Curable composition, film, optical filter, solid-state imaging element, and image display device

Abstract

This curable composition contains a resin, a polymerizable compound, and a photopolymerization initiator. The photopolymerization initiator contains: an oxime compound C1 having an absorption coefficient of 75000 mL / (g·cm) or more at a wavelength of 248 nm; and an oxime compound C2 which is a compound different from the oxime compound C1 and which has an absorption coefficient of 3000 mL / (g·cm) or more at a wavelength of 365 nm. The present invention also pertains to a film, an optical filter, a solid-state imaging element, and an image display device, in all of which the curable composition is used.

Description

Curable composition, film, optical filter, solid-state imaging device and image display device

[0001] The present invention relates to a curable composition containing a polymerizable compound and a photopolymerization initiator. The present invention also relates to a film, an optical filter, a solid-state imaging device, and an image display device using the curable composition.

[0002] Curable compositions containing a polymerizable compound and a photopolymerization initiator can be polymerized and cured by irradiation with light, and are therefore used in optical filters, photocurable inks, photosensitive printing plates, various photoresists, and the like.

[0003] Patent Document 1 describes the production of a color filter for a solid-state imaging device using a curable composition containing a pigment, a binder resin, a polymerizable compound, and an oxime ester initiator.

[0004] Japanese Patent Application Laid-Open No. 2022-113705

[0005] In recent years, efforts have been made to improve the resolution of solid-state imaging devices equipped with optical filters such as color filters, and further miniaturization of pixel sizes for optical filters such as color filters has been studied.

[0006] However, when pixels are formed by patterning a curable composition using a method such as photolithography, the rectangularity of the resulting pixels tends to decrease as the pixel size becomes smaller.

[0007] Therefore, an object of the present invention is to provide a curable composition capable of forming pixels with excellent rectangularity. Another object of the present invention is to provide a film, an optical filter, a solid-state imaging device, and an image display device using the curable composition.

[0008] The present inventors have conducted research and found that the above object can be achieved by using a curable composition described below, and have thus completed the present invention.

[0009] <1> A curable composition comprising a resin, a polymerizable compound, and a photopolymerization initiator, wherein the photopolymerization initiator comprises: an oxime compound C1 having an absorption coefficient of 75,000 mL / (g cm) or more at a wavelength of 248 nm; and an oxime compound C2, which is a compound different from the oxime compound C1 and has an absorption coefficient of 3,000 mL / (g cm) or more at a wavelength of 365 nm. <2> The curable composition according to <1>, comprising 25 to 400 parts by mass of the oxime compound C2 relative to 100 parts by mass of the oxime compound C1. <3> The curable composition according to <1> or <2>, comprising 50 to 200 parts by mass of the oxime compound C2 relative to 100 parts by mass of the oxime compound C1. <4> The curable composition according to any one of <1> to <3>, comprising 50 to 200 parts by mass of the oxime compound C2 relative to 100 parts by mass of the oxime compound C1. <5> The curable composition according to any one of <1> to <4>, wherein the polymerizable compound includes a polymerizable compound having an ethylene oxide repeating chain. <6> The curable composition according to any one of <1> to <5>, wherein the oxime compound C1 is contained in an amount of 25 to 200 parts by mass per 100 parts by mass of the polymerizable compound. <7> The curable composition according to any one of <1> to <6>, wherein the resin includes a resin having a crosslinkable group. <8> The curable composition according to any one of <1> to <7>, wherein the oxime compound C1 is an oxime compound having an indole ring. <9> The curable composition according to any one of <1> to <8>, wherein the oxime compound C1 has at least one skeleton selected from an anthraquinone skeleton, a xanthone skeleton, a dibenzofuran skeleton, a fluorenone skeleton, an indanedione skeleton, and a coumaranone skeleton. <10> The curable composition according to any one of <1> to <9>, wherein the oxime compound C1 has an alkyl group substituted with a cycloalkyl group. <11> The curable composition according to any one of <1> to <10>, further comprising a colorant, wherein the content of the colorant in the total solid content of the curable composition is 50 mass% or more.<12> The curable composition according to any one of <1> to <11>, further comprising a colorant, containing 10 to 30 parts by mass of the polymerizable compound relative to 100 parts by mass of the colorant, and containing 3 to 10 parts by mass of the oxime compound C1 and the oxime compound C2 in total relative to 100 parts by mass of the colorant. <13> A film obtained using the curable composition according to any one of <1> to <12>. <14> An optical filter having the film according to <13>. <15> A solid-state imaging device having the film according to <13>. <16> An image display device having the film according to <13>.

[0010] According to the present invention, it is possible to provide a curable composition capable of forming pixels with excellent rectangularity. The present invention also makes it possible to provide a film, an optical filter, a solid-state imaging device, and an image display device.

[0011] The present invention will be described in detail below. In this specification, the term "to" is used to mean that the numerical values ​​before and after the term are included as the lower and upper limits. In the description of groups (atomic groups) in this specification, a term without specifying whether it is substituted or unsubstituted encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (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. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation. As used herein, "(meth)acrylate" refers to either or both of acrylate and methacrylate, "(meth)acrylic" refers to either or both of acrylic and methacrylic, and "(meth)acryloyl" refers to either or both of acryloyl and methacryloyl. In the structural formulae herein, Me refers to a methyl group, Et refers to an ethyl group, Bu refers to a butyl group, and Ph refers to a phenyl group. As used herein, the weight-average molecular weight and number-average molecular weight are polystyrene-equivalent values ​​measured by GPC (gel permeation chromatography). As used herein, the term "total solids" refers to the total mass of all components of a composition excluding the solvent. As used herein, the term "pigment" refers to a coloring material that is difficult to dissolve in a solvent. As used herein, the term "process" refers not only to an independent process, but also to a process that cannot be clearly distinguished from other processes, as long as the intended effect of the process is achieved.

[0012] <Curable Composition> The curable composition of the present invention is a curable composition containing a resin, a polymerizable compound, and a photopolymerization initiator, wherein the photopolymerization initiator contains an oxime compound C1 having an absorption coefficient of 75,000 mL / (g cm) or more at a wavelength of 248 nm, and an oxime compound C2 which is a compound different from the oxime compound C1 and has an absorption coefficient of 3,000 mL / (g cm) or more at a wavelength of 365 nm.

[0013] The curable composition of the present invention allows for the formation of pixels with excellent rectangularity. The reason for this effect is presumed to be as follows. By using oxime compound C1 and oxime compound C2 as photopolymerization initiators, the curable composition of the present invention prevents the radical concentration in the film from becoming too high during exposure, suppressing deactivation due to recombination of radicals generated from the photopolymerization initiators, and allowing the polymerization reaction of the polymerizable compound to proceed almost uniformly across the thickness of the film. This is presumed to be why pixels with excellent rectangularity were formed. Furthermore, the curable composition of the present invention allows for pixels with excellent rectangularity to be formed even when the exposure wavelength is changed during exposure. Furthermore, the curable composition of the present invention allows for sufficient polymerization reaction to proceed even at the bottom of the film (the support side), thereby allowing for the formation of pixels with excellent adhesion.

[0014] The curable composition of the present invention is preferably used as a curable composition for an optical filter. Examples of optical filters include color filters, infrared transmission filters, and infrared cut filters, and color filters are preferred. The curable composition of the present invention is also preferably used for solid-state imaging devices. More specifically, the curable composition is preferably used as a curable composition for optical filters used in solid-state imaging devices, and more preferably used as a curable composition for forming colored pixels of color filters used in solid-state imaging devices.

[0015] The color filter may have colored pixels that transmit light of a specific wavelength. Examples of the colored pixels include red, green, blue, magenta, cyan, and yellow pixels. The colored pixels of the color filter may be formed using a curable composition containing a chromatic colorant.

[0016] The infrared cut filter preferably has a maximum absorption wavelength in the wavelength range of 700 to 1800 nm, more preferably in the wavelength range of 700 to 1300 nm, and even more preferably in the wavelength range of 700 to 1000 nm. The transmittance of the infrared cut filter over the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. The transmittance at at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less. The ratio of the absorbance Amax at the infrared cut filter's maximum absorption wavelength 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 curable composition containing an infrared-absorbing colorant.

[0017] The infrared transmission filter is a filter that transmits at least a portion of infrared light. The infrared transmission filter is preferably a filter that blocks at least a portion of visible light and transmits at least a portion of infrared light. Examples of the infrared transmission filter include a filter that satisfies the spectral characteristics of 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. The infrared transmission filter is preferably a filter that satisfies any one of the following spectral characteristics (1) to (5): (1): A filter that has 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 800 to 1500 nm. (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.

[0018] The curable composition of the present invention can also be used as a light-shielding film.

[0019] The solids concentration of the curable 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 even more preferably 15% by mass or less.

[0020] Each component used in the curable composition of the present invention will be described below.

[0021] <<Resin>> The curable composition of the present invention contains a resin. The resin is blended, for example, for the purpose of dispersing pigments and the like in the curable composition or for the purpose of using as a binder. Note that a resin that is mainly used to disperse pigments and the like in the curable composition is also called a dispersant. However, such uses of the resin are only examples, and the resin can also be used for purposes other than these uses.

[0022] 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 ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and siloxane resins. Further, examples of the resin include the resins described in paragraphs 0091 to 0099 of WO 2022 / 065215, the blocked polyisocyanate resins described in JP 2016-222891 A, the resins described in JP 2020-122052 A, the resins described in JP 2020-111656 A, the resins described in JP 2020-139021 A, the resins described in JP 2017-138503 A containing a structural unit having a ring structure in the main chain and a structural unit having a biphenyl group in the side chain, and the resins described in paragraphs 0199 to 0199 of JP 2020-186373 A. 0233, the alkali-soluble resin described in JP 2020-186325 A, the resin represented by formula 1 described in Korean Patent Publication No. 10-2020-0078339, the copolymer containing an epoxy group and an acid group described in WO 2022 / 030445, the resin described in JP 2018-135514 A, the copolymer described in JP 2020-041046 A, the resin described in JP 2023-033156 A, the resin described in JP 2023-030386 A, and the resin described in JP 2023-027753 A can also be used.

[0023] The weight average molecular weight (Mw) of the resin is preferably 3,000 to 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.

[0024] The resin to be used is preferably a resin having an acid group, such as a carboxy group, a phosphate group, a sulfo group, or a phenolic hydroxy group.

[0025] The acid value of the resin having acid groups is preferably 30 to 500 mgKOH / g. The lower limit is more preferably 40 mgKOH / g or more, and particularly preferably 50 mgKOH / g or more. The upper limit is more preferably 400 mgKOH / g or less, even more preferably 300 mgKOH / g or less, and particularly preferably 200 mgKOH / g or less. The weight average molecular weight (Mw) of the resin having acid groups is preferably 5,000 to 100,000, and more preferably 5,000 to 50,000. The number average molecular weight (Mn) of the resin having acid groups is preferably 1,000 to 20,000.

[0026] The resin having an acid group preferably contains a repeating unit having an acid group on a side chain, and more preferably contains 5 to 70 mol% of the repeating units having an acid group on a side chain based on all repeating units of the resin. The upper limit of the content of repeating units having an acid group on a side chain is preferably 50 mol% or less, more preferably 30 mol% or less. The lower limit of the content of repeating units having an acid group on a side chain is preferably 10 mol% or more, more preferably 20 mol% or more.

[0027] For resins having acid groups, please refer to the descriptions in paragraphs

[0558] to

[0571] of JP 2012-208494 A (corresponding to paragraphs

[0685] to

[0700] of U.S. Patent Application Publication No. 2012 / 0235099 A) and paragraphs

[0076] to

[0099] of JP 2012-198408 A, the contents of which are incorporated herein by reference. Alternatively, commercially available resins having acid groups can be used. There are no particular limitations on the method for introducing acid groups into the resin, and examples include the method described in Japanese Patent No. 6,349,629 A. Furthermore, examples of methods for introducing acid groups into the resin include a method in which an acid anhydride is reacted with a hydroxy group generated by a ring-opening reaction of an epoxy group to introduce the acid group.

[0028] A resin having a basic group can also be used as the resin. The resin having a basic group is preferably a resin containing a repeating unit having a basic group in the side chain, more preferably a copolymer having a repeating unit having a basic group in the side chain and a repeating unit not containing a basic group, and even more preferably a block copolymer having a repeating unit having a basic group in the side chain and a repeating unit not containing 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 mgKOH / g. The lower limit is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more. The upper limit is preferably 200 mgKOH / g or less, more preferably 100 mgKOH / g or less.

[0029] Commercially available resins having basic groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, and BYK-LPN6919 (all manufactured by BYK-Chemie), and Solsperse 112. 00, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 7100 (all manufactured by The Lubrizol Group, Japan), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), and the like. In addition, the resin having a basic group may be the block copolymer (B) described in paragraphs 0063 to 0112 of JP-A-2014-219665, the block copolymer A1 described in paragraphs 0046 to 0076 of JP-A-2018-156021, or the vinyl resin having a basic group described in paragraphs 0150 to 0153 of JP-A-2019-184763, the contents of which are incorporated herein by reference.

[0030] It is also preferable to use a resin having an acid group and a resin having a basic group. According to this embodiment, the storage stability of the curable composition can be further improved. When a resin having an acid group and a resin having a basic group are used in combination, the content of the resin having a basic group is preferably 20 to 500 parts by mass, more preferably 30 to 300 parts by mass, and even more preferably 50 to 200 parts by mass per 100 parts by mass of the resin having an acid group.

[0031] It is also preferable to use a resin having an aromatic carboxy group as the resin. In a resin having an aromatic carboxy group, the aromatic carboxy group may be contained in the main chain of the repeating unit or may be contained in a side chain of the repeating unit. It is preferable that the aromatic carboxy group is contained in the main chain of the repeating unit. In this specification, an aromatic carboxy group refers to a group having a structure in which one or more carboxy groups are bonded to an aromatic ring. In the aromatic carboxy group, the number of carboxy groups bonded to the aromatic ring is preferably 1 to 4, and more preferably 1 to 2. Examples of resins having an aromatic carboxy group include the resins described in paragraphs 0082 to 0107 of WO 2021 / 166858.

[0032] It is also preferable to use a resin having a crosslinkable group as the resin. Examples of the crosslinkable group include a (meth)acryloyl group, an epoxy group, and an oxetanyl group. When a resin having a crosslinkable group is used, the content of the resin having a crosslinkable group in the resin contained in the curable composition is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more.

[0033] The resin is preferably at least one selected from the group consisting of graft polymers, star polymers, block copolymers, and resins in which at least one end of the polymer chain is capped with an acid group. Such resins are preferably used as dispersants.

[0034] Examples of graft polymers include resins having repeating units with graft chains. Examples of graft chains include graft chains containing at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure, and a poly(meth)acrylic structure. The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an alkoxy group, and an alkylthioether group. Of these, from the viewpoint of improving the dispersibility of the pigment, groups having a steric repulsion effect are preferred, and alkyl or alkoxy groups having 5 to 30 carbon atoms are preferred. The alkyl and alkoxy groups may be linear, branched, or cyclic, with linear or branched being preferred.

[0035] Specific examples of the graft polymer include the resins described in paragraphs 0025 to 0094 of JP-A-2012-255128, paragraphs 0022 to 0097 of JP-A-2009-203462, and paragraphs 0102 to 0166 of JP-A-2012-255128.

[0036] Examples of star polymers include resins having a structure in which multiple polymer chains are bonded to a core portion. Specific examples of star polymers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP 2013-043962 A.

[0037] The block copolymer is preferably a block copolymer of a polymer block having a repeating unit containing an acid group or a basic group (hereinafter also referred to as block A) and a polymer block having a repeating unit not containing an acid group or a basic group (hereinafter also referred to as block B). As the block copolymer, the block copolymer (B) described in paragraphs 0063 to 0112 of JP-A No. 2014-219665 and the block copolymer A1 described in paragraphs 0046 to 0076 of JP-A No. 2018-156021 can also be used, the contents of which are incorporated herein by reference.

[0038] The resin having at least one end of the polymer chain capped with an acid group includes a resin having a structure in which at least one end of the polymer chain containing at least one structure selected from a polyester structure, a polyether structure, and a poly(meth)acrylic structure is capped with an acid group. The acid group capping the end of the polymer chain includes a carboxy group, a sulfo group, and a phosphate group.

[0039] The resin can also be used as a dispersant. Examples of dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the term "acidic dispersant (acidic resin)" refers to a resin in which the amount of acid groups is greater than the amount of basic groups. As the acidic dispersant (acidic resin), a resin in which the amount of acid groups is 70 mol% or more is preferred when the total amount of the acid groups and the basic groups is taken as 100 mol%. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxy group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH / g. Furthermore, the term "basic dispersant (basic resin)" refers to a resin in which the amount of basic groups is greater than the amount of acid groups. As the basic dispersant (basic resin), a resin in which the amount of basic groups is greater than 50 mol% is preferred when the total amount of the acid groups and the basic groups is taken as 100 mol%. The basic group possessed by the basic dispersant is preferably an amino group.

[0040] Dispersants are also commercially available, and specific examples thereof include the Disperbyk series manufactured by BYK-Chemie (e.g., Disperbyk-111, 161, 2001, etc.), the Solsperse series manufactured by Lubrizol Japan Co., Ltd. (e.g., Solsperse 20000, 76500, etc.), the Ajisper series manufactured by Ajinomoto Fine-Techno Co., Ltd., A208F (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), H-3606 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and Sandet ET (manufactured by Sanyo Chemical Industries, Ltd.). In addition, the products described in paragraph 0129 of JP-A No. 2012-137564 and the products described in paragraph 0235 of JP-A No. 2017-194662 can also be used as dispersants.

[0041] The content of the resin in the total solid content of the curable composition is preferably 1 to 60% by mass. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 20% by mass or more. The upper limit is preferably 50% by mass or less, and more preferably 40% by mass or less. The content of the resin having an acid group in the total solid content of the curable composition is preferably 1 to 60% by mass. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 20% by mass or more. The upper limit is preferably 50% by mass or less, and more preferably 40% by mass or less. The curable composition of the present invention may contain only one type of resin, or may contain two or more types of resin. When two or more types of resins are contained, it is preferable that the total amount thereof is within the above range.

[0042] <<Polymerizable Compound>> The curable composition of the present invention contains a polymerizable compound. Examples of the polymerizable compound include a compound having an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group. The polymerizable compound used in the present invention is preferably a radically polymerizable compound.

[0043] The polymerizable compound may be in any chemical form, such as a monomer, prepolymer, or oligomer, but is preferably a monomer. The molecular weight of the polymerizable compound is preferably 100 to 2500. The upper limit is preferably 2000 or less, more preferably 1500 or less. The lower limit is preferably 150 or more, more preferably 250 or more.

[0044] The ethylenically unsaturated bond-containing group value (hereinafter referred to as C═C value) of the polymerizable compound is preferably 2 to 14 mmol / g from the viewpoint of storage stability of the curable composition. The lower limit is preferably 3 mmol / g or more, more preferably 4 mmol / g or more, and even more preferably 5 mmol / g or more. The upper limit is preferably 12 mmol / g or less, more preferably 10 mmol / g or less, and even more preferably 8 mmol / g or less. The C═C value of the polymerizable compound is a value calculated by dividing the number of ethylenically unsaturated bond-containing groups contained in one molecule of the polymerizable compound by the molecular weight of the polymerizable compound.

[0045] The polymerizable compound is preferably a compound containing three or more ethylenically unsaturated bond-containing groups, more preferably a compound containing 3 to 15 ethylenically unsaturated bond-containing groups, and even more preferably a compound containing 3 to 6 ethylenically unsaturated bond-containing groups. Furthermore, the polymerizable compound is preferably a trifunctional to 15-functional (meth)acrylate compound, and more preferably a trifunctional to hexafunctional (meth)acrylate compound. Specific examples of the polymerizable compound include the compounds described in paragraphs 0075 to 0083 of WO 2022 / 065215 and the compounds described in Taiwan Patent Application Publication No. 201832008.

[0046] Preferred polymerizable compounds include dipentaerythritol tri(meth)acrylate (commercially available product: KAYARAD D-330, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available product: KAYARAD D-320, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product: KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available products: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., and NK Ester A-DPH-12E, manufactured by Shin-Nakamura Chemical Co., Ltd.), and compounds having a structure in which the (meth)acryloyl group is bonded via an ethylene glycol and / or propylene glycol residue (e.g., SR454, SR499, commercially available from Sartomer). Examples of polymerizable compounds include diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available product: M-460, manufactured by Toagosei Co., Ltd.), pentaerythritol tetraacrylate (NK Ester A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 1,6-hexanediol diacrylate (KAYARAD, manufactured by Nippon Kayaku Co., Ltd.). 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 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-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), Light Acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), dendrimer structure or hyperbranched structure described in JP-A-2023-043479, and the like can also be used.

[0047] As the polymerizable compound, a polymerizable compound having an ethylene oxide repeating chain can also be used. According to this embodiment, the effects of the present invention are more pronounced. Examples of the polymerizable compound having an ethylene oxide repeating chain include a compound represented by formula (EO-1).

[0048] R in formula (EO-1) Ｅ１ represents a hydrogen atom or a methyl group.

[0049] L in formula (EO-1) Ｅ１ represents an m-valent linking group. Ｅ１ The m-valent linking group represented by is a hydrocarbon group, a heterocyclic group, —O—, —S—, —NR Ａ１ -, -CO-, -COO-, -OCO-, -SO ２ - and groups formed by combining two or more of these groups. Ａ１ 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 a substituent or may not have a substituent. The cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be a monocyclic ring or a fused ring. The heterocyclic group may be a monocyclic ring or a fused ring. The heterocyclic group is preferably a 5- or 6-membered ring. The heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. Examples of heteroatoms constituting the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom.

[0050] In formula (EO-1), n ​​represents an integer of 1 to 20, and m represents an integer of 2 to 10. n is preferably an integer of 1 to 15, and more preferably an integer of 1 to 10. m is preferably an integer of 2 to 8, and more preferably an integer of 2 to 6.

[0051] As the polymerizable compound, a polymerizable compound having a fluorene skeleton can also be used. The polymerizable compound having a fluorene skeleton is preferably a bifunctional polymerizable compound. Examples of the polymerizable compound having a fluorene skeleton include compounds having a partial structure represented by the following formula (Fr):

[0052] In the formula, * represents a bond, and R ｆ１ and R ｆ２ each independently represents a substituent, and m and n each independently represent an integer of 0 to 5. When m is 2 or more, m R ｆ１ may be the same or different, and m R ｆ１ Two of the R ｆ１ When n is 2 or more, n R ｆ２ may be the same or different, and n R ｆ２ Two of the R ｆ２ They may be bonded to each other to form a ring. ｆ１ and R ｆ２ The substituent represented by is a halogen atom, a cyano group, a nitro group, an alkyl group, an aryl group, a heteroaryl group, -OR ｆ１１ , -COR ｆ１２ , -COOR ｆ１３ , -OCOR ｆ１４ , -NR ｆ１５ R ｆ１６ , -NHCOR ｆ１７ , -CONR ｆ１８ R ｆ１９ , -NHCONR ｆ２０ R ｆ２１ , -NHCOOR ｆ２２ , -SR ｆ２３ , -SO ２ R ｆ２４ , -SO ２ OR ｆ２５ , -NHSO ２ R ｆ２６ or -SO ２ NR ｆ２７ R ｆ２８ Examples include: R ｆ１１ ~R ｆ２８ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.

[0053] Specific examples of polymerizable compounds having a fluorene skeleton include compounds having the following structure: Furthermore, commercially available polymerizable compounds having a fluorene skeleton include OGSOL EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomers having a fluorene skeleton).

[0054] The content of the polymerizable compound in the total solid content of the curable 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.

[0055] The curable composition preferably contains 5 to 100 parts by mass of the polymerizable compound per 100 parts by mass of the resin. According to this embodiment, pixels with better rectangularity can be formed. The upper limit of the content of the polymerizable compound is preferably 70 parts by mass or less, and more preferably 50 parts by mass or less. The lower limit of the content of the polymerizable compound is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more.

[0056] When the curable composition further contains a colorant, the curable composition preferably contains 10 to 30 parts by mass of a polymerizable compound per 100 parts by mass of the colorant. According to this embodiment, the generation of development residues can be further suppressed. The upper limit of the content of the polymerizable compound is preferably 25 parts by mass or less, and more preferably 20 parts by mass or less. The lower limit of the content of the polymerizable compound is preferably 15 parts by mass or more. The colorant will be described later.

[0057] The curable composition of the present invention may contain only one polymerizable compound or may contain two or more polymerizable compounds. When two or more polymerizable compounds are contained, the total amount thereof is preferably within the above range.

[0058] <<Photopolymerization Initiator>> The curable composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator.

[0059] Examples of the photopolymerization initiator 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, etc. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a hexaarylbiimidazole compound, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, or a 3-aryl-substituted coumarin compound, more preferably a compound selected from an oxime compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound, and even more preferably an oxime compound.Examples of the photopolymerization initiator include the compounds described in paragraphs 0065 to 0111 of JP-A No. 2014-130173, the compounds described in Japanese Patent No. 6301489, and the compounds described in MATERIAL STAGE 37-60pp, vol. 19, No. peroxide-based photopolymerization initiators described in JP-A-2019-3, 2019, photopolymerization initiators described in WO 2018 / 221177, photopolymerization initiators described in WO 2018 / 110179, photopolymerization initiators described in JP-A-2019-043864, photopolymerization initiators described in JP-A-2019-044030, peroxide-based initiators described in JP-A-2019-167313, aminoacetophenone-based initiators having an oxazolidine group described in JP-A-2020-055992, Oxime-based photopolymerization initiators described in JP-A-0459, polymers described in JP-A-2020-172619, compounds represented by formula 1 described in WO 2020 / 152120, compounds described in JP-A-2021-181406, photopolymerization initiators described in JP-A-2022-013379, compounds represented by formula (1) described in JP-A-2022-015747, fluorine-containing fluorene oxime ester-based photoinitiators described in JP-T-2021-507058, Chinese Patent Application Publication No. 1107643 Initiators described in Patent Publication No. 67, initiators described in JP-T-2022-518535, initiators described in WO 2021 / 175855, compounds described in Taiwan Patent Application Publication No. 202200534, compounds described in JP-A-2022-078550, compounds described in Korean Patent Publication No. 10-2017-0087330, compounds described in WO 2022 / 075452, oxime ester compounds described in Chinese Patent Application Publication No. 110066225, Korean Patent Publication No. 10-2017-0087330, Examples of the photopolymerization initiator include compounds described in WO 2019 / 013112, compounds having a triarylamine or N-arylcarbazole skeleton described in paragraphs 0042 to 0062, oxime ester photopolymerization initiators described in Japanese Patent No. 7219378, photopolymerization initiators described in Korean Patent Publication No. 10-2021-0146174, photopolymerization initiators described in WO 2019 / 013112, and photopolymerization initiators described in JP 2023-033731 A.

[0060] Specific examples of hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole.

[0061] 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, Omnirad 379EG (all manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (all manufactured by BASF), etc. Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (all manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (all manufactured by BASF), etc.

[0062] Examples of the oxime compound include the compounds described in paragraph 0142 of WO 2022 / 085485, the compounds described in Japanese Patent No. 5430746, the compounds described in Japanese Patent No. 5647738, the compounds represented by the general formula (1) of JP-A-2021-173858, and the compounds described in paragraphs 0022 to 0024, and the compounds represented by the general formula (1) of JP-A-2021-170089 and the compounds described in paragraphs 0117 to 0120. Specific examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), and the like. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, and Irgacure OXE04 (manufactured by BASF), TR-PBG-301, TR-PBG-304, and TR-PBG-327 (manufactured by TRONLY), and ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in JP-A-2012-014052). Furthermore, it is also preferable to use, as the oxime compound, a compound that is not colorable or a compound that is highly transparent and does not easily discolor. Commercially available products include ADEKA ARCLES NCI-730, NCI-831, and NCI-930 (manufactured by ADEKA Corporation).

[0063] As the photopolymerization initiator, an oxime compound having a fluorene ring, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, an oxime compound having a fluorine atom, an oxime compound having a nitro group, an oxime compound having a benzofuran skeleton, an oxime compound in which a substituent having a hydroxy group is bonded to a carbazole skeleton, or a compound described in paragraphs 0143 to 0149 of WO 2022 / 085485 can also be used.

[0064] As the photopolymerization initiator, a compound represented by formula (OX-1) can also be used.

[0065] In formula (OX-1), X １ａ represents a divalent linking group containing at least one ring selected from the group consisting of an aromatic ring and a heterocyclic ring; １ａ represents a hydrogen atom or an acyl group; R ２ａ represents an alkyl group or an aryl group; R ３ａ and R ４ａ each independently represents a hydrogen atom or an alkyl group; Alk １ and Alk ２ each independently represents an alkyl group; R ３ａ and R ４ａ may be bonded to form a ring, Alk １ and Alk ２ may be bonded to form a ring, and n represents 0 or 1.

[0066] X in formula (OX-1) １ａ Examples of the divalent linking group represented by include a divalent aromatic ring group, a divalent heterocyclic group, a divalent group in which two or more aromatic rings are bonded via a single bond or a linking group, a divalent group in which two or more heterocycles are bonded via a single bond or a linking group, and a divalent group in which an aromatic ring and a heterocycle are bonded via a single bond or a linking group. Examples of the linking group that bonds the above-mentioned aromatic rings, heterocyclic groups, or aromatic rings and heterocycles include -CH ２ -, -O-, -CO-, -S-, -NR ｘ - and groups combining these. ｘrepresents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.

[0067] X in formula (OX-1) １ａ is preferably a group represented by any one 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 further preferably a group represented by formula (X-2) or formula (X-6). In the formula R Ｘ１ ~R Ｘ９ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.

[0068] R Ｘ１ ~R Ｘ９ The number of carbon atoms in the alkyl group represented by 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 a substituent. Examples of the substituent include a halogen atom, an aryl group, and a heterocyclic group.

[0069] 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 a substituent. Examples of the substituent include a halogen atom, an aryl group, and a heterocyclic group.

[0070] R Ｘ１ ~R Ｘ９ The number of carbon atoms in the alkynyl group represented by is preferably 2 to 15, and more preferably 2 to 10. The alkynyl group may be linear, branched, or cyclic. The alkynyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, and a heterocyclic group.

[0071] R Ｘ１ ~R Ｘ９The number of carbon atoms in the aryl group represented by 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, and a heterocyclic group.

[0072] R Ｘ１ ~R Ｘ９ The heterocyclic group represented by is preferably a 5-membered or 6-membered ring. The heteroatoms contained in the heterocyclic group are preferably oxygen atoms, nitrogen atoms, and sulfur atoms. The number of heteroatoms contained in the heterocyclic group is preferably 1 to 3. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.

[0073] R in formula (OX-1) １ａ represents a hydrogen atom or an acyl group, and is preferably an acyl group. １ａ The acyl group represented by is —C(O)—R １０１ It is preferable that R １０１ represents an aryl group or a heterocyclic group, and is preferably an aryl group.

[0074] R １０１ The number of carbon atoms in the aryl group represented by R is preferably 6 to 20, and more preferably 6 to 12. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heterocyclic group. １０１ The aryl group represented by is preferably a phenyl group, a methylphenyl group or a naphthyl group, more preferably a methylphenyl group or a naphthyl group.

[0075] R １０１ The heterocyclic group represented by is preferably a 5-membered or 6-membered ring. The heteroatoms contained in the heterocyclic group are preferably oxygen atoms, nitrogen atoms, and sulfur atoms. The number of heteroatoms contained in the heterocyclic group is preferably 1 to 3. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.

[0076] R in formula (OX-1)２ａ represents an alkyl group or an aryl group, and is preferably an alkyl group because the reactivity of the generated radical is high. 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 a substituent, but is preferably an unsubstituted alkyl group. R ２ａ The alkyl group represented by R 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, still more preferably 6 to 10, and particularly preferably 6. The aryl group may have a substituent, but is preferably an unsubstituted aryl group.

[0077] R in formula (OX-1) ３ａ and R ４ａ R each independently represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom. 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 a substituent, but is preferably an unsubstituted alkyl group. R ３ａ and R ４ａ may be bonded to form a ring. The ring formed is preferably a 5- or 6-membered ring, and more preferably a 5- or 6-membered aliphatic hydrocarbon ring.

[0078] Alk of formula (OX-1) １ and Alk ２each 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 a substituent, but is preferably an unsubstituted alkyl group. Alk １ and Alk ２ may be bonded to form a ring, and preferably form a ring. The ring formed is preferably a 5- or 6-membered ring, more preferably a 5- or 6-membered aliphatic hydrocarbon ring, and more preferably a cyclopentane ring or a cyclohexane ring.

[0079] In formula (OX-1), n ​​represents 0 or 1, and is preferably 0.

[0080] Specific examples of the compound represented by formula (OX-1) include the compounds described in paragraphs 0092 to 0096 of JP-A No. 2012-113104 and the compound described in paragraph 0041 of JP-A No. 2012-189997.

[0081] As the photopolymerization initiator, a compound represented by formula (OX-2) can also be used.

[0082] In formula (OX-2), R １ｂ and R ２ｂ each independently represents a substituent, R ３ｂ ~R ７ｂ each independently represents a hydrogen atom or a substituent, Ar １ｂ represents an aromatic ring group or a heterocyclic group which may have a substituent; n represents 0 or 1;

[0083] R １ｂ and R ２ｂExamples of the substituent represented by include an alkyl group and an aryl group, and an alkyl group is preferred. The alkyl group preferably has 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 a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkenyl group, an alkynyl group, and a heterocyclic group. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, even more preferably 6 to 10 carbon atoms, and particularly preferably 6 carbon atoms. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heterocyclic group.

[0084] R ３ｂ ~R ７ｂ Examples of the substituent represented by R include a halogen atom, an alkyl group, and an aryl group. Examples of the alkyl group and the aryl group include those described above. ３ｂ ~R ７ｂ is preferably a hydrogen atom.

[0085] Ar １ｂ represents an aromatic ring group or a heterocyclic group which may have a substituent, Ar １ｂ is preferably an aromatic ring group which may have a substituent. The aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, a nitro group, and an acyl group, and an acyl group is preferred. Examples of the acyl group include the acyl groups described above.

[0086] As the photopolymerization initiator, a compound represented by formula (OX-3) can also be used.

[0087] In formula (OX-3), Ar １ｃ represents a (k+m+1)-valent aromatic ring group or a (k+m+1)-valent heterocyclic group; Ar ２ｃ represents a (k+2)-valent aromatic ring group or a (k+2)-valent heterocyclic group; R １ｃ ~R ３ｃeach independently represents a substituent; １ｃ is a single bond or CR １１ｃ R １２ｃ represents R １１ｃ and R １２ｃ each independently represents a hydrogen atom, an alkyl group, or an aryl group; １ｃ represents -O- or -S-; k represents 0 or 1; m represents an integer of 0 to 4; and n represents 0 or 1.

[0088] R １ｃ and R ２ｃ Examples of the substituent represented by include an alkyl group and an aryl group, and an alkyl group is preferred. The alkyl group preferably has 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 a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkenyl group, an alkynyl group, and a heterocyclic group. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, even more preferably 6 to 10 carbon atoms, and particularly preferably 6 carbon atoms. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heterocyclic group. R ２ｃ is preferably an alkyl group having a branched or cyclic structure.

[0089] R ３ｃ Examples of the substituent represented by include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an acyl group, and an acyl group is preferred. Examples of the acyl group include the acyl groups described above.

[0090] Ar １ｃ represents 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.

[0091] Ar ２ｃrepresents 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.

[0092] k represents 0 or 1, and is preferably 0.

[0093] m represents an integer of 0 to 4, preferably 0 or 1, and more preferably 1.

[0094] In the present invention, an oxime compound C1 having an absorption coefficient of 75,000 mL / (g cm) or more at a wavelength of 248 nm and an oxime compound C2 which is a compound different from the oxime compound C1 and has an absorption coefficient of 3,000 mL / (g cm) or more at a wavelength of 365 nm are used in combination as a photopolymerization initiator.

[0095] As the oxime compound C1 and the oxime compound C2, compounds having the above-mentioned absorption coefficients can be selected from the compounds mentioned above.

[0096] In this specification, the absorption coefficient of a sample at the above wavelengths is a value measured as follows. That is, the sample was dissolved in methanol to prepare a measurement solution, and the absorbance of this measurement solution was measured and calculated. Specifically, the measurement solution was placed in a 1 cm wide glass cell, and the absorbance was measured using a UV-Vis-NIR spectrometer (Cary 5000) manufactured by Agilent Technologies. The absorption coefficients (mL / (g cm)) at wavelengths of 365 nm and 248 nm were calculated using the following formula: In the above formula, ε represents the extinction coefficient (mL / (g·cm)), A represents the absorbance, c represents the concentration of the sample (g / mL), and l represents the optical path length (cm).

[0097] The extinction coefficient of the oxime compound C1 at a wavelength of 248 nm is 75,000 mL / (g cm) or more, preferably 80,000 mL / (g cm) or more, more preferably 90,000 mL / (g cm) or more, and even more preferably 94,000 mL / (g cm) or more. The upper limit is preferably 150,000 mL / (g cm) or less.

[0098] The extinction coefficient of oxime compound C1 at a wavelength of 365 nm is preferably 10 to 15,000 mL / (g cm), more preferably 10 to 10,000 mL / (g cm), even more preferably 10 to 5,000 mL / (g cm), and still more preferably 10 to 2,500 mL / (g cm). The extinction coefficient of oxime compound C1 at a wavelength of 365 nm is preferably smaller than the extinction coefficient of oxime compound C2 at a wavelength of 365 nm.

[0099] For oxime compound C1, the difference between the extinction coefficient at a wavelength of 248 nm and the extinction coefficient at a wavelength of 365 nm is preferably 80,000 mL / (g cm) or more, more preferably 90,000 mL / (g cm) or more, and even more preferably 100,000 mL / (g cm) or more. The upper limit is preferably 150,000 mL / (g cm) or less.

[0100] The oxime compound C1 preferably has at least one skeleton selected from an anthraquinone skeleton, a xanthone skeleton, a dibenzofuran skeleton, a fluorenone skeleton, an indandione skeleton, and a coumaranone skeleton. Among the above skeletons, the carbonyl group portion may be an oxime ester structure. Among these, an anthraquinone skeleton, a xanthone skeleton, a dibenzofuran skeleton, a fluorenone skeleton, and a coumaranone skeleton are more preferred, a xanthone skeleton, a dibenzofuran skeleton, and a fluorenone skeleton are even more preferred, and a dibenzofuran skeleton is particularly preferred.

[0101] The oxime compound C1 preferably has an indole ring, since this can further suppress the generation of development residues.

[0102] The oxime compound C1 preferably has an alkyl group substituted with a cycloalkyl group, since this can improve storage stability. Examples of the alkyl group substituted with a cycloalkyl group include a group represented by formula (R-1).

[0103]

[0104] In formula (R-1), * represents a linking bond.

[0105] In formula (R-1), L １ represents an alkylene group. １ The number of carbon atoms in the alkylene group represented by is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 to 3, still more preferably 1 or 2, and particularly preferably 2. １ is preferably a methylene group or an ethylene group, more preferably an ethylene group.

[0106] In formula (R-1), L ２ is -(CH ２ ) ｍ -, and m represents an integer of 1 to 4. m is preferably 3 or 4, and more preferably 3.

[0107] A preferred embodiment of the oxime compound C1 is an oxime compound having an indole ring and at least one skeleton selected from an anthraquinone skeleton, a xanthone skeleton, a dibenzofuran skeleton, a fluorenone skeleton, an indandione skeleton, and a coumaranone skeleton, with an oxime compound having an indole ring and a dibenzofuran skeleton being more preferred. An oxime compound having an indole ring and a dibenzofuran skeleton is preferred in that it can increase the difference between the absorption coefficient at a wavelength of 248 nm and the absorption coefficient at a wavelength of 365 nm. It is also preferred that the oxime compound further has an alkyl group substituted with a cycloalkyl group. The alkyl group substituted with a cycloalkyl group is preferably a group represented by the above formula (R-1).

[0108] Another preferred embodiment of the oxime compound C1 is an oxime compound having at least one skeleton selected from the group consisting of an anthraquinone skeleton, a xanthone skeleton, a dibenzofuran skeleton, a fluorenone skeleton, an indandione skeleton, and a coumaranone skeleton, and an alkyl group substituted with a cycloalkyl group. The alkyl group substituted with a cycloalkyl group is preferably a group represented by the above formula (R-1).

[0109] Specific examples of the oxime compound C1 include photopolymerization initiators C1-1 to C1-19 described in the examples below.

[0110] The extinction coefficient of the oxime compound C2 at a wavelength of 365 nm is 3,000 mL / (g cm) or more, preferably 5,000 mL / (g cm) or more, more preferably 7,000 mL / (g cm) or more, and even more preferably 10,000 mL / (g cm) or more. The upper limit is preferably 40,000 mL / (g cm) or less.

[0111] The extinction coefficient of the oxime compound C2 at a wavelength of 248 nm is preferably 10 to 72,000 mL / (g cm), more preferably 10 to 65,000 mL / (g cm), even more preferably 10 to 60,000 mL / (g cm), and still more preferably 10 to 55,000 mL / (g cm).

[0112] For oxime compound C2, the difference between the extinction coefficient at a wavelength of 248 nm and the extinction coefficient at a wavelength of 365 nm is preferably 15,000 mL / (g cm) or more, more preferably 20,000 mL / (g cm) or more, and even more preferably 25,000 mL / (g cm) or more. The upper limit is preferably 50,000 mL / (g cm).

[0113] The difference between the extinction coefficient of oxime compound C1 at a wavelength of 248 nm and the extinction coefficient of oxime compound C2 at a wavelength of 248 nm is preferably 15,000 mL / (g cm) or more, more preferably 25,000 mL / (g cm) or more, and even more preferably 35,000 mL / (g cm) or more.

[0114] The difference between the extinction coefficient of oxime compound C1 at a wavelength of 365 nm and the extinction coefficient of oxime compound C2 at a wavelength of 365 nm is preferably 3000 mL / (g cm) or more, more preferably 5000 mL / (g cm) or more, and even more preferably 7000 mL / (g cm) or more.

[0115] The oxime compound C2 is preferably an oxime compound having a carbazole ring, a benzocarbazole ring, or a diphenyl sulfide group.

[0116] Specific examples of the oxime compound C2 include photopolymerization initiators C2-1 to C1-12 and C2-X described in the examples below.

[0117] The photopolymerization initiator used in the curable composition of the present invention may further contain a photopolymerization initiator (another photopolymerization initiator) other than the oxime compound C1 and the oxime compound C2. Examples of the other photopolymerization initiator include an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound.

[0118] The total content of oxime compound C1 and oxime compound C2 in the photopolymerization initiator used in the curable composition of the present invention is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 70 to 100% by mass. The photopolymerization initiator used in the curable composition of the present invention preferably consists essentially of oxime compound C1 and oxime compound C2. When the photopolymerization initiator consists essentially of oxime compound C1 and oxime compound C2, this means that the content of oxime compound C1 and oxime compound C2 in the photopolymerization initiator is 99% by mass or more, more preferably 99.9% by mass or more, and even more preferably only oxime compound C1 and oxime compound C2.

[0119] The content of the photopolymerization initiator in the total solid content of the curable composition is preferably 1 to 15% by mass. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more. The upper limit is preferably 12% by mass or less, more preferably 10% by mass or less.

[0120] The total content of oxime compound C1 and oxime compound C2 in the total solid content of the curable composition is preferably 1 to 15 mass %, the lower limit is preferably 2 mass % or more, more preferably 3 mass % or more, and the upper limit is preferably 12 mass % or less, more preferably 10 mass % or less.

[0121] The curable composition preferably contains 25 to 400 parts by mass of oxime compound C2 per 100 parts by mass of oxime compound C1. When the content of oxime compound C2 is within the above range, pixels with excellent rectangular shape and adhesion can be formed even if the exposure wavelength varies. From the viewpoints of rectangular shape and adhesion, the upper limit of the content of oxime compound C2 is preferably 300 parts by mass or less, and more preferably 200 parts by mass or less. From the viewpoints of rectangular shape and adhesion, the lower limit of the content of oxime compound C2 is preferably 30 parts by mass or more, and more preferably 50 parts by mass or more. It is particularly preferable that the curable composition contains 50 to 200 parts by mass of oxime compound C2 per 100 parts by mass of oxime compound C1.

[0122] The curable composition preferably contains 25 to 200 parts by mass of the oxime compound C1 per 100 parts by mass of the polymerizable compound.

[0123] When the curable composition further contains a colorant, the curable composition preferably contains 3 to 10 parts by mass of oxime compound C1 and oxime compound C2 in total per 100 parts by mass of the colorant. According to this embodiment, the generation of development residues can be further suppressed. The upper limit of the content is preferably 8 parts by mass or less, and more preferably 6 parts by mass or less. The lower limit of the content is preferably 3 parts by mass or more, and more preferably 4 parts by mass or more. Colorants will be described later.

[0124] The curable composition of the present invention may contain only one type of oxime compound C1, or may contain two or more types. When two or more types of oxime compounds C1 are contained, it is preferable that the total amount thereof falls within the above-mentioned range. The curable composition of the present invention may contain only one type of oxime compound C2, or may contain two or more types. When two or more types of oxime compounds C2 are contained, it is preferable that the total amount thereof falls within the above-mentioned range.

[0125] <<Colorant>> The curable composition of the present invention preferably contains a colorant. Examples of the colorant include a white colorant, a black colorant, a chromatic colorant, and an infrared-absorbing colorant. Pigment derivatives can also be used as the colorant. In the present invention, the white colorant includes not only pure white colorants but also light gray colorants close to white (for example, off-white, light gray, etc.).

[0126] The colorant may be a pigment or a dye. A pigment and a dye may be used in combination. The pigment may be either an inorganic pigment or an organic pigment, but is preferably an organic pigment from the viewpoints of a wide range of color variations, ease of dispersion, safety, and the like. The colorant preferably contains a pigment. Furthermore, the pigment preferably contains at least one selected from a chromatic pigment and an infrared absorbing pigment, and more preferably contains a chromatic pigment.

[0127] The average primary particle diameter of the pigment and pigment derivative is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, 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 and pigment derivative can be determined from a photograph obtained by observing the primary particles of the pigment and pigment derivative using a transmission electron microscope. Specifically, the projected area of ​​the primary particles of the pigment is determined, and the corresponding circle-equivalent diameter is calculated as the primary particle diameter of the pigment. In addition, the average primary particle diameter in the present invention is the arithmetic mean value of the primary particle diameters of 400 primary particles of the pigment. Furthermore, primary particles of the pigment refer to independent particles without aggregation. The same applies to the average primary particle diameter of pigment derivatives.

[0128] The crystallite size of the pigment and pigment derivative is preferably 0.1 to 50 nm, more preferably 0.5 to 30 nm, and even more preferably 1 to 15 nm. The crystallite size can be determined from the half-width of the diffraction angle peak using an X-ray diffractometer and calculated using the Scherrer equation. The crystallite size of the organic pigment and pigment derivative can be adjusted by known methods such as adjusting the production conditions or pulverizing the product after production.

[0129] The specific surface area of ​​pigments and pigment derivatives is 1 to 300 m ２ / g. The lower limit is 10 m ２ / g or more, and ２ / g or more is more preferable. ２ / g or less, and ２ The value of the specific surface area can be determined according to the BET (Brunauer, Emmett and Teller) method in accordance with DIN 66131: Determination of the specific surface area of ​​solids by gas adsorption.

[0130] The colorant contained in the curable composition of the present invention preferably contains a pigment and a pigment derivative. Examples of the pigment derivative include compounds having a structure in which an acid group or a basic group is bonded to a colorant skeleton. Details of the pigment derivative will be described later. The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, per 100 parts by mass of the pigment. Only one type of pigment derivative may be used, or two or more types may be used in combination.

[0131] The colorant contained in the curable composition of the present invention may contain a pigment and a dye. When a pigment and a dye are contained, the content of the dye is preferably 10 to 100 parts by mass per 100 parts by mass of the pigment. The upper limit is preferably 80 parts by mass or less, more preferably 70 parts by mass or less. The lower limit is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 40 parts by mass or more. Only one type of dye may be used, or two or more types may be used in combination. It is also preferable that the colorant contained in the curable composition of the present invention is substantially free of dye. According to this embodiment, a film having excellent light resistance and heat resistance can be formed. "Substantially free of dye" means that the content of the dye in the colorant is 0.1% by mass or less, preferably 0.01% by mass or less, and more preferably zero.

[0132] (Chromatic Colorant) Examples of chromatic colorants include colorants having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. Examples include yellow colorants, orange colorants, red colorants, green colorants, purple colorants, and blue colorants. The chromatic colorant is preferably a pigment (chromatic pigment), more preferably a red pigment, yellow pigment, or blue pigment, and even more preferably a red pigment or blue pigment. Specific examples of chromatic color pigments include those shown below.

[0133] Examples of red colorants include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, and thioindigo compounds, and diketopyrrolopyrrole compounds, anthraquinone compounds, and azo compounds are preferred, and diketopyrrolopyrrole compounds are more preferred. Furthermore, the red colorant is preferably a red pigment. Furthermore, the red pigment is preferably a diketopyrrolopyrrole pigment.

[0134] Specific examples of red colorants 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 150,155,166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,269,270,272,279,291,294,295,296,297. In addition, as a red colorant, a compound described in paragraph number 0034 of WO 2022 / 085485, or a brominated diketopyrrolopyrrole compound described in JP-A-2020-085947 can also be used.

[0135] As the red colorant, C.I. Pigment Red 122, 177, 224, 254, 255, 264, 269, and 272 are preferred, and C.I. Pigment Red 254, 264, and 272 are more preferred.

[0136] Examples of green coloring materials include phthalocyanine compounds and squarylium compounds, and the phthalocyanine compounds are preferred. The green coloring material is preferably a green pigment. The green pigment is preferably a phthalocyanine pigment.

[0137] 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. Furthermore, halogenated zinc phthalocyanine pigments having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms per molecule can also be used as green colorants. Specific examples include the compounds described in WO 2015 / 118720. Furthermore, compounds described in paragraph 0029 of WO 2022 / 085485, aluminum phthalocyanine compounds described in JP-A 2020-070426, and diarylmethane compounds described in JP-A 2020-504758 can also be used as green colorants.

[0138] As the green colorant, C.I. Pigment Green 7, 36, 58, 62, and 63 are preferred, and C.I. Pigment Green 36 and 58 are more preferred.

[0139] Examples of orange colorants include diketopyrrolopyrrole compounds and azo compounds, and diketopyrrolopyrrole compounds are preferred. The orange colorant is preferably an orange pigment. The orange pigment is preferably a diketopyrrolopyrrole pigment. Specific examples of orange colorants include orange pigments such as 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.

[0140] Examples of yellow colorants include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds, and perylene compounds. The yellow colorant is preferably a yellow pigment. The yellow pigment is preferably at least one selected from isoindoline pigments, quinophthalone pigments, and azo pigments. 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 , 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, 236 and the like.

[0141] Furthermore, as the yellow coloring material, an azobarbituric acid nickel complex having the following structure can also be used.

[0142] In addition, as a yellow colorant, the compounds described in paragraphs 0031 to 0033 of WO 2022 / 085485, the methine dyes described in JP-A 2019-073695, and the methine dyes described in JP-A 2019-073696 can be used.

[0143] Examples of the purple colorant include an oxazine compound, a quinacridone compound, a perylene compound, and an indigo compound, and the oxazine compound is preferred. The purple colorant is preferably a purple pigment. Specific examples of the purple colorant include purple pigments such as C.I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.

[0144] Examples of blue colorants include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred. The blue colorant is preferably a blue pigment. The blue pigment is preferably a phthalocyanine 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 having phosphorus atoms can also be used as blue colorants. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP-A No. 2012-247591 and paragraph 0047 of JP-A No. 2011-157478.

[0145] Dyes can also be used as chromatic colorants. There are no particular limitations on the dyes, and known dyes can be used. Examples include pyrazole azo dyes, anilino azo dyes, triarylmethane dyes, anthraquinone dyes, anthrapyridone dyes, benzylidene dyes, oxonol dyes, pyrazolotriazole azo dyes, pyridone azo dyes, cyanine dyes, phenothiazine dyes, pyrrolopyrazole azomethine dyes, xanthene dyes, phthalocyanine dyes, benzopyran dyes, indigo dyes, and pyrromethene dyes.

[0146] A dye polymer can also be used as a chromatic colorant. The dye polymer is preferably a dye dissolved in a solvent when used. The dye polymer may also form particles. When the dye polymer is particulate, it is typically used in a dispersed state in a solvent. A particulate dye polymer can be obtained, for example, by emulsion polymerization, and specific examples of the compounds and production methods described in JP-A 2015-214682 include those described in JP-A 2015-214682. The dye polymer has two or more dye structures in one molecule, preferably three or more dye structures. The upper limit is not particularly limited, but can be 100 or less. The multiple dye structures in one molecule may be the same dye structure or different dye structures. The weight-average molecular weight (Mw) of the dye polymer is preferably 2,000 to 50,000. The lower limit is more preferably 3,000 or more, and even more preferably 6,000 or more. The upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less. As the dye multimer, compounds described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, WO 2016 / 031442, etc. can also be used.

[0147] As chromatic colorants, triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, xanthene compounds described in JP 2020-117638 A, phthalocyanine compounds described in WO 2020 / 174991 A, isoindoline compounds described in JP 2020-160279 A or salts thereof, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069442 A, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069730 A, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069070 A Compounds represented by the formula (I) described in Korean Patent Publication No. 10-2020-0069067, compounds represented by the formula (I) described in Korean Patent Publication No. 10-2020-0069062, halogenated zinc phthalocyanine pigments described in Japanese Patent No. 6809649, isoindoline compounds described in Japanese Patent Publication No. 2020-180176, phenothiazine compounds described in Japanese Patent Publication No. 2021-187913, halogenated zinc phthalocyanines described in International Publication No. 2022 / 004261, and halogenated zinc phthalocyanines described in International Publication No. 2021 / 250883 can be used. The other colorant may be a rotaxane, and the dye skeleton may be used in the cyclic structure of the rotaxane, in the rod-shaped structure, or in both structures. Other colorants include quinophthalone compounds represented by formula 1 in Korean Patent Publication No. 10-2020-0030759, polymer dyes described in Korean Patent Publication No. 10-2020-0061793, colorants described in JP-A-2022-029701, isoindoline compounds described in WO 2022 / 014635, aluminum phthalocyanine compounds described in WO 2022 / 024926, and JP-A-2022-0458 Compounds described in Patent Publication No. 95, compounds described in WO 2022 / 050051, compounds described in JP 2020-090676, compounds described in JP 2020-055956, compounds described in JP 2021-031681, compounds described in JP 2022-056354, compounds described in US Patent Application Publication No. 2021 / 0355327, compounds described in WO 2022 / 065357,Compounds described in JP 2020-045436 A, compounds described in Korean Patent Publication No. 10-2021-0146726 A, compounds described in JP 2018-178039 A, compounds described in Chinese Patent Publication No. 113881244 A, compounds described in Chinese Patent Publication No. 113881245 A, compounds described in Chinese Patent Publication No. 113881246 A, compounds described in JP 2022-1048 A compounds described in JP-A-2022-096701, compounds described in JP-A-2020-023652, green pigments described on pages 80 to 84 of the Journal of the Color Materials Association (published in 2022), compounds described in JP-A-2022-143135, compounds described in JP-A-2022-140287, compounds described in WO 2022 / 136308, Chinese Patent Application Publication No. 11306134 Perylene compounds described in Korean Patent Publication No. 10-2017-0018993, cyan pigments described in Korean Patent Publication No. 10-2017-0018993, isoindoline compounds described in Japanese Patent Application Laid-Open No. 2020-180176, compounds described in Japanese Patent Application Laid-Open No. 2023-013209, compounds described in Japanese Patent Application Laid-Open No. 2023-013166, xanthene compounds described in International Publication No. 2023 / 286526, compounds described in Japanese Patent Application Laid-Open No. 2021-155746 Compounds described in JP-A-2021-155747, compounds described in JP-A-2021-155748, compounds described in JP-A-2021-155749, compounds described in WO 2018 / 051876, compounds described in JP-A-2020-083981, compounds described in JP-A-2023-056463, compounds described in JP-T-2023-515473, and the like can also be used.

[0148] Two or more chromatic colorants may be used in combination. When two or more chromatic colorants are used in combination, the combination of the two or more chromatic colorants may form a black color. Examples of such combinations include the following embodiments (1) to (7). When the curable composition contains two or more chromatic colorants and exhibits a black color through the combination of the two or more chromatic colorants, the curable composition of the present invention can be preferably used as a curable composition for forming an infrared transmission filter. (1) An embodiment containing a red colorant and a blue colorant. (2) An embodiment containing a red colorant, a blue colorant, and a yellow colorant. (3) An embodiment containing a red colorant, a blue colorant, a yellow colorant, and a purple colorant. (4) An embodiment containing a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant. (5) An embodiment containing a red colorant, a blue colorant, a yellow colorant, and a green colorant. (6) An embodiment containing a red colorant, a blue colorant, and a green colorant. (7) An embodiment containing a yellow coloring material and a purple coloring material.

[0149] (White coloring material) Examples of the white coloring material include inorganic pigments such as titanium oxide, 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. As the white coloring material, the white pigments described in paragraphs 0040 to 0043 of WO 2022 / 085485 can be used.

[0150] (Black Colorant) The black colorant is not particularly limited, and known materials can 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 black colorant refers to a colorant that exhibits absorption over the entire wavelength range of 400 to 700 nm.

[0151] Examples of inorganic black colorants include carbon black, titanium black, graphite, etc., with carbon black and titanium black being preferred, and titanium black being more preferred. Titanium black is a black particle containing titanium atoms, and low-order titanium oxide or titanium oxynitride is preferred. As the titanium black, the titanium black described in paragraph 0044 of WO 2022 / 085485 can be used. As the inorganic black colorant, zirconium nitride powder described in JP 2023-048173 A can also be used.

[0152] 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 may be a compound described in paragraph 0166 of International Publication No. 2022 / 065215. Furthermore, examples of organic black colorants include perylene black (such as Lumogen Black FK4280) described in paragraphs 0016 to 0020 of JP-A-2017-226821 and black azo pigments described in JP-A-2022-121935.

[0153] (Infrared absorbing colorant) 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 wavelength range of more than 700 nm to 1800 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of more than 700 nm to 1400 nm, even more preferably a compound having a maximum absorption wavelength in the wavelength range of more than 700 nm to 1200 nm, and particularly preferably a compound having a maximum absorption wavelength in the wavelength range of more than 700 nm to 1000 nm. In addition, the absorbance A of the infrared absorbing colorant at a wavelength of 500 nm is １ and absorbance A at the maximum absorption wavelength ２ Ratio A １ / A ２ is preferably 0.08 or less, more preferably 0.04 or less. The infrared absorbing colorant is preferably a pigment, more preferably an organic pigment.

[0154] Examples of infrared absorbing colorants include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyrromethene 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 WO 2022 / 065215. Examples of infrared absorbing colorants include the compounds described in paragraph 0121 of WO 2022 / 065215, squarylium compounds described in JP 2020-075959 A, Copper complexes described in Korean Patent Publication No. 10-2019-0135217, croconic acid compounds described in JP 2021-195515, near-infrared absorbing dyes described in JP 2022-022070, croconium compounds described in WO 2019 / 021767, compounds described in JP 2019-127549, compounds described in WO 2022 / 059619, and JP 2022-151682 Compounds described in JP-A-2022-188858, squarylium compounds described in JP-A-2022-184710, compounds described in JP-A-2022-189736, squarylium compounds described in JP-A-2023-004570, squarylium compounds described in WO 2019 / 230660, and compounds described in WO 2020 / 218615 can also be used.

[0155] (Pigment Derivative) A pigment derivative can also be used as the colorant. In the present invention, it is preferable to use a pigment and a pigment derivative in combination. Examples of the pigment derivative include compounds having a structure in which an acid group or a basic group is bonded to a colorant skeleton.

[0156] Examples of dye skeletons that constitute the pigment derivative include a quinoline dye skeleton, a benzimidazolone dye skeleton, a benzisoindole dye skeleton, a benzothiazole dye skeleton, an iminium dye skeleton, a squarylium dye skeleton, a croconium dye skeleton, an oxonol dye skeleton, a pyrrolopyrrole dye skeleton, a diketopyrrolopyrrole dye skeleton, an azo dye skeleton, an azomethine dye skeleton, a phthalocyanine dye skeleton, a naphthalocyanine dye skeleton, an anthraquinone dye skeleton, a quinacridone dye skeleton, a dioxazine dye skeleton, a perinone dye skeleton, a perylene dye skeleton, a thioindigo dye skeleton, an isoindoline dye skeleton, an isoindolinone dye skeleton, a quinophthalone dye skeleton, a dithiol dye skeleton, a triarylmethane dye skeleton, and a pyrromethene dye skeleton.

[0157] Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonic acid amide group, an imidic acid group, and salts thereof. Examples of the atom or atomic group constituting the salt include an alkali metal ion (Li ＋ , Na ＋ , K. ＋ etc.), alkaline earth metal ions (Ca ２＋ , Mg ２＋ Examples of the carboxylic acid amide group include -NHCOR, ... Ｘ１ As the sulfonic acid amide group, a group represented by -NHSO is preferred. ２ R Ｘ２ As the imide acid group, a group represented by -SO ２ NHSO ２ R Ｘ３ , -CONHSO ２ R Ｘ４ , -CONHCOR Ｘ５ or -SO ２ NHCOR Ｘ６ A group represented by the formula: ２ NHSO ２ R Ｘ３ is more preferred. Ｘ１ ~R Ｘ６ R each independently represents an alkyl group or an aryl group. Ｘ１ ~RＸ６ The alkyl group and aryl group represented by may have a substituent. The substituent is preferably a halogen atom, more preferably a fluorine atom.

[0158] Examples of basic groups include amino groups, pyridinyl groups and their salts, ammonium salts, and phthalimidomethyl groups. Examples of atoms or atomic groups that constitute salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.

[0159] Specific examples of pigment derivatives include the compounds described in the examples below, the compounds described in paragraph 0124 of WO 2022 / 085485, the benzimidazolone compounds or salts thereof described in JP 2018-168244 A, compounds having an isoindoline skeleton described in general formula (1) of Japanese Patent No. 6996282, compounds described in JP 2019-172968 A, and compounds described in the specification of Chinese Patent Application Publication No. 115124889.

[0160] The content of the colorant in the total solid content of the curable composition is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, and still more preferably 60% by mass or more, and the upper limit is preferably 80% by mass or less, more preferably 77.5% by mass or less, and even more preferably 75% by mass or less.

[0161] The content of the pigment in the total solid content of the curable composition is preferably 30% by mass or more, more preferably 45% by mass or more, and even more preferably 55% by mass or more, and the upper limit is preferably 80% by mass or less, more preferably 77.5% by mass or less, and even more preferably 75% by mass or less.

[0162] The content of the pigment 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. The total content of the pigment and pigment derivative in the colorant is preferably 25 to 100% by mass, more preferably 55 to 100% by mass, and even more preferably 75 to 100% by mass.

[0163] <<Solvent>> The curable composition of the present invention preferably contains a solvent. Examples of the solvent include organic solvents. The type of solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the curable composition. Examples of organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. For details of these, please refer to paragraph

[0223] of WO 2015 / 166779, the contents of which are incorporated herein by reference. Furthermore, ester-based solvents substituted with a cyclic alkyl group and ketone-based solvents substituted with a cyclic alkyl group 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 ... Examples of suitable ethylene glycol monomethyl ether acetate include 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, it may be preferable to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents for environmental reasons (for example, the amount may be 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 solvents).

[0164] The metal content of the organic solvent is preferably low. The metal content of the organic solvent is preferably, for example, 10 parts per billion (ppb) by mass or less. If necessary, an organic solvent with a mass ppt (parts per trillion) level may be used, and such an organic solvent is provided, for example, by Toyo Gosei Co., Ltd. (The Chemical Daily, November 13, 2015).

[0165] 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 filter material is preferably polytetrafluoroethylene, polyethylene, or nylon.

[0166] The organic solvent may contain isomers (compounds having the same number of atoms but different structures). The organic solvent may contain only one type of isomer or multiple types of isomers.

[0167] The organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.

[0168] The content of the solvent in the curable composition is preferably from 10 to 95% by mass, more preferably from 20 to 90% by mass, and even more preferably from 30 to 90% by mass.

[0169] From the viewpoint of environmental regulations, it is preferable that the curable composition of the present invention is substantially free of environmentally restricted substances. In the present invention, "substantially free of environmentally restricted substances" means that the content of environmentally restricted substances in the curable 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 restricted substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These substances are registered as environmentally restricted substances under the REACH (Registration Evaluation Authorization and Restriction of Chemicals) regulations, the PRTR (Pollutant Release and Transfer Register) Act, the VOC (Volatile Organic Compounds) regulations, etc., and their usage amounts and handling methods are strictly regulated. These compounds may be used as solvents when producing the components used in the curable composition, and may be mixed into the curable composition as residual solvents. From the viewpoints of human safety and environmental considerations, it is preferable to reduce these substances as much as possible. Examples of methods for reducing environmentally restricted substances include a method in which the system is heated or depressurized to a temperature above the boiling point of the environmentally restricted substance, thereby distilling off the environmentally restricted substance from the system. Furthermore, when distilling off a small amount of environmentally regulated substances, it is useful to perform azeotropy with a solvent having a boiling point equivalent to that of the solvent in question in order to increase efficiency. Furthermore, when a radically polymerizable compound is contained, a polymerization inhibitor or the like may be added prior to distillation under reduced pressure to prevent intermolecular crosslinking due to the progress of a radical polymerization reaction during distillation under reduced pressure. These distillation methods can be used at any stage, such as the stage of raw materials, the stage of a product obtained by reacting the raw materials (e.g., a resin solution or a polyfunctional monomer solution after polymerization), or the stage of a curable composition prepared by mixing these compounds.

[0170] <<Polyalkyleneimine>> The curable composition of the present invention can also contain a polyalkyleneimine. The polyalkyleneimine is used, for example, as a dispersing aid for pigments. A dispersing aid is a material for improving the dispersibility of coloring materials such as pigments in a curable composition. The polyalkyleneimine is a polymer obtained by ring-opening polymerization of an alkyleneimine. The polyalkyleneimine is preferably a polymer having a branched structure containing a primary amino group, a secondary amino group, and a tertiary amino group. The alkyleneimine preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, even more preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.

[0171] The molecular weight of the polyalkyleneimine is preferably 200 or more, 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. Regarding the molecular weight value of the polyalkyleneimine, if the molecular weight 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, if the molecular weight of the specific amine compound cannot be calculated from the structural formula or calculation is difficult, the number average molecular weight value measured by the boiling point elevation method is used. If the number average molecular weight cannot be measured by the boiling point elevation method or is difficult to measure, the number average molecular weight value measured by the viscosity method is used. If the number average molecular weight cannot be measured by the viscosity method or is difficult to measure, the number average molecular weight value measured in terms of polystyrene by GPC (gel permeation chromatography) is used.

[0172] 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.

[0173] 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. It is particularly preferred that the polyalkyleneimine be polyethyleneimine. Furthermore, the polyethyleneimine preferably contains primary amino groups in an amount of 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on the total of primary amino groups, secondary amino groups, and tertiary amino groups. 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.).

[0174] The content of the polyalkyleneimine in the total solid content of the curable 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. The content of the polyalkyleneimine is preferably 0.5 to 20 parts by mass per 100 parts by mass of the 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 polyalkyleneimine may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.

[0175] <<Compound Having a Cyclic Ether Group>> The curable composition of the present invention can contain a compound having a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. The epoxy group may be an alicyclic epoxy group. The alicyclic epoxy group refers to a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed. 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 per molecule, and compounds having two or more epoxy groups are preferred. The epoxy compound is preferably a compound having 1 to 100 epoxy groups per 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. As the epoxy compound, the compounds described in paragraphs 0034 to 0036 of JP-A-2013-011869, paragraphs 0147 to 0156 of JP-A-2014-043556, and paragraphs 0085 to 0092 of JP-A-2014-089408, and the compounds described in JP-A-2017-179172 can also be used.

[0176] The compound having a cyclic ether group may be a low molecular weight compound (for example, a molecular weight of less than 2000, or even less than 1000) or a high molecular weight compound (macromolecule) (for example, a molecular weight of 1000 or more, and in the case of a polymer, 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 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is more preferably 10,000 or less, particularly preferably 5,000 or less, and even more preferably 3,000 or less.

[0177] Commercially available examples of compounds having a cyclic ether group 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).

[0178] The content of the compound having a cyclic ether group in the total solid content of the curable composition is preferably 0.1 to 20% by mass. The lower limit is, for example, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is, for example, more preferably 15% by mass or less, and even more preferably 10% by mass or less. Only one type of compound having a cyclic ether group may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is in the above range.

[0179] <<UV Absorber>> The curable composition of the present invention may contain an UV absorber. Examples of UV 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 WO 2022 / 085485, the reactive triazine UV absorber described in JP 2021-178918 A, the UV absorber described in JP 2022-007884 A, the compound described in Korean Patent Publication No. 10-2022-0014454, and the compound described in JP 2023-013321 A can also be used. The content of the UV absorber in the total solids content of the curable composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. In the present invention, the ultraviolet absorber may be used alone or in combination of two or more kinds. When two or more kinds are used, it is preferable that the total amount is in the above range.

[0180] <<Polymerization Inhibitor>> The curable composition of the present invention may contain a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Of these, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the curable composition is preferably 0.0001 to 5 mass%. One type of polymerization inhibitor may be used alone, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

[0181] <<Silane Coupling Agent>> The curable composition of the present invention may contain a silane coupling agent. Examples of the silane coupling agent include silane compounds having a hydrolyzable group, and preferably silane compounds having a hydrolyzable group and other functional groups. The hydrolyzable group refers to a substituent directly bonded to a silicon atom that can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group, with an alkoxy group being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than the hydrolyzable group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group, and a phenyl group, with an amino group, a (meth)acryloyl group, and an epoxy group being preferred. Specific examples of the silane coupling agent include the compound described in paragraph 0177 of WO 2022 / 085485 and the compound described in JP 2019-183020 A. The content of the silane coupling agent in the total solid content of the curable composition is preferably 0.01 to 15.0 mass%, more preferably 0.05 to 10.0 mass%. Only one type of silane coupling agent may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0182] <<Surfactant>> The curable composition of the present invention may contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant may be used. The surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant, and more preferably a silicone-based surfactant. For details of the surfactant, reference may be made to the surfactants described in paragraphs 0238 to 0245 of WO 2015 / 166779, the contents of which are incorporated herein by reference.

[0183] As the fluorine-based surfactant, compounds described in paragraphs 0167 to 0173 of WO 2022 / 085485 can be used.

[0184] Examples of nonionic surfactants include the compounds described in paragraph 0174 of WO 2022 / 085485.

[0185] Silicone surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, and SF 8419. OIL (all manufactured by Dow Toray Industries, Inc.), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (all manufactured by BYK-Chemie). As the silicone surfactant, compounds having the following structure can also be used.

[0186] The content of the surfactant in the total solid content of the curable composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% by mass to 3.0% by mass. The surfactant may be one type or two or more types. When two or more types are used, it is preferable that the total amount is in the above range.

[0187] <<Antioxidant>> The curable composition of the present invention may contain an antioxidant. Examples of antioxidants include phenolic compounds, phosphite ester compounds, and thioether compounds. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. Preferred phenolic compounds include hindered phenolic compounds. Compounds having a substituent at the position adjacent to the phenolic hydroxy group (ortho position) are preferred. As the substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. Furthermore, as the antioxidant, compounds having a phenolic group and a phosphite ester group in the same molecule are also preferred. Furthermore, phosphorus-based antioxidants can also be suitably used. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, and ethylbis(2,4-di-tert-butyl-6-methylphenyl)phosphite. Commercially available antioxidants include, for example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO-80, and ADK STAB AO-330 (manufactured by ADEKA Corporation). Examples of the antioxidant include the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, the compounds described in WO 2017 / 006600, the compounds described in WO 2017 / 164024, and the compounds described in Korean Patent Publication No. 10-2019-0059371. The content of the antioxidant in the total solid content of the curable composition is preferably 0.01 to 20 mass %, more preferably 0.3 to 15 mass %. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is in the above range.

[0188] <<Other Components>> The curable composition of the present invention may contain, as necessary, sensitizers, plasticizers, and other auxiliary agents (e.g., conductive particles, fillers, defoamers, flame retardants, leveling agents, release promoters, fragrances, surface tension modifiers, chain transfer agents, etc.). By appropriately incorporating these components, properties such as film physical properties can be adjusted. As these components, compounds described in paragraph 0182 of WO 2022 / 085485 can be used. As the chain transfer agent, thiol compounds described in JP 2020-109068 A can also be used.

[0189] The curable composition of the present invention may contain a metal oxide in order to adjust the refractive index of the resulting film. Examples of the metal oxide include TiO ２ , ZrO ２ , Al ２ O ３ , SiO ２ The primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, and even more preferably 5 to 50 nm. The metal oxide may have a core-shell structure. In this case, the core may be hollow.

[0190] The curable composition of the present invention may contain a light resistance improver. Examples of the light resistance improver include the compounds described in paragraph 0183 of WO 2022 / 085485.

[0191] It is also preferable that the curable composition of the present invention is substantially free of terephthalic acid esters. Here, "substantially free" means that the content of terephthalic acid esters in the total amount of the curable composition is 1,000 ppb by mass or less, more preferably 100 ppb by mass or less, and particularly preferably zero.

[0192] In view of environmental regulations, the curable composition of the present invention preferably has a melamine content of 10,000 ppm by mass or less.

[0193] The curable composition of the present invention preferably has a free metal content of 100 ppm or less, more preferably 50 ppm or less. The free halogen content is preferably 100 ppm or less, more preferably 50 ppm or less. Methods for reducing the free metals and halogens in the curable composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification with an ion-exchange resin.

[0194] From the viewpoint of environmental regulations, the use of perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts may be restricted. When the content of the above-mentioned compounds in the curable composition of the present invention is reduced, the content of perfluoroalkyl sulfonic acids (particularly perfluoroalkyl sulfonic acids having a perfluoroalkyl group of 6 to 8 carbon atoms) and their salts, and perfluoroalkyl carboxylic acids (particularly perfluoroalkyl carboxylic acids having a perfluoroalkyl group of 6 to 8 carbon atoms) and their salts is preferably in the range of 0.01 ppb to 1,000 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 solids content of the curable composition. The curable composition of the present invention may be substantially free of perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts. For example, by using a compound that can replace perfluoroalkyl sulfonic acid and its salt, and a compound that can replace perfluoroalkyl carboxylic acid and its salt, a curable composition that is substantially free of perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt may be selected. Examples of compounds that can replace restricted compounds include compounds that are exempt from restrictions 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 salt, and perfluoroalkyl carboxylic acid and its salt. The curable composition of the present invention may contain perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt, within the maximum allowable range.

[0195] From the viewpoint of environmental regulations, the use of fluorine-containing compounds may be restricted. When the content of the fluorine-containing compound in the curable composition is reduced, the content of the fluorine-containing compound in the curable composition is preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass or less. The curable composition may be substantially free of fluorine-containing compounds.

[0196] The water content of the curable composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, and more preferably 0.1 to 1.0% by mass. The water content can be measured by the Karl Fischer method.

[0197] The curable composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface state (flatness, etc.), adjusting the film thickness, etc. The viscosity value can be appropriately selected as needed, but is preferably 0.3 mPa·s to 50 mPa·s, and more preferably 0.5 mPa·s to 20 mPa·s at 25°C. The viscosity can be measured, for example, using a cone-plate type viscometer with the temperature adjusted to 25°C.

[0198] <<Storage Container>> The container for storing the curable composition is not particularly limited, and any known container can be used. In addition, the container described in paragraph 0187 of WO 2022 / 085485 can be used as the storage container.

[0199] <Method for preparing curable composition> The curable composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the curable composition, all components may be simultaneously dissolved and / or dispersed in a solvent to prepare the curable composition, or, if necessary, each component may be prepared as two or more appropriate solutions or dispersions, which are mixed at the time of use (application) to prepare the curable composition.

[0200] Furthermore, the preparation of the curable composition preferably includes a process for dispersing the pigment. In the process for dispersing the pigment, mechanical forces used to disperse the pigment include compression, squeezing, impact, shear, and cavitation. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a paint shaker, a microfluidizer, a high-speed impeller, a sand grinder, a flow jet mixer, high-pressure wet atomization, and ultrasonic dispersion. When grinding the pigment in a sand mill (bead mill), it is preferable to use small-diameter beads, increase the bead packing ratio, or otherwise increase the grinding efficiency under such conditions. After the grinding process, it is preferable to remove coarse particles by filtration, centrifugation, or the like. In addition, the process and disperser for dispersing pigments can be suitably used, for example, the process and disperser described in "Dispersion Technology Encyclopedia," published by Joho Kiko Co., Ltd., July 15, 2005, or "Dispersion Technology and Industrial Applications Focused on Suspension (Solid / Liquid Dispersion System) - Comprehensive Data Collection," published by the Management Development Center Publishing Department, October 10, 1978, and paragraph 0022 of JP 2015-157893 A. In addition, in the process for dispersing pigments, particle refinement may be performed in a salt milling process. For details on the materials, equipment, processing conditions, etc. used in the salt milling process, see, for example, JP 2015-194521 A and JP 2012-046629 A. Examples of materials for beads used in dispersion include zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, and glass. The beads may also be made of an inorganic compound having a Mohs hardness of at least 2. The curable composition may contain 1 to 10,000 ppm of the beads.

[0201] When preparing the curable composition, it is preferable to filter the curable composition with a filter for the purpose of removing foreign matter, reducing defects, etc. Examples of the type of filter and filtration method used for filtration include the filters and filtration methods described in paragraphs 0196 to 0199 of WO 2022 / 085485.

[0202] <Film> The film of the present invention is a film obtained from the curable composition of the present invention described above. The film of the present invention can be used for optical filters such as color filters, infrared transmission filters, and infrared cut filters.

[0203] The thickness of the film of the present invention can be adjusted appropriately depending on the purpose. For example, the 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 thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

[0204] When the film of the present invention is used as a color filter, the film of the present invention preferably has a green, red, blue, cyan, magenta, or yellow hue. The film of the present invention can also be preferably used as a color pixel of a color filter. Examples of the color pixel include a red pixel, a green pixel, a blue pixel, a magenta pixel, a cyan pixel, and a yellow pixel.

[0205] <Method for Producing Film> Next, a method for producing a film of the present invention will be described. The film of the present invention can be produced via a step of applying the curable composition of the present invention. The method for producing a film preferably further includes a step of forming a pattern (pixels). As a method for forming the pattern (pixels), a photolithography method is preferred. By forming a pattern by a photolithography method using the curable composition of the present invention, the generation of development residues can be further suppressed.

[0206] The pattern formation by the photolithography method preferably includes the steps of forming a composition layer on a support using the curable composition of the present invention, exposing the composition layer to light in a pattern, and developing and removing the unexposed areas of the composition layer to form a pattern (pixels). If necessary, a step of baking the composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided.

[0207] In the step of forming a composition layer, a composition layer is formed on a support using the curable composition of the present invention. The support is not particularly limited and can be appropriately selected depending on the application. Examples include a glass substrate and a silicon substrate, with a silicon substrate being preferred. The silicon substrate may also be formed with a charge-coupled device (CCD), a complementary metal-oxide semiconductor (CMOS), a transparent conductive film, or the like. A black matrix is ​​sometimes formed on the silicon substrate to isolate each pixel. The silicon substrate may also be provided with an underlayer to improve adhesion with an upper layer, prevent diffusion of substances, or flatten the substrate surface. The surface contact angle of the underlayer is preferably 20 to 70° when measured with diiodomethane. It is also preferably 30 to 80° when measured with water.

[0208] Known methods can be used as the coating method for the curable composition. For example, a dropping method (drop casting); a slit coating method; a spray method; a roll coating method; a rotary coating method (spin coating); a casting coating method; a slit and spin method; a pre-wetting method (for example, the method described in JP 2009-145395 A); inkjet (for example, on-demand method, piezo method, thermal method), various printing methods such as nozzle jet and other ejection printing, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing; a transfer method using a mold or the like; a nanoimprint method, etc. can also be mentioned. In addition, the coating method described in paragraph 0207 of WO 2022 / 085485 A can also be used.

[0209] The composition layer formed on the support may be dried (prebaked). When a film is produced by a low-temperature process, prebaking may not be performed. When prebaking is performed, the prebaking temperature is preferably 150°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower. The lower limit can be, for example, 50°C or higher, or can also be 80°C or higher. The prebaking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Prebaking can be performed using a hot plate, an oven, or the like.

[0210] Next, the composition layer is exposed to light in a pattern (exposure step). For example, the composition layer can be exposed to light in a pattern by using a stepper exposure machine, a scanner exposure machine, or the like, through a mask having a predetermined mask pattern. This allows the exposed portion to be cured.

[0211] Examples of radiation (light) that can be used for exposure include g-line and i-line. Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light with a wavelength of 300 nm or less include KrF line (wavelength 248 nm) and ArF line (wavelength 193 nm), with KrF line (wavelength 248 nm) being preferred. Long-wave light sources of 300 nm or more can also be used.

[0212] The exposure may be performed by continuous irradiation with light or by pulsed irradiation (pulse exposure), which is an exposure method in which light irradiation and pauses are repeated in short cycles (for example, milliseconds or less).

[0213] The irradiation amount (exposure amount) is, for example, 0.03 to 2.5 J / cm ２ is preferred, and 0.05 to 1.0 J / cm ２ The oxygen concentration during exposure can be appropriately selected. In addition to being performed in the atmosphere, exposure may be performed in a low-oxygen atmosphere with an oxygen concentration of 19% by volume or less (e.g., 15% by volume, 5% by volume, or substantially oxygen-free), or in a high-oxygen atmosphere with an oxygen concentration of more than 21% by volume (e.g., 22% by volume, 30% by volume, or 50% by volume). The exposure illuminance can be appropriately set, and is usually 1000 W / m ２ ~100000W / m ２ (For example, 5000 W / m ２ , 15000W / m ２ , or 35,000 W / m ２ The oxygen concentration and exposure illuminance may be appropriately combined. For example, an oxygen concentration of 10% by volume and an illuminance of 10,000 W / m ２ , oxygen concentration 35% by volume, illuminance 20,000 W / m ２etc.

[0214] Next, the unexposed portions of the composition layer are developed and removed to form a pattern (pixels). The unexposed portions of the composition layer can be developed and removed using a developer. As a result, the unexposed portions of the composition layer in the exposure step are dissolved into the developer, leaving only the photocured portions. 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 residue removability, the process of shaking off the developer every 60 seconds and then supplying fresh developer may be repeated several times.

[0215] Examples of the developer include organic solvents and alkaline developers, and alkaline developers are preferably used. Regarding the developer and the washing (rinsing) method after development, the developer and washing method described in paragraph 0214 of WO 2022 / 085485 can be used.

[0216] After development and drying, it is preferable to perform additional exposure treatment or heating treatment (post-baking). The additional exposure treatment or post-baking is a post-development curing treatment to ensure complete curing. The heating temperature in post-baking is, for example, preferably 100 to 300°C, more preferably 200 to 270°C. Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to achieve the above conditions for the developed film. When additional exposure treatment is performed, it is preferable that the light used for exposure has a wavelength of 400 nm or less. The additional exposure treatment may also be performed by the method described in Korean Patent Publication No. 10-2017-0122130.

[0217] <Optical Filter> The optical filter of the present invention has the above-described film of the present invention. Types of optical filters include color filters, infrared cut filters, and infrared transmission filters, and a color filter is preferred. The color filter preferably has the film of the present invention as its pixel, and more preferably has the film of the present invention as a colored pixel.

[0218] The optical filter may have a protective layer provided on the surface of the film of the present invention. By providing a protective layer, various functions can be imparted, such as oxygen blocking, low reflectivity, hydrophilicity / hydrophobicity, and blocking of light of specific wavelengths (ultraviolet rays, infrared rays, etc.). The thickness of the protective layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm. Methods for forming the protective layer include a method of applying a resin composition for forming the protective layer, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive. Components constituting the protective layer include (meth)acrylic resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide 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 For example, in the case of a protective layer intended to block oxygen, the protective layer may contain a polyol resin and SiO ２ and Si ２ N ４ In the case of a protective layer intended to reduce reflection, the protective layer preferably contains a (meth)acrylic resin and a fluorine resin.

[0219] When forming a protective layer by applying a resin composition, known methods such as spin coating, casting, screen printing, and inkjet printing can be used as the method for applying the resin composition. Known organic solvents (e.g., propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used as the organic solvent contained in the resin composition. When forming the protective layer by chemical vapor deposition, known chemical vapor deposition methods (thermal chemical vapor deposition, plasma chemical vapor deposition, photochemical vapor deposition) can be used as the chemical vapor deposition method.

[0220] The protective layer may contain additives such as organic or inorganic fine particles, absorbers for light of specific wavelengths (e.g., ultraviolet light, infrared light, etc.), refractive index adjusters, antioxidants, adhesives, and surfactants, as needed. Examples of organic or inorganic fine particles include polymeric fine particles (e.g., silicone resin fine particles, polystyrene fine particles, and melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, silica, calcium carbonate, and barium sulfate. Known absorbers for light of specific wavelengths can be used. 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, of the total mass of the protective layer.

[0221] As the protective layer, the protective layers described in paragraphs 0073 to 0092 of JP-A-2017-151176 can also be used.

[0222] The optical filter may have a structure in which each pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern.

[0223] <Solid-state imaging device> The solid-state imaging device of the present invention has the above-described film of the present invention. The configuration of the solid-state imaging device is not particularly limited as long as it has the film of the present invention and functions as a solid-state imaging device, but examples thereof include the following configurations.

[0224] The substrate includes a plurality of photodiodes constituting a light-receiving area of ​​a solid-state imaging device (such as a CCD (charge-coupled device) image sensor or a CMOS (complementary metal-oxide semiconductor) image sensor) and transfer electrodes made of polysilicon or the like. A light-shielding film is formed on the photodiodes and transfer electrodes, with only the light-receiving portions of the photodiodes exposed. A device protection film made of silicon nitride or the like is formed on the light-shielding film so as to cover the entire light-shielding film and the light-receiving portions of the photodiodes. A color filter is also provided on the device protection film. Furthermore, the device protection film may include a light-collecting means (e.g., a microlens, etc.; the same applies hereinafter) below the color filter (on the side closer to the substrate), or on the color filter. The color filter may have a structure in which each color pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern. In this case, the partition walls preferably have a lower refractive index than the color pixels. Examples of imaging devices having such a structure include those described in JP 2012-227478 A, JP 2014-179577 A, and WO 2018 / 043654 A. Furthermore, as shown in JP 2019-211559 A, an ultraviolet absorbing layer may be provided within the structure of the solid-state imaging element to improve light resistance. An imaging device equipped with the solid-state imaging element of the present invention can be used for digital cameras, electronic devices with imaging functions (such as mobile phones), as well as in-vehicle cameras and surveillance cameras.

[0225] <Image Display Device> The image display device of the present invention has the above-described film of the present invention. Examples of image display devices include liquid crystal display devices and organic electroluminescence display devices. Definitions of image display devices and details of each image display device are described, for example, in "Electronic Display Devices" (written by Akio Sasaki, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (written by Nobuaki Ibuki, published by Sangyo Tosho Co., Ltd. in 1989). Liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology" (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994). There are no particular limitations on the liquid crystal display device to which the present invention can be applied, and the present invention can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology."

[0226] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, in the structural formulas shown below, Me is a methyl group.

[0227] <Preparation of Dispersion> (Formulation 1) A mixture of 15 parts by mass in total of pigment and derivative, 5 parts by mass of dispersant in terms of solid content, and 80 parts by mass of solvent was mixed and dispersed for 3 hours using a bead mill (zirconia beads 0.1 mm diameter). Thereafter, the mixture was mixed at a pressure of 2000 kg / cm using a high-pressure disperser NANO-3000-10 equipped with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.). ２ The dispersion treatment was carried out under the conditions of a flow rate of 500 g / min. This dispersion treatment was repeated a total of 10 times to obtain a dispersion liquid. The pigment, derivative, dispersant, and solvent used were the materials shown in the table below.

[0228]

[0229] The details of the materials listed with abbreviations in the table above are as follows: (Pigments) P-1: C.I. Pigment Green 36 (phthalocyanine compound, green pigment) P-2: C.I. Pigment Green 58 (phthalocyanine compound, green pigment) P-3: C.I. Pigment Yellow 129 (azomethine compound, yellow pigment) P-4: C.I. Pigment Yellow 139 (isoindoline compound, yellow pigment) P-5: C.I. Pigment Yellow 150 (azo compound, yellow pigment) P-6: C.I. Pigment Yellow 185 (isoindoline compound, yellow pigment) P-7: C.I. Pigment Red 254 (diketopyrrolopyrrole compound, red pigment) P-8: C.I. Pigment Red 272 (diketopyrrolopyrrole compound, red pigment) P-9: C.I. Pigment Blue 15:6 (phthalocyanine compound, blue pigment) P-10: C.I. Pigment Violet 23 (dioxazine compound, purple pigment) P-11: C.I. Pigment Red 291 (diketopyrrolopyrrole compound, red pigment)

[0230] (Derivatives) Syn-1 and Syn-2: Compounds having the following structure

[0231] (Dispersant) D-1: Resin having the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight average molecular weight: 18,000) D-2: Resin having the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight average molecular weight: 20,000) D-3: Resin having the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight average molecular weight: 23,000) D-4: Epomin SP-003 (manufactured by Nippon Shokubai Co., Ltd., polyethyleneimine, molecular weight 300) D-5: Epomin SP-006 (manufactured by Nippon Shokubai Co., Ltd., polyethyleneimine, molecular weight 600) D-6: Epomin SP-012 (manufactured by Nippon Shokubai Co., Ltd., polyethyleneimine, molecular weight 1200) D-7: Epomin SP-018 (manufactured by Nippon Shokubai Co., Ltd., polyethyleneimine, molecular weight 1800)

[0232] (Solvent) S-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0233] <Preparation of Curable Compositions> Each material was mixed in the proportions of formulations 1 to 8 shown below, and filtered through a nylon filter with a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) to prepare each curable composition. In the tables below, the value of the colorant content (total content of pigment and derivative) in the total solid content of the curable composition is shown in the column "Colorant concentration (mass%)".

[0234]

[0235]

[0236]

[0237]

[0238] The details of the materials indicated by the abbreviations in the table showing the formulation of the curable composition are as follows:

[0239] (Dispersion) Dispersion 1 to 19, C1: Dispersion 1 to 19, C1 described above

[0240] (Monomer (polymerizable compound)) M-1: Compound having the following structure M-2: Compound of the following structure M-3: Compound having the following structure M-4: A mixture of compounds having the following structure (a mixture of the compound on the left (a hexafunctional (meth)acrylate compound) and the compound on the right (a pentafunctional (meth)acrylate compound) in a molar ratio of 7:3) M-X: a compound having the following structure

[0241] (Photopolymerization initiator) C1-1 to C1-19: Compounds having the following structure

[0242] C2-1 to C2-12, C2-X: Compounds having the following structures

[0243] (Binder) B-1: 30% by mass PGMEA solution of a resin having the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units; weight average molecular weight: 20,000). B-2: 30% by mass PGMEA solution of a resin having the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units; weight average molecular weight: 23,000) B-3: 30% by mass PGMEA solution of a resin having the following structure (the number attached to the main chain is the molar ratio; weight-average molecular weight: 11,000) B-4: 30% by mass PGMEA solution of a resin having the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight average molecular weight: 11,000)

[0244] (Surfactant) Su-1: Compound having the following structure (silicone surfactant)

[0245] (Polymerization inhibitor) In-1: p-methoxyphenol

[0246] (Solvent) S-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0247] <Evaluation of Rectangularity> (Exposure with KrF Beam) CT-4000L (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied to an 8-inch (20.32 cm) silicon wafer using a spin coater so that the thickness after post-baking would be 0.1 μm, and the wafer was heated on a hot plate at 220°C for 300 seconds to form an undercoat layer, thereby obtaining a silicon wafer with an undercoat layer. Next, each curable composition was applied by spin coating onto the undercoat layer of the silicon wafer with an undercoat layer so that the film thickness after post-baking would be 0.4 μm. Next, the wafer was heated at 100°C for 3 minutes using a hot plate. Next, the obtained composition layer was exposed to light (KrF beam) with a wavelength of 248 nm through a mask having a 0.7 μm square pattern using a KrF scanner exposure machine at an illuminance of 35,000 W / m ２ , exposure dose 110 mJ / cm ２The silicon wafer on which the exposed coating film was formed was placed on the horizontal rotating table of a spin-shower developer (DW-30 model, manufactured by Chemitronics Corporation), and puddle development was performed for 60 seconds at 23°C using a 60% diluted solution of CD-2000 (manufactured by Fujifilm Electronic Materials Co., Ltd.), forming a colored pattern on the silicon wafer. The silicon wafer on which the colored pattern was formed was fixed to the horizontal rotating table using a vacuum chuck system, and while the silicon wafer was rotated at a rotation speed of 50 rpm using a rotation device, pure water was supplied in a shower-like manner from a spray nozzle from above the center of rotation to perform a rinse treatment, and then spray-dried. Furthermore, a heat treatment (post-bake) was performed for 300 seconds using a hot plate at 230°C to form a colored pattern (pixel). The cross section of the prepared pixel was observed with a scanning electron microscope, and the ratio of the length of the upper side of the pixel to the length of the lower side of the pixel (pixel ratio) was measured, and the rectangularity was evaluated using the following evaluation criteria. -Evaluation criteria- 5: Pixel ratio is 0.98 or more 4: Pixel ratio is 0.96 or more and less than 0.98 3: Pixel ratio is 0.94 or more and less than 0.96 2: Pixel ratio is 0.92 or more and less than 0.94 1: Pixel ratio is less than 0.92

[0248] (Exposure with i-line) In the evaluation of <Evaluation of rectangularity> (Exposure with KrF line) above, pixels were formed in the same manner except that KrF line was replaced with i-line, and rectangularity was evaluated according to the following evaluation criteria. -Evaluation criteria- 5: Pixel ratio is 0.95 or more 4: Pixel ratio is 0.93 or more and less than 0.95 3: Pixel ratio is 0.91 or more and less than 0.93 2: Pixel ratio is 0.89 or more and less than 0.91 1: Pixel ratio is less than 0.89

[0249] <Evaluation of Adhesion> (Exposure to KrF Beams) Each of the curable compositions obtained above was applied to the undercoat layer of the undercoat layer-attached silicon wafer by spin coating so that the film thickness after application would be 0.4 μm, and then heated at 100° C. for 3 minutes using a hot plate to form a composition layer. Next, using a KrF scanner exposure machine, the obtained composition layer was irradiated with light (KrF beams) with a wavelength of 248 nm through a mask having a 0.7 μm square pattern at an illuminance of 35,000 W / m ２ , exposure dose 20 to 200 mJ / cm２ The composition layer after exposure was then subjected to shower development at 23°C for 60 seconds using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) as a developer. Thereafter, the layer was rinsed by spin shower using pure water to form pixels. The obtained pixels were subjected to a 110 mJ / cm ２ Of the areas exposed with an exposure dose of 1071 x 1071, 1071 areas were observed under an optical microscope and the number of peeled pixels was counted. Based on the number of peeled pixels, adhesion was evaluated according to the following evaluation criteria. -Evaluation criteria- 5: Number of peeled pixels is 3 or less 4: Number of peeled pixels is more than 3 but not more than 5 3: Number of peeled pixels is more than 5 but not more than 10 2: Number of peeled pixels is more than 10 but not more than 20 1: Number of peeled pixels is more than 20

[0250] (Exposure with i-ray) Pixels were formed in the same manner as in the above <Evaluation of Adhesion> (Exposure with KrF ray) except that KrF ray was replaced with i-ray, and the adhesion was evaluated using the same evaluation criteria.

[0251]

[0252]

[0253] As shown in the above table, the curable compositions of the examples were excellent in the evaluation of rectangularity and adhesion whether exposed to KrF rays or i rays.

[0254] The films obtained from the curable compositions of the examples can be suitably used in optical filters, solid-state imaging devices, and image display devices.

Claims

1. A curable composition comprising a resin, a polymerizable compound, and a photopolymerization initiator, the photopolymerization initiator comprising: an oxime compound C1 having an absorption coefficient of 75,000 mL / (g cm) or more at a wavelength of 248 nm; and an oxime compound C2 which is a compound different from the oxime compound C1 and has an absorption coefficient of 3,000 mL / (g cm) or more at a wavelength of 365 nm.

2. The curable composition according to claim 1, comprising 25 to 400 parts by mass of the oxime compound C2 per 100 parts by mass of the oxime compound C1.

3. The curable composition according to claim 1 or 2, wherein the oxime compound C1 has an absorption coefficient at a wavelength of 365 nm of 10 to 5,000 mL / (g·cm).

4. The curable composition according to claim 1, comprising 50 to 200 parts by mass of the oxime compound C2 relative to 100 parts by mass of the oxime compound C1.

5. The curable composition according to claim 1 or 2, wherein the polymerizable compound comprises a polymerizable compound having an ethylene oxide repeating chain.

6. The curable composition according to claim 1 or 2, comprising 25 to 200 parts by mass of the oxime compound C1 relative to 100 parts by mass of the polymerizable compound.

7. The curable composition according to claim 1 or 2, wherein the resin comprises a resin having a crosslinkable group.

8. The curable composition according to claim 1 or 2, wherein the oxime compound C1 is an oxime compound having an indole ring.

9. The curable composition according to claim 1 or 2, wherein the oxime compound C1 has at least one skeleton selected from the group consisting of an anthraquinone skeleton, a xanthone skeleton, a dibenzofuran skeleton, a fluorenone skeleton, an indandione skeleton and a coumaranone skeleton.

10. The curable composition according to claim 1 or 2, wherein the oxime compound C1 has an alkyl group substituted with a cycloalkyl group.

11. The curable composition according to claim 1 or 2, further comprising a coloring material, the content of the coloring material being 50 mass % or more of the total solid content of the curable composition.

12. The curable composition according to claim 1 or 2, further comprising a colorant, the polymerizable compound being contained in an amount of 10 to 30 parts by mass per 100 parts by mass of the colorant, and the oxime compound C1 and oxime compound C2 being contained in a total amount of 3 to 10 parts by mass per 100 parts by mass of the colorant.

13. A film obtained by using the curable composition according to claim 1 or 2.

14. An optical filter having the film according to claim 13.

15. A solid-state imaging device having the film according to claim 13.

16. An image display device comprising the film according to claim 13.

Images