. 10-2019-0135217, croconic acid compound described in Japanese Patent Application Publication No. 2021-195515, infrared absorbing dye described in Japanese Patent Application Publication No. 2022-022070, croconium compound described in International Publication No. 2019 / 021767, compound described in Japanese Patent Application Publication No. 2019-127549, International Publication No. 2022 / 059619 The compounds described in JP 2022-151682, the compounds described in JP 2022-188858, the compounds described in JP 2022-184710, the compounds described in JP 2022-189736, the compounds described in JP 2023-004570, the compounds described in International Publication No. 2019 / 230660 Qualyllium compounds, compounds described in International Publication No. 2020 / 218615, diiminium compounds described in Japanese Patent Publication No. 2023-068643, squarylium compounds described in Japanese Patent Publication No. 2023-052770, phthalocyanine compounds described in Korean Patent Publication No. 10-2022-0163680, indigo monoboron complexes described in Japanese Patent Publication No. 2023-073064, phthalocyanine compounds described in Japanese Patent Publication No. 2023-066025, phthalocyanine compounds described in Japanese Patent Publication No. 2020-041127, indigo compounds described in Japanese Patent Publication No. 2023-073064, indigo compounds described in Korean Patent Publication No. 10-2023-0016355, squarylium compounds described in International Publication No. 2019 / 230570,Diiminium compounds described in Japanese Patent Publication No. 2023-095824, infrared absorbing colorants described in Japanese Patent Publication No. 2024-047265, compounds described in Japanese Patent Publication No. 2024-043503, extended phthalocyanine described in Japanese Patent Publication No. 2021-047255, compounds described in International Publication No. 2024 / 058103, compounds described in Japanese Patent Publication No. 2024-071077, U.S. Patent Application Publication No. 2021 / 0036 Infrared absorbing colorants described in Specification No. 251, infrared absorbing colorants described in Japanese Patent Publication No. 2024-079641, cyanine compounds described in International Publication No. 2024 / 106293, squarylium compounds described in Korean Registered Patent No. 10-2622663, squarylium compounds described in Japanese Patent Publication No. 2024-071077, and cyanine compounds described in International Publication No. 2024 / 128016 can also be used.

[0195] The colorant content in the total solids of the photocurable composition is preferably 30 to 80% by mass. The upper limit is preferably 70% by mass or less, and more preferably 65% ​​by mass or less. The lower limit is preferably 35% by mass or more, and more preferably 40% by mass or more.

[0196] The pigment content in the total solids of the photocurable composition is preferably 20 to 80% by mass. The upper limit is preferably 75% by mass or less, more preferably 65% ​​by mass or less, and even more preferably 63% by mass or less. The lower limit is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more.

[0197] The pigment content in the colorant is preferably 20 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 70 to 100% by mass.

[0198] <<Polymerization Inhibitor>> The photocurable composition of the present invention contains a polymerization inhibitor. Examples of polymerization inhibitors include 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogal, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), nitrobenzene, and N-nitrosophenylhydroxyamine salts (ammonium salts, cerium salts, etc.). The polymerization inhibitor is preferably an N-oxy radical compound or a phenol compound, more preferably an N-oxy radical compound, and even more preferably an N-oxy radical compound having a six-membered ring structure. The polymerization inhibitor, which is an N-oxy radical compound, is presumed to interact with the five-membered or six-membered aliphatic ring of the specific compound (the compound represented by formula (1)) and exist in the vicinity of the specific compound in the film. Even when exposed to high light intensity, it can efficiently deactivate excessively generated radicals and further improve the light intensity dependence. In particular, the light intensity dependence can be improved more significantly with N-oxy radical compounds having a six-membered ring structure. The polymerization inhibitor is especially preferably 2,2,6,6-tetramethylpiperidine-1-oxyl or 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl for the reason that it can more significantly improve the light intensity dependence. The content of the polymerization inhibitor is preferably 0.001 to 10 parts by mass per 100 parts by mass of the specific compound (the compound represented by formula (1)). The upper limit is preferably 1 part by mass or less, and more preferably 0.5 parts by mass or less. The lower limit is preferably 0.01 parts by mass or more, and more preferably 0.03 parts by mass or more. The content of polymerization inhibitor in the total solids of the photocurable composition is preferably 0.0001 to 5% by mass. There may be only one type of polymerization inhibitor, or there may be two or more types. If there are two or more types, it is preferable that the total amount is within the above range.

[0199] <<Chain Transfer Agent>> The photocurable composition of the present invention preferably contains a chain transfer agent. Examples of chain transfer agents include thiol compounds, thiocarbonylthio compounds, and dimers of aromatic α-methylalkenyls, with thiol compounds being preferred. Examples of chain transfer agents include those described in paragraphs 0093 to 0113 of International Publication No. 2019 / 188652.

[0200] The thiol compound used as a chain transfer agent is a compound having one or more thiol groups, and preferably a compound having two or more thiol groups. The upper limit of the number of thiol groups contained in the thiol compound is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. It is particularly preferable that the thiol compound is a compound having two thiol groups.

[0201] The thiol compound is preferably a compound represented by the following formula (SH-1). Ｓ１ - (SH) ｎ ...Formula (SH-1) (wherein SH represents a thiol group, L １ (This represents an n-valence base, where n is an integer greater than or equal to 1.)

[0202] L in equation (SH-1) Ｓ１ The n-valent groups represented by include hydrocarbon groups, heterocyclic groups, -O-, -S-, and -NR Ｓ１ -, -CO-, -COO-, -OCO-, -SO ２ - Or, a group consisting of a combination of these. R Ｓ１The group represents a hydrogen atom, an alkyl group, or an aryl group, with a hydrogen atom being preferred. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be cyclic or acyclic. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The hydrocarbon group may have substituents or may not have substituents. The cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be monocyclic or fused rings. The heterocyclic group may be monocyclic or fused rings. A five-membered ring or a six-membered ring is preferred for the heterocyclic group. The heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. Examples of heteroatoms constituting the heterocyclic group include nitrogen atoms, oxygen atoms, and sulfur atoms. １ The number of carbon atoms constituting the compound is preferably 3 to 100, and more preferably 6 to 50.

[0203] In formula (SH-1), n ​​represents an integer greater than or equal to 1. The upper limit of n is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. The lower limit of n is preferably 2 or greater.

[0204] Specific examples of thiol compounds include those described in paragraphs 0100-0103 of International Publication No. 2019 / 188652. Commercially available thiol compounds include PEMP (manufactured by SC Organic Chemicals Co., Ltd.), Suncellar M (manufactured by Sanshin Chemical Industry Co., Ltd.), Karenz MTBD1, Karenz MTPE1, Karenz MTNR1, and Karenz MTTPMB (all manufactured by Resonac Co., Ltd.). Thiol compounds described in Japanese Patent Publication No. 2020-109068 can also be used as chain transfer agents.

[0205] As a chain transfer agent, ether-bonded thiol compounds, Multiol Y-2, Y-3, and Y-4 (manufactured by Sakai Chemical Industry Co., Ltd.), described in International Publication No. 2020 / 170944, can also be used.

[0206] The molecular weight of the chain transfer agent is preferably 200 or more. The upper limit is preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less, because it can increase the SH valency per unit weight.

[0207] The content of the chain transfer agent in the total solid content of the photocurable composition is preferably 0.001 to 5% by mass. The upper limit is preferably 3% by mass or less, and more preferably 1% by mass or less. The lower limit is preferably 0.05% by mass or more, and more preferably 0.01% by mass or more. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount is within the above range.

[0208] <<Amine Compound>> The curable compound of the present invention preferably contains an amine compound. According to this embodiment, the efficiency of radical generation from the photopolymerization initiator during exposure can be further improved, and the polymerization reaction of the polymerizable compound can be further promoted.

[0209] The molecular weight of the amine compound is preferably 100 to 1000. The upper limit is preferably 800 or less, and more preferably 500 or less. The lower limit is preferably 150 or more, and more preferably 200 or more.

[0210] The amine compound is preferably a compound having 1 to 8 amino groups in one molecule, more preferably a compound having 1 to 4 amino groups, and even more preferably a compound having 1 to 2 amino groups.

[0211] The amine compound is preferably colorless. That is, the molar extinction coefficient of the amine compound at wavelengths of 400 to 700 nm is 200 L·mol. －１ ・cm －１ Preferably less than 100 L / mol －１ ・cm －１ It is more preferable that it be less than [a certain value].

[0212] The amine compound may be a primary, secondary, or tertiary amine, but a tertiary amine is preferred.

[0213] In amine compounds, the three groups connected to the nitrogen atom are preferably selected from a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group. Of these, the combination of an alkyl group and an aryl group is most preferred.

[0214] For the purpose of improving alkali developability and reducing residue, amine compounds preferably have one of the following groups: a carboxyl group, a sulfonic acid group, a phosphate group, or a hydroxyl group.

[0215] The amine compound is preferably a compound represented by formula (B-1). In formula (B-1), R ａ and R ｂ Each of these independently represents a monovalent organic group having 1 to 10 carbon atoms, which may contain heteroatoms, and R ｃ The symbol represents a monovalent organic group that may contain a heteroatom, and m represents an integer from 0 to 5.

[0216] R ａ , R ｂ and R ｃ The organic group represented by includes alkyl groups, aryl groups, and heteroaryl groups, with alkyl groups being preferred. Alkyl groups, aryl groups, and heteroaryl groups may have substituents. Examples of substituents include carboxyl groups, sulfonic acid groups, phosphoric acid groups, and hydroxyl groups, with hydroxyl groups being preferred. m represents an integer from 0 to 5, preferably an integer from 0 to 3, more preferably 0 or 1, and even more preferably 0.

[0217] Specific examples of amine compounds include Michla's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminocinnamyridenein. Danone, p-dimethylaminobenzylidene in danone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3- Examples include cetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, and 2-(p-dimethylaminobenzoyl)styrene. These can be used individually or in combinations of, for example, two to five types.

[0218] The content of the amine compound is preferably 5 to 1000 parts by mass per 100 parts by mass of the specified compound described above. The upper limit is preferably 500 parts by mass or less, and more preferably 200 parts by mass or less. The lower limit is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more. Only one amine compound may be used, or two or more may be used. When two or more are used, it is preferable that their total amount is within the above range.

[0219] <<Acid Anhydrides>> The photocurable composition of the present invention may contain acid anhydrides. Examples of acid anhydrides include carboxylic acid anhydrides and sulfonic acid anhydrides, with carboxylic acid anhydrides being preferred. Specific examples of acid anhydrides include acetic anhydride, propionic anhydride, isobutyric anhydride, butyric anhydride, 2-methylbutyric anhydride, pivalic anhydride, isovaleric anhydride, valeric anhydride, 2-methylvaleric anhydride, 3-methylvaleric anhydride, 4-methylvaleric anhydride, hexanoic anhydride, 2-methylhexanoic anhydride, 3-methylhexanoic anhydride, 4-methylhexanoic anhydride, 5-methylhexanoic anhydride, heptanoic anhydride, 2-methylheptanoic anhydride, 3-methylheptanoic anhydride, 4-methylheptanoic anhydride, 5-methylheptanoic anhydride, Examples include aliphatic carboxylic acid anhydrides such as 6-methylheptanoic anhydride, 3-phenylpropionic anhydride, phenylacetic anhydride, methacrylic anhydride, acrylic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, and glutaric anhydride; aromatic carboxylic acid anhydrides such as benzoic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride; and sulfocarboxylic acid anhydrides such as 2-sulfobenzoic anhydride.

[0220] The acid anhydride content is preferably 1 to 200 parts by mass per 100 parts by mass of the specified compound described above. The upper limit is preferably 100 parts by mass or less, and more preferably 50 parts by mass or less. The lower limit is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more. Only one type of acid anhydride may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount is within the above range.

[0221] <<Pigment Derivatives>> The photocurable composition of the present invention may contain pigment derivatives. Pigment derivatives are used, for example, as dispersion aids. A dispersion aid is a material used to improve the dispersibility of colorants such as pigments in a photocurable composition.

[0222] Examples of pigment derivatives include compounds having at least one structure selected from the group consisting of a dye structure and a triazine structure, and an acidic group or a basic group.

[0223] Examples of the above-mentioned pigment structures include quinoline pigment structure, benzimidazolone pigment structure, benzoisoindole pigment structure, benzothiazole pigment structure, iminium pigment structure, squarylium pigment structure, crokonium pigment structure, oxonol pigment structure, pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, azo pigment structure, azomethine pigment structure, phthalocyanine pigment structure, naphthalocyanine pigment structure, anthraquinone pigment structure, quinacridone pigment structure, dioxazine pigment structure, perinone pigment structure, perylene pigment structure, thiaidine indigo pigment structure, thioindigo pigment structure, isoindoline pigment structure, isoindolinone pigment structure, quinophthalone pigment structure, dithiol pigment structure, triarylmethane pigment structure, pyromethene pigment structure, and the like.

[0224] Examples of acidic groups found in pigment derivatives include carboxyl groups, sulfo groups, phosphate groups, boronic acid groups, imido acid groups, and salts thereof. Examples of atoms or groups of atoms constituting the salt include alkali metal ions (Li ＋ Na ＋ _K ＋ (Ca) ２＋ Mg ２＋ Examples include ammonium ions, imidazolium ions, pyridinium ions, and phosphonium ions. Examples of imido acid groups include -SO ２ NHSO ２ R Ｘ１ , -CONHSO ２ R Ｘ２ , -CONHCOR Ｘ３ or -SO ２ NHCOR Ｘ４A group represented by -SO is preferred, ２ NHSO ２ R Ｘ１ , -CONHSO ２ R Ｘ２ , or -SO ２ NHCOR Ｘ４ A group represented by -SO is more preferred. ２ NHSO ２ R Ｘ１ or -CONHSO ２ R Ｘ２ This is even more preferable. Ｘ１ ~R Ｘ４ Each of these independently represents an alkyl group or an aryl group. Ｘ１ ~R Ｘ４ The alkyl and aryl groups represented by may have substituents. The substituents are preferably halogen atoms, and more preferably fluorine atoms. Ｘ１ ~R Ｘ４ Each of these is preferably an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom, and more preferably an alkyl group containing a fluorine atom. The alkyl group containing a fluorine atom has 1 to 10 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 3. The aryl group containing a fluorine atom has 6 to 20 carbon atoms, more preferably 6 to 12, and even more preferably 6.

[0225] Basic groups found in pigment derivatives include amino groups, pyridinyl groups and their salts, ammonium groups, and phthalimidomethyl groups. Atoms or groups of atoms that make up the salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.

[0226] As for the amino group, -NR ｘ１１ R ｘ１２ Examples include the group represented by and the cyclic amino group.

[0227] -NR ｘ１１ R ｘ１２ In the group represented by R ｘ１１ and R ｘ１２Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and is preferably an alkyl group. That is, the amino group is preferably a dialkylamino group. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but linear or branched is preferred, and linear is more preferred. The alkyl group may have substituents. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. The aryl group may have substituents.

[0228] Examples of cyclic amino groups include pyrrolidine, piperidine, piperazine, and morpholine groups. These groups may also have substituents.

[0229] Pigment derivatives with excellent visible transparency (hereinafter also referred to as transparent pigment derivatives) can also be used. The maximum molar extinction coefficient (εmax) of the transparent pigment derivative in the wavelength range of 400 to 700 nm is 3000 L·mol －１ ・cm －１ Preferably, the following: 1000 L·mol －１ ・cm －１ It is more preferable that the following conditions apply: 100 L·mol －１ ・cm －１ It is even more preferable that the following conditions are met: The lower limit of εmax is, for example, 1 L·mol －１ ・cm －１ That is all. 10 L·mol －１ ・cm －１ That's fine too.

[0230] Specific examples of pigment derivatives include the compounds described in the examples below, the compounds described in paragraph 0124 of International Publication No. 2022 / 085485, the benzimidazolone compounds or salts thereof described in Japanese Patent Application Publication No. 2018-168244, the compounds having an isoindoline skeleton described in general formula (1) of Japanese Patent No. 6996282, the compounds described in Japanese Patent Application Publication No. 2019-172968, the compounds described in Chinese Patent Application Publication No. 115124889, the quinophthalone-based dye derivatives described in Japanese Patent Application Publication No. 2024-046989, the dispersion aids described in Japanese Patent Application Publication No. 2024-066986, the dispersion aids described in Japanese Patent Application Publication No. 2024-066995, the compounds described in Japanese Patent Application Publication No. 2022-018967, and the dispersion aids described in Japanese Patent Application Publication No. 2024-066992.

[0231] The content of the pigment derivative is preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass, per 100 parts by mass of pigment. Furthermore, the total content of the pigment derivative and colorant is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, of the total solid content of the photocurable composition. The upper limit is preferably 80% by mass or less, and more preferably 70% by mass or less. Only one type of pigment derivative may be used, or two or more types may be used in combination.

[0232] <<Polyalkyleneimines>> The photocurable composition of the present invention may also contain polyalkyleneimines. Polyalkyleneimines are used, for example, as dispersing aids for pigments. Dispersing aids are materials used to improve the dispersibility of colorants such as pigments in a photocurable composition. A polyalkyleneimine is a polymer obtained by ring-opening polymerization of alkyleneimines. Preferably, the polyalkyleneimine is a polymer having a branched structure containing primary amino groups, secondary amino groups, and tertiary amino groups. The number of carbon atoms in the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2.

[0233] The molecular weight of the polyalkyleneimine is preferably 200 or more, and more preferably 250 or more. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less. When the molecular weight of the polyalkyleneimine can be calculated from the structural formula, the molecular weight of the polyalkyleneimine is the value calculated from the structural formula. On the other hand, when the molecular weight of a specific amine compound cannot be calculated from the structural formula, or when it is difficult to calculate, the number-average molecular weight measured by the boiling point elevation method is used. Furthermore, when it cannot be measured by the boiling point elevation method, or when it is difficult to measure, the number-average molecular weight measured by the viscosity method is used. Furthermore, when it cannot be measured by the viscosity method, or when it is difficult to measure by the viscosity method, the number-average molecular weight in polystyrene equivalent values ​​measured by GPC (gel permeation chromatography) is used.

[0234] The amine value of the polyalkyleneimine is preferably 5 mmol / g or more, more preferably 10 mmol / g or more, and even more preferably 15 mmol / g or more.

[0235] Specific examples of alkyleneimines include ethyleneimine, propyleneimine, 1,2-butyleneimine, and 2,3-butyleneimine, with ethyleneimine or propyleneimine being preferred, and ethyleneimine being more preferred. Polyalkyleneimines are particularly preferably polyethyleneimine. Furthermore, polyethyleneimine preferably contains 10 mol% or more of primary amino groups relative to the total of primary, secondary, and tertiary amino groups, more preferably 20 mol% or more, and even more preferably 30 mol% or more. Commercially available polyethyleneimines include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by Nippon Shokubai Co., Ltd.).

[0236] The polyalkylene imine content in the total solids of the photocurable composition is preferably 0.1 to 5% by mass. The lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is preferably 4.5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. Furthermore, the polyalkylene imine content is preferably 0.5 to 20 parts by mass per 100 parts by mass of pigment. The lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more. The upper limit is preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less. Only one type of polyalkylene imine may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount is within the above range.

[0237] <<Solvent>> The photocurable composition of the present invention preferably contains a solvent. Examples of solvents include organic solvents. The type of solvent is not particularly limited as long as it satisfies the solubility of each component and the applicability of the composition. Examples of organic solvents include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. For further details, refer to paragraph 0223 of International Publication No. 2015 / 166779, which is incorporated herein by reference. In addition, ester solvents and ketone solvents substituted with cyclic alkyl groups can also be preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene Examples include propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, and isopropyl alcohol.However, the amount of aromatic hydrocarbons used as organic solvents (benzene, toluene, xylene, ethylbenzene, etc.) may be reduced for environmental reasons (for example, it may be reduced to 50 ppm by mass (parts per million) or less, 10 ppm by mass or less, or 1 ppm by mass or less relative to the total amount of organic solvent).

[0238] It is preferable that the metal content of the organic solvent be low. The metal content of the organic solvent is preferably, for example, 10 ppb (parts per billion) or less by mass. If necessary, an organic solvent with a metal content at the ppt (parts per trillion) level by mass may be used; such organic solvents are provided, for example, by Toyo Gosei Co., Ltd. (Chemical Daily, November 13, 2015).

[0239] Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin-film distillation, etc.) and filtration using a filter. The pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon.

[0240] Organic solvents may contain isomers (compounds with the same number of atoms but different structures). Furthermore, they may contain only one type of isomer or multiple types.

[0241] It is preferable that the peroxide content in the organic solvent is 0.8 mmol / L or less, and more preferably that it is substantially peroxide-free.

[0242] The solvent content in the photocurable composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 90% by mass.

[0243] The photocurable composition of the present invention preferably contains substantially no environmentally regulated substances from the viewpoint of environmental regulations. In this invention, "substantially free of environmentally regulated substances" means that the content of environmentally regulated substances in the photocurable composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, more preferably 10 ppm by mass or less, and particularly preferably 1 ppm by mass or less. Examples of environmentally regulated substances include benzene; alkylbenzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene, etc. These substances are registered as environmentally regulated substances under the REACH (Registration Evaluation Authorization and Restriction of Chemicals) regulations, the PRTR (Pollutant Release and Transfer Register) law, and the VOC (Volatile Organic Compounds) regulations, and their usage and handling methods are strictly regulated. These compounds may be used as solvents when manufacturing components used in photocurable compositions, and may be mixed into the photocurable composition as residual solvents. From the standpoint of human safety and environmental considerations, it is preferable to reduce these substances as much as possible. One method for reducing environmentally regulated substances is to heat or reduce the pressure in the system to above the boiling point of the environmentally regulated substance and distillate it off the system. Furthermore, when removing small amounts of environmentally regulated substances by distillation, it is useful to azeotrope with a solvent having a boiling point equivalent to that of the solvent in question in order to increase efficiency. In addition, if the mixture contains compounds that exhibit radical polymerization, polymerization inhibitors may be added during reduced-pressure distillation to suppress the progression of radical polymerization reactions and the resulting crosslinking between molecules. These distillation methods can be implemented at any stage, including the raw material stage, the product stage (e.g., the polymerized resin solution or polyfunctional monomer solution), or the stage of the photocurable composition prepared by mixing these compounds.

[0244] <<Compounds Having Cyclic Ether Groups>> The photocurable composition of the present invention may contain compounds having cyclic ether groups. Examples of cyclic ether groups include epoxy groups and oxetanyl groups. The epoxy group may be an alicyclic epoxy group. An alicyclic epoxy group refers to a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are fused. The compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter also referred to as an epoxy compound). Examples of epoxy compounds include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferred. The epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups contained in the epoxy compound can be, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups contained in the epoxy compound is preferably 2 or more.

[0245] As compounds having a cyclic ether group, you can use the compounds described in paragraphs 0034 to 0036 of Japanese Patent Publication No. 2013-011869, paragraphs 0147 to 0156 of Japanese Patent Publication No. 2014-043556, paragraphs 0085 to 0092 of Japanese Patent Publication No. 2014-089408, the compounds described in Japanese Patent Publication No. 2017-179172, the xanthene type epoxy resin described in Japanese Patent Publication No. 2021-195421, and the xanthene type epoxy resin described in Japanese Patent Publication No. 2021-195422.

[0246] The compound having a cyclic ether group may be a low molecular weight compound (for example, with a molecular weight of less than 2000, and even less than 1000) or a high molecular weight compound (macromolecule) (for example, with a molecular weight of 1000 or more, or in the case of a polymer, with a weight-average molecular weight of 1000 or more). The weight-average molecular weight of the compound having a cyclic ether group is preferably 200 to 100000, and more preferably 500 to 50000. The upper limit of the weight-average molecular weight is preferably 10000 or less, more preferably 5000 or less, and even more preferably 3000 or less.

[0247] Examples of commercially available compounds containing cyclic ether groups include EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (all manufactured by NOF Corporation, epoxy group-containing polymers).

[0248] The content of compounds having cyclic ether groups in the total solid content of the photocurable composition is preferably 0.1 to 20% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. Only one compound having a cyclic ether group may be used, or two or more compounds may be used. When two or more compounds are used, it is preferable that their total amount is within the above range.

[0249] <<Ultraviolet Absorbers>> The photocurable composition of the present invention may contain ultraviolet absorbers. Examples of ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, and dibenzoyl compounds. Specific examples of such compounds include the compound described in paragraph 0179 of International Publication No. 2022 / 085485, the reactive triazine ultraviolet absorber described in Japanese Patent Application Publication No. 2021-178918, the ultraviolet absorber described in Japanese Patent Application Publication No. 2022-007884, the compound described in Korean Patent Publication No. 10-2022-0014454, the compound described in Japanese Patent Application Publication No. 2023-013321, and the compound described in Japanese Patent Application Publication No. 2023-178225. The content of ultraviolet absorbers in the total solid content of the photocurable composition is preferably 0.01 to 10% by mass, and more preferably 0.01 to 5% by mass. Only one type of ultraviolet absorber may be used, or two or more types may be used. If two or more types are used, it is preferable that their total amount falls within the above range.

[0250] <<Silane Coupling Agent>> The photocurable composition of the present invention may contain a silane coupling agent. Examples of silane coupling agents include silane compounds having a hydrolyzable group, and it is preferable that the silane compound has a hydrolyzable group and other functional groups. A hydrolyzable group is a substituent that is directly bonded to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of hydrolyzable groups include halogen atoms, alkoxy groups, and acyloxy groups, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl groups, allyl groups, (meth)acryloyl groups, thiol groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, isocyanate groups, and phenyl groups, with amino groups, (meth)acryloyl groups, and epoxy groups being preferred. Specific examples of silane coupling agents include the compounds described in paragraph 0177 of International Publication No. 2022 / 085485 and the compounds described in Japanese Patent Publication No. 2019-183020. The content of the silane coupling agent in the total solid content of the photocurable composition is preferably 0.1 to 15% by mass. The upper limit is preferably 10% by mass or less, and more preferably 5% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. There may be only one type of silane coupling agent, or there may be two or more types. If there are two or more types, it is preferable that the total amount is within the above range.

[0251] <<Surfactants>> The photocurable composition of the present invention may contain a surfactant. Various surfactants can be used, such as fluorinated surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants. The surfactant is preferably a silicone surfactant or a fluorinated surfactant, and more preferably a silicone surfactant. For surfactants, refer to the surfactants described in paragraphs 0238 to 0245 of International Publication No. 2015 / 166779, which are incorporated herein by reference.

[0252] As fluorinated surfactants, compounds described in paragraphs 0167-0173 of International Publication No. 2022 / 085485 can be used.

[0253] Examples of nonionic surfactants include the compounds described in paragraph 0174 of International Publication No. 2022 / 085485.

[0254] Examples of silicone-based surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, and SF 8419. Examples include OIL (manufactured by Dow Toray Industries, Inc.), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (manufactured by Bic Chemie, Inc.), etc. Furthermore, compounds with the following structure can also be used as silicone-based surfactants.

[0255] As surfactants, polymers described in International Publication No. 2021 / 131726, silicone-containing copolymers described in International Publication No. 2024 / 024440, and silicone-containing copolymers described in International Publication No. 2024 / 024441 can also be used.

[0256] The surfactant content in the total solids of the photocurable composition is preferably 0.001% to 5.0% by mass, and more preferably 0.005% to 3.0% by mass. The surfactant may be one type or two or more types. If two or more types are used, the total amount is preferably within the above range.

[0257] <<Antioxidants>> The photocurable composition of the present invention may contain antioxidants. Examples of antioxidants include phenolic antioxidants, amine antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Examples of phenolic antioxidants include hindered phenol compounds. Phenolic antioxidants are preferably compounds having a substituent at the ortho position adjacent to the phenolic hydroxyl group. As for the substituents, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Antioxidants are also preferably compounds having a phenolic group and a phosphite ester group in the same molecule. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosfepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosfepin-2-yl)oxy]ethyl]amine, ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphate, and tris(2,4-di-tert-butylphenyl) phosphite. Examples of commercially available antioxidants include ADEKA stab AO-20, ADEKA stab AO-30, ADEKA stab AO-40, ADEKA stab AO-50, ADEKA stab AO-50F, ADEKA stab AO-60, ADEKA stab AO-60G, ADEKA stab AO-80, and ADEKA stab AO-330 (all manufactured by ADEKA Corporation), and JP-650 (manufactured by Johoku Chemical Industry Co., Ltd.). The antioxidants can also be compounds described in paragraphs 0023-0048 of Japanese Patent No. 6268967, compounds described in International Publication No. 2017 / 006600, compounds described in International Publication No. 2017 / 164024, and compounds described in Korean Published Patent No. 10-2019-0059371. The antioxidant content in the total solids of the photocurable composition is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass. Only one type of antioxidant may be used, or two or more types may be used. If two or more types are used, it is preferable that their total amount falls within the above range.

[0258] <<Other Components>> The photocurable composition of the present invention may optionally contain sensitizers, plasticizers, and other auxiliary agents (e.g., conductive particles, fillers, defoamers, flame retardants, leveling agents, peel accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). By appropriately including these components, properties such as film properties can be adjusted. These components can be compounds described in paragraph 0182 of International Publication No. 2022 / 085485, compounds having two or more triethoxysilyl groups described in Japanese Patent Application Publication No. 2023-180607, and the like.

[0259] The photocurable composition of the present invention may contain a lightfastness modifier. Examples of lightfastness modifiers include the compounds described in paragraph 0183 of International Publication No. 2022 / 085485.

[0260] The photocurable composition of the present invention may contain compounds derived from biomass raw materials, compounds containing radioactive carbon atoms, and compounds having a percentage modern carbon content of 50% or more. The content of compounds derived from biomass raw materials relative to the total compounds contained in the curable composition of the present invention may be 20% by mass or more.

[0261] The photocurable composition of the present invention preferably contains substantially no terephthalate ester. Here, "substantially free" means that the terephthalate ester content is 1,000 ppb by mass or less of the total amount of the photocurable composition, more preferably 100 ppb by mass or less, and particularly preferably zero.

[0262] From the viewpoint of environmental regulations, the photocurable composition of the present invention preferably has a melamine content of 10,000 ppm by mass or less.

[0263] The photocurable composition of the present invention preferably has a free metal content of 100 ppm or less, and more preferably 50 ppm or less. Furthermore, the free halogen content is preferably 100 ppm or less, and more preferably 50 ppm or less. Methods for reducing free metals and halogens in the photocurable composition include washing with deionized water, filtration, ultrafiltration, and purification with ion exchange resin.

[0264] From an environmental perspective, the use of perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts may be restricted. In the photocurable composition of the present invention, when the content of the above-mentioned compounds is reduced, the content of perfluoroalkyl sulfonic acid (particularly perfluoroalkyl sulfonic acid with 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts, and perfluoroalkyl carboxylic acid (particularly perfluoroalkyl carboxylic acid with 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts is preferably in the range of 0.01 ppb to 1000 ppb, more preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb, relative to the total solid content of the photocurable composition. The photocurable composition of the present invention may substantially not contain perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts. For example, a photocurable composition substantially free of perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts, may be selected by using compounds that can substitute for perfluoroalkyl sulfonic acid and its salts, and compounds that can substitute for perfluoroalkyl carboxylic acid and its salts. Examples of compounds that can substitute for regulated compounds include compounds that have been excluded from regulation due to differences in the number of carbon atoms in the perfluoroalkyl group. However, the above does not preclude the use of perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts. The photocurable composition of the present invention may contain perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts, to the maximum permissible extent.

[0265] The water content of the photocurable composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, and more preferably in the range of 0.1 to 1.0% by mass. The water content can be measured by the Karl Fischer method.

[0266] The photocurable composition of the present invention can be used by adjusting its viscosity for purposes such as adjusting the film surface (flatness, etc.) and adjusting the film thickness. The viscosity value can be appropriately selected as needed, but for example, 0.3 mPa·s to 50 mPa·s is preferred at 25°C, and 0.5 mPa·s to 20 mPa·s is more preferred. As a method for measuring viscosity, for example, a cone-plate type viscometer can be used and the measurement can be taken while the temperature has been adjusted to 25°C.

[0267] <<Container>> There are no particular limitations on the container used to contain the photocurable composition, and any known container can be used. Alternatively, the container described in paragraph 0187 of International Publication No. 2022 / 085485 can be used as the container.

[0268] <Method for preparing the photocurable composition> The photocurable composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the photocurable composition, all components may be dissolved and / or dispersed simultaneously in a solvent to prepare the photocurable composition, or, if necessary, each component may be prepared as two or more solutions or dispersions and mixed at the time of use (coating) to prepare the photocurable composition.

[0269] The preparation of a photocurable composition preferably includes a process for dispersing the pigment. Examples of mechanical forces used for pigment dispersion include compression, squeezing, impact, shearing, and cavitation. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, and ultrasonic dispersion. Furthermore, in the grinding of pigments using a sand mill (bead mill), it is preferable to process the material under conditions that enhance grinding efficiency, such as by using small-diameter beads or increasing the bead packing density. It is also preferable to remove coarse particles after the grinding process by filtration or centrifugation. Furthermore, the processes and dispersers for dispersing the pigments can suitably be those described in "Complete Collection of Dispersion Technologies, published by Joho Kiko Co., Ltd., July 15, 2005," "Comprehensive Data Collection on Dispersion Technologies and Industrial Applications Focusing on Suspensions (Solid / Liquid Dispersion Systems), published by Keiei Kaihatsu Center Publishing Department, October 10, 1978," and paragraph 0022 of Japanese Patent Publication No. 2015-157893. In addition, in the process of dispersing the pigments, particle refinement treatment may be performed in a salt milling step. For materials, equipment, and processing conditions used in the salt milling step, for example, refer to the descriptions in Japanese Patent Publication No. 2015-194521 and Japanese Patent Publication No. 2012-046629. Examples of bead materials used for dispersion include zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, and glass. Furthermore, inorganic compounds with a Mohs hardness of 2 or higher can be used as beads. The photocurable composition may contain 1 to 10,000 ppm of the above-mentioned beads.

[0270] In preparing a photocurable composition, it is preferable to filter the photocurable composition with a filter for purposes such as removing foreign matter and reducing defects. Examples of filters and filtration methods used for filtration include those described in paragraphs 0196 to 0199 of International Publication No. 2022 / 085485.

[0271] <Membrane> The membrane of the present invention is a membrane obtained from the photocurable composition of the present invention described above. The membrane of the present invention can be used in optical filters such as color filters, infrared transmission filters and infrared cut filters.

[0272] The film thickness of the film of the present invention can be appropriately adjusted depending on the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

[0273] When the film of the present invention is used as a color filter, it is preferable that the film has a hue of green, red, blue, cyan, magenta, or yellow. Furthermore, the film of the present invention can be preferably used as a colored pixel of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.

[0274] <Method for Manufacturing Pixels> A method for manufacturing pixels using the photocurable composition of the present invention will now be described. The method for manufacturing pixels includes the steps of forming a composition layer on a support using the photocurable composition of the present invention, exposing the composition layer in a pattern, and developing and removing the unexposed parts of the composition layer. If necessary, a step of drying the composition layer (pre-bake step) and a step of heat-treating the developed pattern (pixel) (post-bake step) may be provided.

[0275] In the step of forming the composition layer, the photocurable composition of the present invention is used to form a composition layer on a support. The support is not particularly limited and can be appropriately selected according to the application. For example, a glass substrate, a silicon substrate, etc. may be mentioned, and a silicon substrate is preferred. Further, on the silicon substrate, a charge-coupled device (CCD), a complementary metal - oxide semiconductor (CMOS), a transparent conductive film, etc. may be formed. Further, on the silicon substrate, a black matrix for isolating each pixel may be formed. Further, on the silicon substrate, an underlayer may be provided for improving adhesion to the upper layer, preventing diffusion of substances, or planarizing the substrate surface. The surface contact angle of the underlayer is preferably 20 to 70° when measured with diiodomethane. Further, it is preferably 30 to 80° when measured with water.

[0276] As a method for applying the photocurable composition, known methods can be used. For example, the drop casting method; the slit coating method; the spray method; the roll coating method; the spin coating method; the casting coating method; the slit and spin method; the prewet method (for example, the method described in JP - A - 2009 - 145395); inkjet (for example, the on - demand system, the piezo system, the thermal system), discharge - type printing such as nozzle jet, various printing methods such as flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing; transfer methods using a mold, etc.; nanoimprint method, etc. can be mentioned. Further, the coating method described in paragraph 0207 of WO 2022 / 085485 can also be used.

[0277] The composition layer formed on the support may be dried (pre - baked). When manufacturing a film by a low - temperature process, pre - baking may not be necessary. When pre - baking is performed, the pre - baking temperature is preferably 150°C or lower, more preferably 120°C or lower, and still more preferably 110°C or lower. The lower limit can be, for example, 50°C or higher, and can also be 80°C or higher. The pre - baking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and still more preferably 80 to 220 seconds. Pre - baking can be performed on a hot plate, an oven, etc.

[0278] Next, the composition layer is exposed in a pattern (exposure step). For example, the composition layer can be exposed in a pattern by exposing it through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. Thereby, the exposed portion can be cured.

[0279] Examples of the light that can be used for exposure include g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), KrF line (wavelength 248 nm), ArF line (wavelength 193 nm), and the like. The light used for exposure is preferably in the wavelength range of 150 to 400 nm, and more preferably excimer laser light in the wavelength range of 150 to 400 nm. A light source with a long wavelength of 400 nm or more can also be used for exposure.

[0280] In the exposure step, it is preferable to expose the composition layer in a pattern by irradiating it with light having a wavelength of 150 to 400 nm (preferably excimer laser light having a wavelength of 150 to 400 nm).

[0281] During exposure, the light may be continuously irradiated for exposure, or may be irradiated in pulses for exposure (pulse exposure). Note that pulse exposure is an exposure method in which light irradiation and休止 are repeated in a cycle of a short time (for example, at the millisecond level or less) for exposure.

[0282] The irradiation amount (exposure amount) is, for example, preferably 0.03 to 2.5 J / cm ２ and more preferably 0.05 to 1.0 J / cm ２ The oxygen concentration during exposure can be appropriately selected. In addition to performing it in the atmosphere, for example, it may be exposed in a low oxygen atmosphere where the oxygen concentration is 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially oxygen-free), or in a high oxygen atmosphere where the oxygen concentration exceeds 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume). Also, the exposure illuminance can be appropriately set. For example, it is preferably 100 to 100000 W / m ２ and more preferably 500 to 50000 W / m ２ In general, it is 10000 to 50000 W / m ２However, in order to increase the light contrast, 1000 W / m ２ The following may also apply. In this invention, the exposure time can be shortened even at such low light levels, thereby improving the yield.

[0283] Next, the unexposed areas of the composition layer are developed and removed to form a pattern (pixels). The unexposed areas of the composition layer can be developed and removed using a developer. This causes the unexposed areas of the composition layer in the exposure process to dissolve in the developer, leaving only the photocured parts. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. In addition, to improve the ability to remove residue, the developer may be emptied every 60 seconds, and the process of supplying fresh developer may be repeated several times.

[0284] Examples of developing solutions include organic solvents and alkaline developers, with alkaline developers being preferred. For the developing solution and the rinsing method after development, the developing solution and rinsing method described in paragraph 0214 of International Publication No. 2022 / 085485 may be used.

[0285] After development and drying, it is preferable to perform additional exposure or heat treatment (post-bake). Additional exposure and post-bake are curing treatments after development to ensure complete hardening. The heating temperature in post-bake is preferably 100 to 300°C, and more preferably 200 to 270°C. Post-bake can be performed continuously or in batches using heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to achieve the above conditions. When performing additional exposure, it is preferable that the light used for exposure has a wavelength of 400 nm or less. The additional exposure may also be performed by the method described in Korean Published Patent No. 10-2017-0122130.

[0286] <Optical Filter> The optical filter of the present invention includes the film of the present invention described above. Examples of types of optical filters include color filters, infrared cut filters, and infrared transmission filters, with color filters being preferred. The color filter preferably has the film of the present invention as its pixels, and more preferably has the film of the present invention as its colored pixels.

[0287] The optical filter may have a protective layer on the surface of the film of the present invention. By providing a protective layer, various functions such as oxygen barrier, low reflectivity, hydrophilicity, and shielding of light of specific wavelengths (ultraviolet rays, infrared rays, etc.) can be imparted. The thickness of the protective layer is preferably 0.01 to 10 μm, and more preferably 0.1 to 5 μm. Methods for forming the protective layer include applying a resin composition for forming the protective layer, chemical vapor deposition, and attaching molded resin with an adhesive. The components that make up the protective layer include (meth)acrylic resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene etherphosphine oxide resin, polyimide resin, polyamide-imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluororesin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al ２ O ３ Mo, SiO ２ Si ２ N ４ These are some examples, and two or more of these components may be included. For example, in the case of a protective layer intended for oxygen barrier, the protective layer may be made of polyol resin and SiO ２ And, Si ２ N ４ It is preferable that it contains [a certain substance]. Furthermore, in the case of a protective layer intended for low reflectivity, it is preferable that the protective layer contains (meth)acrylic resin and fluororesin.

[0288] When forming a protective layer by coating a resin composition, known methods such as spin coating, casting, screen printing, and inkjet printing can be used as the coating method for the resin composition. The organic solvent contained in the resin composition can be a known organic solvent (for example, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.). When forming the protective layer by chemical vapor deposition, known chemical vapor deposition methods (thermochemical vapor deposition, plasma chemical vapor deposition, photochemical vapor deposition) can be used.

[0289] The protective layer may contain additives such as organic and inorganic fine particles, light absorbers of specific wavelengths (e.g., ultraviolet, infrared, etc.), refractive index adjusters, antioxidants, adhesives, and surfactants, as needed. Examples of organic and inorganic fine particles include polymer fine particles (e.g., silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium dioxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, silica, calcium carbonate, and barium sulfate. Known light absorbers can be used for light absorbers of specific wavelengths. The content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by mass and more preferably 1 to 60% by mass relative to the total mass of the protective layer.

[0290] As a protective layer, the protective layer described in paragraphs 0073 to 0092 of Japanese Patent Publication No. 2017-151176 can also be used.

[0291] The optical filter may have a structure in which each pixel is embedded in a space partitioned, for example, in a grid pattern by a partition wall.

[0292] <Solid-State Image Sensor> The solid-state image sensor of the present invention has the film of the present invention described above. The configuration of the solid-state image sensor is not particularly limited as long as it has the film of the present invention and functions as a solid-state image sensor, but for example, the following configuration can be given.

[0293] The device has a substrate on which multiple photodiodes and transfer electrodes made of polysilicon or the like constitute the light-receiving area of ​​a solid-state image sensor (such as a CCD (charge-coupled device) image sensor or a CMOS (complementary metal-oxide-semiconductor) image sensor), a light-shielding film with an opening only for the light-receiving portion of the photodiode is placed on the photodiode and transfer electrodes, a device protection film made of silicon nitride or the like is formed on the light-shielding film to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode, and a color filter is placed on the device protection film. Furthermore, the device may have a configuration in which a light-gathering means (for example, a microlens; the same applies hereinafter) is placed on the device protection film and below the color filter (on the side closer to the substrate), or a configuration in which the light-gathering means is placed on the color filter. The color filter may also have a structure in which each colored pixel is embedded in a space partitioned by partitions, for example in a grid pattern. In this case, it is preferable that the partitions have a lower refractive index than each colored pixel. Examples of imaging devices having such a structure include those described in Japanese Patent Publication No. 2012-227478, Japanese Patent Publication No. 2014-179577, and International Publication No. 2018 / 043654. Furthermore, as shown in Japanese Patent Publication No. 2019-211559, the light resistance may be improved by providing an ultraviolet absorption layer within the structure of the solid-state image sensor. The imaging device equipped with the solid-state image sensor of the present invention can be used not only in digital cameras and electronic devices with imaging functions (such as mobile phones), but also in in-vehicle cameras and surveillance cameras.

[0294] <Image Display Device> The image display device of the present invention has the film of the present invention described above. Examples of image display devices include liquid crystal display devices and organic electroluminescent display devices. For definitions of image display devices and details of each image display device, see, for example, "Electronic Display Devices" (by Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990) and "Display Devices" (by Yoshiaki Ibuki, Sangyo Tosho Co., Ltd., published in 1989). Liquid crystal display devices are described, for example, in "Next-Generation Liquid Crystal Display Technology" (edited by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published in 1994). There are no particular restrictions on the liquid crystal display devices to which the present invention can be applied; for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "Next-Generation Liquid Crystal Display Technology".

[0295] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the structural formulas shown below, Me represents a methyl group, Ph represents a phenyl group, and iPr represents an isopropyl group.

[0296] <Manufacturing of Dispersion> The materials listed in the table below are mixed to obtain a mixture. The resulting mixture is then dispersed using an Ultra Apex Mill manufactured by Kotobuki Kogyo Co., Ltd. as a circulating dispersion device (bead mill) to produce the dispersion. If two or more materials are listed in the "Type" column of the table, the total amount of each material used in equal amounts should be recorded in the "Parts by Mass" column.

[0297]

[0298] The details of the materials listed in the table above are as follows:

[0299] (Colorants) PG36: C.I. Pigment Green 36 (green pigment) PG58: C.I. Pigment Green 58 (green pigment) PY129: C.I. Pigment Yellow 129 (yellow pigment) PY138: C.I. Pigment Yellow 138 (yellow pigment) PY139: C.I. Pigment Yellow 139 (yellow pigment) PY150: C.I. Pigment Yellow 150 (yellow pigment) PY185: C.I. Pigment Yellow 185 (yellow pigment) PY215: C.I. Pigment Yellow 215 (yellow pigment) PR177: C.I. Pigment Red 177 (red pigment) PR254: C. I. Pigment Red 254 (red pigment) PR264: C. I. Pigment Red 264 (red pigment) PR272: C. I. Pigment Red 272 (red pigment) PR291: C. I. Pigment Red 291 (red pigment) PO71: C. I. Pigment Orange 71 (orange pigment) PB15:6: C. I. Pigment Blue 15:6 (blue pigment) PV23: C. I. Pigment Violet 23 (purple pigment) P-1: Compound with the following structure (pyrrolopyrrole compound, infrared absorbing pigment) P-2: Compound with the following structure (squallium compound, infrared absorbing pigment) P-3: Titanium Black (TiOxNy) (black pigment, manufactured by Mitsubishi Materials Corporation) P-4: Titanium Oxide (white pigment, TTO-51(C), manufactured by Ishihara Sangyo Co., Ltd.) P-5: Compound with the following structure (magenta dye)

[0300] (Dispersing agent) Syn-1, Syn-2, Syn-4 to Syn-7: Compounds with the following structure Syn-3: Compound with the following structure (a / b / c = 10 / 70 / 20 (mol%), weight-average molecular weight 600)

[0301] (Resin) C2-1: Resin with the following structure (the values ​​attached to the main chain are molar ratios, and the values ​​attached to the side chains are the number of repeating units. Weight-average molecular weight 20,000, acid value 67 mgKOH / g) C2-2: Resin with the following structure (the numerical values attached to the main chain are molar ratios, and the numerical values attached to the side chain are the number of repeating units. Weight average molecular weight 23,000, acid value 59 mg KOH / g) C2-3: Resin with the following structure (the numerical values attached to the main chain are molar ratios, and the numerical values attached to the side chain are the number of repeating units. Weight average molecular weight 18,000, acid value 69 mg KOH / g) C2-4: Resin with the following structure (the numerical values attached to the main chain are molar ratios, and the numerical values attached to the side chain are the number of repeating units. Weight average molecular weight 23,000, acid value 67 mg KOH / g) C2-5: Resin with the following structure (weight average molecular weight 10,000, acid value 85 mg KOH / g) C2-6: Resin with the following structure (weight average molecular weight 18,000, acid value 82 mg KOH / g) C2-7: Resin with the following structure (weight average molecular weight 8,000, acid value 50 mg KOH / g) C2-8: Resin with the following structure (the numerical values attached to the main chain are molar ratios, and the numerical values attached to the side chain are the number of repeating units. Weight average molecular weight 28,000, acid value 95 mg KOH / g)

[0302] (Solvent) S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Propylene glycol monomethyl ether (PGME) S-3: Cyclopentanone S-4: 3-Methoxybutanol

[0303] <Manufacture of photocurable composition> Mix the materials of the types shown in the following table, 0.2 parts by mass of KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a surfactant, and 0.2 parts by mass of Adeka Stab AO-80 (manufactured by ADEKA Corporation) as an antioxidant to manufacture a photocurable composition. In addition, when there are descriptions of two or more materials in the "Type" column of the table, the total amount using equal amounts of each material is described in the "parts by mass" column.

[0304]

[0305] The details of the materials described in the above table are as follows.

[0306] (Dispersion liquid) Dispersion liquid R1 to R6, G1 to G6, B1 to B3, IR1 to IR2, Bk1 to Bk2, Wh1: The above-mentioned dispersion liquid R1 to R6, G1 to G6, B1 to B3, IR1 to IR2, Bk1 to Bk2, Wh1

[0307] (Resin) B-1: Resin with the following structure (the values ​​appended to the main chain are molar ratios. Weight-average molecular weight 11000, acid value 69 mgKOH / g) B-2: Resin with the following structure (the values ​​attached to the main chain are molar ratios, and the values ​​attached to the side chains are the number of repeating units. Weight-average molecular weight: 21,000) B-3: Resin with the following structure (the values ​​appended to the main chain are molar ratios. Weight-average molecular weight 12000, acid value 80 mgKOH / g) B-4: Resin with the following structure (the values ​​appended to the main chain are molar ratios. Weight-average molecular weight 26,000, polyamic acid resin) B-5: Resin with the following structure (the values ​​appended to the main chain are molar ratios. Weight-average molecular weight 25,000, polyimide resin)

[0308] (Polymerizable compound) M-1: A mixture of compounds with the following structure (a mixture in which the molar ratio of the compound on the left (a hexafunctional (meth)acrylate compound) and the compound on the right (a pentafunctional (meth)acrylate compound) is 7:3). M-2: Compound with the following structure M-3: Compound with the following structure M-4: Compound with the following structure M-5: Compound with the following structure

[0309] (Photopolymerization initiators) A-1 to A-13: Compounds A-1 to A-13 shown as specific examples of specific compounds cA-1: ADEKA Arclus N-1919T (manufactured by ADEKA Corporation) I-1, I-2: Compounds with the following structure (other photopolymerization initiators)

[0310] I-3: TR-PBG-304 (manufactured by TRONLY, other photopolymerization initiator) I-4: A mixture of equal parts of ADEKA Arclus NCI-730, ADEKA Arclus NCI-831, and ADEKA Arclus NCI-930 (all manufactured by ADEKA Corporation) (other photopolymerization initiator)

[0311] (Polymerization inhibitors) K-1: 2,2,6,6-tetramethylpiperidine-1-oxyl K-2: p-methoxyphenol K-3: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl K-4: di-tert-butyl-p-cresol K-5: benzoquinone

[0312] (Additives) T-1 to T-8: Compounds with the following structure

[0313] (Solvents) S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Propylene glycol monomethyl ether (PGME) S-5: Cyclohexanone S-6: 3-Methoxypropanol

[0314] <Dependence on Exposure Illuminance> An underlayer-forming composition (CT-4000L, manufactured by Fujifilm Electronic Materials Co., Ltd.) is applied to an 8-inch (20.32 cm) silicon wafer using a spin coater to a thickness of 0.1 μm after post-baking. The underlayer is then formed by heating at 220°C for 300 seconds using a hot plate, thereby obtaining a silicon wafer with an underlayer. Each photocurable composition is applied to the underlayer of the silicon wafer using a spin coating method to a film thickness of 0.6 μm after application. The composition layer is then formed by heating at 110°C for 2 minutes using a hot plate. Next, the obtained composition layer is exposed to light with a wavelength of 365 nm (i-line) through a mask having a 0.45 μm square pattern using an i-line stepper exposure machine at an illuminance of 20,000 W / m ２ , exposure amount 20-300mJ / cm ２ Exposure conditions (exposure condition 1), or illuminance of 2000 W / cm² ２ , exposure amount 20-300mJ / cm ２The material is exposed by irradiation under exposure conditions (exposure condition 2). Next, the exposed composition layer is shower-developed at 23°C for 60 seconds using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) as the developer. After that, water droplets adhering to the pattern surface are removed with air, and the pattern is allowed to air dry to form the pattern (pixels). The silicon wafer on which the pixels have been formed is observed at a magnification of 20,000x using a scanning electron microscope (S-4800H, Hitachi High-Tech Corporation). The amount of exposure required for the pattern line width to reach 0.5 μm in the observed pixels is calculated. The ratio (Ea / Eb) of the amount of exposure required for the pattern line width to reach 0.5 μm when exposed under exposure condition 1 to reach 0.5 μm when exposed under exposure condition 2 is calculated, and the exposure illuminance dependence is evaluated according to the following criteria. The closer the value of Ea / Eb is to 1, the smaller the exposure illuminance dependence of the exposure amount. -Evaluation Criteria- A: Ea / Eb is 0.95 or higher and less than 1.05 B: Ea / Eb is 0.90 or higher and less than 0.95, or 1.05 or higher and less than 1.10 C: Ea / Eb is 0.80 or higher and less than 0.90, or 1.10 or higher and less than 1.20 D: Ea / Eb is 0.70 or higher and less than 0.80, or 1.20 or higher and less than 1.30 E: Ea / Eb is less than 0.70, or 1.30 or higher

[0315] <Developability> Each photocurable composition is applied by spin coating onto the underlayer of the silicon wafer with the underlayer to a film thickness of 0.6 μm after application, and then heated at 110°C for 2 minutes using a hot plate to form the composition layer. Next, the obtained composition layer is exposed to light with a wavelength of 365 nm (i-line) through a mask having a 0.45 μm square pattern using an i-line stepper exposure machine at an illuminance of 20,000 W / m ２The material is irradiated with the above exposure amount Ea to perform exposure. Next, the exposed composition layer is shower-developed at 23°C for 60 seconds using either a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) (developer 1) or a 0.03% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) (developer 2) as the developer. After that, water droplets adhering to the pattern surface are removed with air, and the pattern is allowed to air dry to form the pattern (pixels). The silicon wafer on which the pixels have been formed is observed at a magnification of 20,000x using a scanning electron microscope (S-4800H, manufactured by Hitachi High-Tech Corporation). The area ratio of the residue (%) in the observed pixels (area ratio of the residue = calculated using software that calculates the area of ​​the residue portion in black and white within the pattern aperture) was calculated. The ratio (Za / Zb) of the area ratio of the residue formed using developer 1 (Za) to the area ratio of the residue formed using developer 2 (Zb) is calculated, and the developability is evaluated according to the following criteria. The closer Za / Zb is to 1, the less dependent it is on the developer concentration and the better the developability. -Evaluation Criteria- A: Za / Zb is 0.95 or more and less than 1.05 B: Za / Zb is 0.90 or more and less than 0.95, or 1.05 or more and less than 1.10 C: Za / Zb is 0.80 or more and less than 0.90, or 1.10 or more and less than 1.20 D: Za / Zb is 0.70 or more and less than 0.80, or 1.20 or more and less than 1.30 E: Za / Zb is less than 0.70, or 1.30 or more

[0316] (Sensitivity) Each photocurable composition was applied by spin coating onto the substrate of the silicon wafer with the above-mentioned substrate so that the film thickness after coating was 0.6 μm. Then, the composition layer was formed by heating at 110°C for 2 minutes using a hot plate. Next, the obtained composition layer was exposed to light with a wavelength of 365 nm (i-line) through a mask having a 0.45 μm square pattern using an i-line stepper exposure machine at an illuminance of 2000 W / m ２ , exposure amount 20-300mJ / cm ２The exposure is performed by varying the irradiation within the specified range. Next, the exposed composition layer is shower-developed at 23°C for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) as the developer. After that, water droplets adhering to the pattern surface are removed with air, and the pattern is allowed to air dry to form the pattern (pixels). The silicon wafer on which the pixels have been formed is observed at a magnification of 20,000x using a scanning electron microscope (S-4800H, Hitachi High-Tech Corporation). The exposure amount Ea required for the pattern line width to reach 0.5 μm in the observed pixels is calculated. -Evaluation criteria- A: Ea is 100 mJ / cm ２ B: Ea is less than 100 mJ / cm² ２ More than 200mJ / cm ２ C:Ea is less than 200 mJ / cm² ２ More than 500mJ / cm ２ D: Ea is less than 500 mJ / cm² ２ More than 1000mJ / cm ２ E: Ea is less than 1000 mJ / cm² ２ That's all.

[0317]

[0318] As shown in the table above, the examples demonstrate excellent evaluation of exposure intensity dependence, developability, and sensitivity.

[0319] Similar results can be obtained even if the silicon wafer with a base layer used in each evaluation is changed to a silicon wafer with a 3 nm thick base layer formed using the base material compositions 1 to 9 shown below.

[0320]

[0321] The details of the materials listed in the table above are as follows:

[0322] (Resin) B-U1: Resin with the following structure (weight-average molecular weight 30,000, the values ​​attached to the main chain are mass ratios, and the values ​​attached to the side chains are the number of repeating units.) B-U2: Cyclomer P (ACA) 230AA (manufactured by Daicel Corporation) B-U3: Resin with the following structure (weight-average molecular weight 30,000, the values ​​attached to the main chain are mass ratios, and the values ​​attached to the side chains are the number of repeating units.) B-U4: Acrycure-RD-F8 (manufactured by Nippon Shokubai Co., Ltd.)

[0323] (Additive) T-U1: EHPE3150 (manufactured by Daicel Corporation, epoxy resin)

[0324] (Surfactants) W-U1: KF-6000 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone-based surfactant) W-U2: KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone-based surfactant)

[0325] (Solvents) S-U1: Propylene glycol monomethyl ether acetate S-U2: Propylene glycol diacetate S-U3: n-butyl acetate S-U4: 2-heptanone S-U5: 3-methoxybutanol

Claims

It comprises a photopolymerization initiator, a polymerizable compound, a colorant, a resin, and a polymerization inhibitor. The photopolymerization initiator comprises a compound represented by formula (1), The resin is a photocurable composition comprising a resin having an acid group; In formula (1), R １ and R ２ Each of these independently represents a substituent, m represents 1 or 0, n represents 1 or 0, x represents 1 or 0, y represents 1 or 0, z represents either 1 or 0. 　 R in formula (1) above １ and R ２ The photocurable composition according to claim 1, wherein each of the terms independently represents an alkyl group, an aryl group, or a heteroaryl group. 　 R in formula (1) above １ and R ２ The photocurable composition according to claim 1, wherein each of the groups independently represents a methyl group, an ethyl group, or a phenyl group. 　 The photocurable composition according to claim 1, wherein the compound represented by formula (1) is a compound represented by any one of formulas (A-1) to (A-13). The photocurable composition according to claim 4, wherein the compound represented by formula (1) is a compound represented by any one of the formulas (A-1) to (A-3). 　 The photocurable composition according to any one of claims 1 to 5, wherein the acid value of the resin having the acid group is 50 to 100 mg KOH / g. 　 The photocurable composition according to any one of claims 1 to 5, comprising an N-oxy radical compound having a six-membered ring structure as the polymerization inhibitor. 　 A method for manufacturing a pixel, comprising the steps of: forming a composition layer on a support using a photocurable composition according to any one of claims 1 to 5; irradiating the composition layer with light of a wavelength of 150 to 400 nm to expose it in a patterned manner; and developing and removing the unexposed portion of the composition layer. 　 A film obtained by curing a photocurable composition according to any one of claims 1 to 5. 　 An optical filter comprising the film described in claim 9. 　 A solid-state image sensor comprising the film described in claim 9. 　 An image display device comprising the film described in claim 9.

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